KR20160110899A - Liquid crystal medium - Google Patents

Abstract

The present invention relates to a liquid crystal (LC) medium including a polymerizable compound, a producing method thereof, optical, electro-optical and electronic purposes, an LC display, and especially a use of an LC display of a polymer sustained alignment (PSA) type, and an LC display comprising the same, and especially a PSA display.

Description

Liquid crystal medium {LIQUID CRYSTAL MEDIUM}

The present invention relates to a liquid crystal (LC) medium comprising a polymerizable compound, a process for its preparation, optical, electro-optical and electrical purposes, in particular LC displays, in particular polymer sustained alignment (PSA) To its use for LC displays, and to LC displays, particularly PSA displays, comprising them.

Liquid crystal display modes with a wide range of interest and commercial uses are the so-called PS ("Polymer Continued") or PSA ("Polymer Continued Orientation") mode, sometimes also referred to as "polymer stabilized" . In a PSA display, an LC mixture (hereinafter also referred to as "host mixture" hereinafter) and a small amount, typically less than 1 wt%, such as 0.2 to 0.4 wt%, of one or more polymerizable compounds, A LC medium comprising a compound is used. After the LC medium is charged into the display, the polymerizable compound is polymerized or cross-linked in situ by ordinary UV photopolymerization, optionally while a voltage is applied to the electrodes of the display. The polymerization is carried out at a temperature at which the LC medium represents a liquid crystal phase, usually at room temperature. Addition of polymeric mesogens or liquid crystal compounds, also known as reactive mesogens or "RM ", to LC host mixtures has proven particularly suitable.

On the other hand, the PS (A) mode is used in various conventional LC display types. Thus, for example, PS-VA ("vertically aligned"), PS-OCB ("optically compensated bend"), PS- PS-UB-FFS ("Ultra Brightness FFS ") and PS-TN (" twisted nematic " The polymerization of RM can occur preferably at an applied voltage in the case of PS-VA and PS-OCB displays, and preferably in the case of PS-IPS displays, with or without an applied voltage. In the PS-OCB display, for example, the bend structure may be stabilized so that the offset voltage may be unnecessary or reduced. In the case of a PS-VA display, the pre- For a PS-VA display, the standard MVA ("multi-zero " (" multidomain VA ") or PVA (" patterned VA ") pixel and electrode layout can be used. It is also possible to use only one structured electrode without protrusions, Improves contrast and transparency.

Also, the so-called posi-VA mode ("positive VA") has proved to be particularly suitable. As in typical VA and PS-VA displays, the initial orientation of the LC molecules in the Posi-VA display is homeotropic (i.e., substantially perpendicular to the substrate in the initial state when no voltage is applied). However, in contrast to conventional VA and PS-VA displays, the LC medium with positive dielectric anisotropy is used in the Forge-VA display. As in the IPS and PS-IPS displays, the two electrodes in the Posi-VA display are aligned on only one of the two substrates, preferably intermeshed comb-shaped (interdigital (interdigital) structure. When a voltage is applied to the interdigital electrodes to generate an electric field substantially parallel to the layer of the LC medium, the LC molecules are switched to an orientation substantially parallel to the substrate. In the Forge-VA display it has also proven advantageous to polymerize in the display by adding RM to the LC medium and then polymerize in the display. This results in significant switching time reduction.

PS-VA displays are described, for example, in EP1170626A2, US6861107, US7169449, US2004 / 0191428A1, US2006 / 0066793A1 and US2006 / 0103804A1. PS-OCB displays are described, for example, in T.-J. Chen et al., Jpn. J. Appl. Phys. 45, 2006, 2702-2704] and [S. H. Kim, L.-C-Chien, Jpn. J. Appl. Phys. 43, 2004, 7643-7647. PS-IPS displays are described, for example, in US 6177972 and Appl. Phys. Lett. 1999, 75 (21), 3264). PS-TN displays are described, for example, in Optics Express 2004, 12 (7), 1221.

The PSA display may be operated as an active-matrix or passive-matrix display. In the case of an active-matrix display, individual pixels are often addressed with integrated non-linear active elements such as transistors (e.g., thin-film transistors or "TFTs"), Are often addressed by a complex method known from the prior art.

The PSA display may also include an orientation layer over one or both of the substrates that form the display cell. The alignment layer is often applied over the electrodes (if such electrodes are present) to contact the LC medium and induce an initial orientation of the LC molecules. The alignment layer may comprise or consist of, for example, a polyimide which may be rubbed or produced by a photo-alignment method.

In particular, in the case of monitors and especially TV products, optimization of the contrast and brightness (and thus transmittance) of the LC display as well as response time is still required. The PSA method can provide a significant advantage here. In particular, in the case of PS-VA, PS-IPS, PS-FFS and PS-Posi-VA displays, the reduction of the response time associated with the pre-calibratable measurement within the test cell can be achieved without significant adverse effects on other parameters.

The prior art presents biphenyl diacrylate or dimethacrylate, which is optionally fluorinated, as an RM for use in PSA displays.

However, not all combinations of the LC host mixture and the RM are suitable for use in a PSA display, for example, because only an unsuitable tilt angle occurs or no tilt angle occurs, or because the voltage holding ratio (VHR) There is a problem that it is not. Also, when used in PSA displays, LC mixtures and RMs known in the prior art have been found to still have some disadvantages. Thus, not all known RMs that are soluble in the LC host mixture are suitable for use in a PSA display. In addition, it is usually difficult to find a selection criterion suitable for the RM in addition to the direct measurement of the pre-cursor on the PSA display. If UV photopolymerization is required without the addition of a photoinitiator to benefit a particular product, the choice of a suitable RM will be narrower.

In addition, the selected combination of LC host mixture / RM should have low rotational viscosity and good electrical properties, especially high VHR. In PSA displays, high VHR after UV light irradiation is particularly important because UV exposure is not only a common exposure during the operation of the final display, but is also an integral part of the display production process.

In particular, it is desirable to have available an improved material for a PSA display that provides a very small pretilt angle. Preferred materials are those that can produce a lower pre-exposure angle after the same exposure time and / or produce at least one identical pre-exposure angle after a shorter exposure time compared to prior art materials. This may allow to reduce display production time ("tact time") and production costs.

A further problem in the manufacture of PSA displays is the presence of residual amounts of un-polymerized RM present after the polymerization step, which is essential for the occurrence of a pre-square in the display, and the removal thereof. Unreacted RMs can be negatively impacted on the display by, for example, polymerizing in an uncontrolled manner during display operation.

Thus, the PSA displays known from the prior art usually have a so-called "image sticking" or "image burn" (i.e., after the electric field is switched off in a pixel, or after another pixel is addressed, Images generated on the LC display by temporary addressing).

The after-image can occur, for example, when an LC host mixture having a low VHR is used. Solar or Display Backlighting The UV component can cause undesirable decomposition reactions of the LC molecules and initiate the generation of ionic or free-radical impurities. They can accumulate, in particular in the electrode or in the orientation layer, where they reduce the effective applied voltage. This effect can also be observed in conventional LC displays without polymer components.

The additional afterimage effect caused by the presence of un-polymerized RM is often observed in PSA displays. Unregulated polymerization of the residual RM is initiated by UV light from sunlight or backlight. In the switched display area, this changes the tilt angle after a number of addressing cycles. As a result, a change in transmittance in the switched area can occur, but remains unchanged in the un-switched area.

Thus, during the production of the PSA display, it is desirable that the polymerization of the RM is allowed to proceed as completely as possible, and the presence of the un-polymerized RM in the display may be excluded or minimized. Thus, there is a need for a mixture of RM and LC hosts to enable or assist rapid and complete polymerization of the RM. In addition, a controlled reaction of the residual RM amount is preferred. This can be achieved by providing improved RMs that polymerize faster and more effectively than prior art RMs.

A further problem observed during the operation of the PSA display is the stability of the pre-exposure square. Thus, it has been observed that by pre-polymerizing RM, the angle of the pre-emergence that occurs during display manufacture can be deteriorated rather than being constant after voltage stress is applied to the display during display operation. This can negatively affect display performance, for example, by increasing the black state transmittance and thereby reducing contrast.

Another problem to be solved is that the RMs of the prior art often have a high melting point and exhibit only a limited solubility in many commonly used LC mixtures. As a result, RM tends to spontaneously crystallize out of the LC mixture. In addition, due to the risk of voluntary polymerization, high solubility at room temperature is required, hindering warming of the LC host mixture to better dissolve the RM. Also, for example, when the LC display is filled with LC media, there is a risk of phase separation (chromatographic effect), which can greatly impair the homogeneity of the display. This can be exacerbated by the fact that the LC medium is often charged into the display at low temperatures to reduce the risk of spontaneous polymerization (see above), which consequently has a negative impact on solubility.

Another problem observed in the prior art is that the use of conventional LC media in LC displays, including but not limited to PSA-type displays, makes it possible for the LC media to be displayed within the display, in particular by using one drop filling (ODF) When charged, it often causes stains on the display. This phenomenon is also known as "ODF mura ". Thus, it is desirable to provide a LC medium that leads to reduced ODF staining.

Another problem observed in the prior art is that LC media used in PSA displays, including but not limited to displays of the PSA type, often exhibit high viscosity and thus high switching times. In order to reduce the viscosity and response time of the LC medium, it has been proposed in the prior art to add an LC mixture having an alkenyl group. However, LC media containing alkenyl groups have often been observed to exhibit reduced reliability and stability, and particularly a decrease in VHR after exposure to UV radiation. Particularly when used in PSA displays, photo-polymerization of RM in PSA displays is usually done by exposure to UV radiation, which is a serious drawback, as it can cause VHR drop in the LC medium.

In the prior art, the LC medium used in the PSA display has been proposed such that the LC host mixture contains one or more terphenyl compounds to enhance polymerization of the RM. However, the addition of the terphenyl compound increases the viscosity of the LC host mixture and thus results in a slower response time. In addition, the addition of terphenyl compounds can lead to reduced reliability and a drop in VHR after UV stress in the LC medium.

It is therefore another task to provide an LC mixture and a LC medium for PSA displays that can exhibit reduced viscosity and a high VHR while simultaneously enabling rapid and complete polymerization of the RM.

Thus, there is still a significant need for PSA displays and LC media and polymeric compounds for use in such displays that do not exhibit the above-described disadvantages or are only slightly visible and have improved properties.

In particular, high resistivity and simultaneous wide operating-temperature range, short response times even at low temperatures, low threshold voltage, low pretilt angles, various gray tones, high contrast and wide viewing angles, high reliability and high VHR values after UV exposure, There is still a significant need for PSA displays and LC mixtures and RMs for use in such displays, which have low melting points and high solubility in the LC host mixture. In the case of PSA displays for mobile products, it is particularly desirable to have an available LC medium exhibiting a low threshold voltage and a high birefringence.

The present invention is based on the object of providing new and suitable materials for use in PSA displays, especially RM, LC host mixtures and LC media comprising them, which have only the disadvantages described above or have only a reduced degree.

In particular, the present invention enables a very high resistivity value, high VHR value, high reliability, low threshold voltage, short response time, high birefringence, excellent UV absorption, especially at longer wavelengths, Enables complete polymerization, allows a low pre-exposure angle to occur as quickly as possible, enables high stability of the pre-warp yarn even after longer time and / or UV exposure, reduces or prevents the occurrence of after-images in the display, To provide a LC medium for use in a PSA display.

It is a further object of the present invention to solve the problems of providing an LC mixture and a LC medium for PSA displays which enable a quick and complete polymerization of RM while showing reduced viscosity and high VHR.

This object is achieved according to the invention by the materials and methods described and claimed herein.

Surprisingly, at least some of the above-mentioned problems include polymeric components and LC host mixtures containing compounds of formula (A), (B) and (T), and additionally, It has been found that this can be solved by using an LC medium which additionally contains one or more amine-based photostabilizer (HALS) or derivatives thereof.

It has thus been found that it is possible to maintain high UV absorption and strong tilt angles required for fast and complete polymerization while maintaining a high VHR when using LC media described and claimed herein in PSA displays.

It has also been found that improvement of the VHR can be achieved by adding a stabilizing compound of formula S to the mixture.

The use of the LC medium according to the invention facilitates a fast and complete UV-photopolymerization reaction, in particular at low UV energy and / or at longer UV wavelengths of from 300 to 380 nm, and in particular greater than 340 nm, to be. In addition, the use of the LC medium according to the present invention enables the rapid generation of large and stable pretilt angles, reduces afterimage and ODF speckles in the display, induces high VHR values after UV light cure, And high birefringence.

US 2012/0268706 A1 describes a stabilizer of formula S and an LC medium comprising it, but does not describe or suggest the polymeric LC media described and claimed hereinafter.

According to the present invention,

- Preferably comprising at least one polymerizable compound, A)

- Also referred to as an "LC host mixture ", preferably consisting of at least one mesogenic or liquid crystalline compound comprising at least one compound of formula A, at least one compound of formula B and at least one compound of formula T Liquid crystal component B):

Wherein the individual radicals in each case are the same or different and each independently of the other have the following meanings:

R ¹ , R ² and R ^Q represent alkyl, alkoxy, oxaalkyl or alkoxyalkyl of 1 to 9 carbon atoms or alkenyl or alkenyloxy of 2 to 9 carbon atoms, all of which are optionally substituted Fluorinated,

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

L ¹ and L ² represent F or Cl, preferably F,

L ^Q1 to L ^Q6 represent H, F or Cl, preferably H or F, and at least one of L ^Q1 to L ^Q6 represents F or Cl, preferably F,

L ^T1 to L ^T6 represent H, F or Cl, preferably H or F, and at least one of L ^T1 to L ^T6 represents F or Cl, preferably F;

(LC) medium, wherein the LC medium comprises one or more compounds of the formula (S): < EMI ID =

[In the above formula,

R ^{a -d} independently of one another are straight-chain or branched alkyl having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, very preferably 1 to 4 carbon atoms, most preferably methyl Lt; / RTI >

X represents H, CH _3, OH or O ^and,

A represents an optionally substituted straight-chain, branched or cyclic alkylene having 1 to 20 carbon atoms.

The liquid crystal component B) of the LC medium according to the invention is hereinafter also referred to as the "LC host mixture ", and preferably the LC compound selected from the non-polymerizable low molecular weight compounds, such as the compounds of the formulas A, B and T And optionally includes additives such as polymerization initiators, inhibitors and the like.

The present invention also relates to LC media or LC displays described above and below, wherein the polymerizable compounds of component A are polymerized.

The present invention also relates to a process for the preparation of a compound of formula (I), which comprises at least one compound of formula A, at least one compound of formula B and at least one compound of formula T or an LC host mixture or LC component B) And at least one polymerizable compound, and optionally further LC compounds and / or additives, to a process for preparing the LC medium as described above and below.

The invention also relates to the use of LC media in LC displays, particularly PSA displays.

The invention also relates to the use of the LC media according to the invention in PSA displays, in particular by in-situ polymerization of the polymerizable compounds of component B) in a PSA display, preferably under the application of an electric or magnetic field, To a PSA display comprising an LC medium for producing an angle of incidence.

The present invention also relates to LC displays, in particular PSA displays, and more preferably PS-VA, PS-IPS or PS-UB-FFS displays comprising at least one compound of formula I or a LC medium according to the invention.

The present invention also relates to an LC display comprising at least one compound of the formula I or a polymer obtainable by the above-described polymerizable component A), or a LC medium according to the invention, which is preferably a PSA Display, and more preferably a PS-VA, PS-IPS or PS-UB-FFS display.

The present invention also relates to a PSA-type LC display comprising two substrates, at least one of which is light transmissive, an electrode provided on each substrate or two electrodes provided only on one of the two substrates, Characterized in that it comprises a layer of a LC medium, wherein the polymeric compound is polymerized between the substrates of the display, comprising at least one polymeric compound and an LC component as described above and hereinafter, between the substrates .

The present invention also relates to a process for the preparation of a liquid crystal display comprising the steps of charging or otherwise providing a LC medium comprising the above and below described one or more polymerizable compounds between the substrates of a display and polymerizing the polymerizable compounds. RTI ID = 0.0 > LC < / RTI > display.

A PSA display according to the present invention has two electrodes, preferably in the form of a transparent layer, applied to one or both of the substrates. In some displays, such as a PS-VA display, one electrode is applied to each of the two substrates. In other displays, such as PS-IPS or PS-UB-FFS displays, both electrodes are applied to only one of the two substrates.

In a preferred embodiment, the polymerizable component is polymerized in the LC display while a voltage is applied to the electrodes of the display.

The polymerizable compound of the polymerizable component is preferably polymerized by photopolymerization, more preferably by UV photopolymerization.

Unless otherwise stated, the polymerizable compounds and RM are preferably selected from achiral compounds.

The term "active layer" and "switchable layer" are used herein to refer to one or more molecules with structural and optical anisotropy, which change the orientation in an external stimulus such as an electric field or a magnetic field to change the transmittance of the layer for polarization or non- , E. G., A layer in an electro-optic display, e. G. An LC display, containing LC molecules.

As used herein, the term " tilt "or" tilt angle "shall be understood to mean the tilted orientation of LC molecules in the LC medium relative to the surface of the cell in an LC display (preferably a PSA display herein). The tilt angles herein represent the average angle (less than 90 DEG) between the longitudinal molecular axis of the LC molecule (LC director) and the plane-parallel outer plate surface that forms the LC cell. A low value of the tilt angle (i. E., A large deviation from a 90 angle) corresponds to a large tilt here. A suitable method for measuring the tilt angle is given in the following examples. Unless otherwise stated, the inclination angle values described above and below relate to this measurement method.

As used herein, the terms "reactive mesogen" and "RM" refer to a compound comprising a mesogenic or liquid crystalline backbone and one or more functional groups attached thereto (suitable for polymerization, also referred to as "polymerizable group" ≪ / RTI >

Unless otherwise stated, the term "polymeric compound" will be understood herein to mean a polymeric monomer compound.

As used herein, the term "low molecular weight compound" will be understood to mean a compound that is, in contrast to a "polymeric compound" or "polymer ", is a monomer and /

As used herein, "non-polymerizable compound" will be understood to mean a compound that does not contain functional groups suitable for polymerization under the conditions usually applied for the polymerization of RM.

As used herein, the term "mesogenic group" is well known to those skilled in the art and is described in the literature, and is inherently (at least in part) due to the anisotropy of attraction and repulsive interactions, And the like. A compound containing a mesogenic group (mesogenic compound) does not necessarily have to have an LC phase itself. Further, it is possible that the mesogenic compound can exhibit the LC phase behavior only after mixing and / or polymerizing with other compounds. Exemplary mesogenic groups are, for example, rigid rod- or disc-shaped units. A summary of terms and definitions used in connection with mesogenic or LC compounds is given in Pure Appl. 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 ", is known to those skilled in the art and is described, for example, in Pure Appl. Chem. 2001, 73 (5), 888] and [C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368. The term "spacer group" or "spacer" herein refers to a flexible group, such as an alkylene group, connecting the polymerizable group (s) and the mesogenic group in the polymerizable mesogenic compound.

In the above and below,

는 트랜스-1,4-사이클로헥실렌 고리를 나타내고,

Quot; represents a trans-1,4-cyclohexylene ring,

는 1,4-페닐렌 고리를 나타낸다.

Represents a 1,4-phenylene ring.

In the above and below, "organic group" represents a carbon or hydrocarbon group.

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

"Halogen" refers to F, Cl, Br or I.

"O ^and" it represents an oxygen radical.

를 나타낸다.-CO-, -C (= O) - and -C (O) - are carbonyl groups,

.

The carbon or hydrocarbon group may be a saturated or unsaturated group. The unsaturated group is, for example, an aryl, alkenyl or alkynyl group. The carbon or hydrocarbon group having more than three carbon atoms may be straight chain, branched chain and / or cyclic, and may also include a spiro bond or a condensed ring.

The terms "alkyl "," aryl ", "heteroaryl ", and the like also encompass multivalents such as alkylene, arylene, heteroarylene, and the like.

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

Preferred carbon and hydrocarbon groups are optionally substituted linear, branched or cyclic, alkyl, alkenyl, alkynyl, alkynyl, alkynyl, alkynyl, Alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy, optionally substituted aryl or aryloxy having 5 to 30, preferably 6 to 25 carbon atoms, or 5 Alkyl, arylalkyl, arylalkyl, arylcarbonyl, aryloxycarbonyl, aryl-carbonyloxy and aryl-carbonyloxy having from 1 to 30, preferably from 6 to 25 carbon atoms, Carbonyloxy wherein at least one carbon atom is also preferably replaced by a heteroatom selected from N, O, S, Se, Te, Si and Ge.

The preferred carbon and hydrocarbon groups of more C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ aryl, C ₄ -C ₂₀ alkyl diene yl, C ₄ - C ₂₀ polyenes yl, C ₆ -C ₂₀ cycloalkyl, C ₄ -C ₁₅ alkenyl, cycloalkyl, C ₆ -C ₃₀ aryl, C ₆ -C ₃₀ Alkylaryl, C ₆ -C ₃₀ arylalkyl, C ₆ -C ₃₀ alkylaryloxy, C ₆ -C ₃₀ Aryl-alkyloxy, C ₂ -C ₃₀ heteroaryl, C ₂ -C ₃₀ heteroaryloxy.

Particularly preferred are C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl, C ₆ -C ₂₅ aryl and C ₂ -C ₂₅ heteroaryl.

Additional preferred carbon and hydrocarbon groups are straight chain having 1 to 20, preferably 1 to 12, carbon atoms, which may be unsubstituted or singly or multiply substituted with F, Cl, Br, I or CN, It represents a chain or cyclic alkyl, wherein one or more non-adjacent CH ₂ groups, independently of each other, O and / or S atom in a manner that is not directly connected to each ^{other, -C (R x) = C} (R x) -, -C ^{≡C-, -N (R x) -} , may be replaced by -O-, -S-, -CO-, -CO- O-, -O-CO-, -O-CO-O-.

R ^x is preferably selected from the group consisting of H, F, Cl, CN, and a straight, branched or cyclic alkyl chain having from 1 to 25 carbon atoms wherein one or more non-adjacent C atoms are also optionally replaced by -O-, -O-, -CO-O-, -O-CO-, -O-CO-O- and at least one H atom may be replaced by F or Cl, or 6 to 30 carbon atoms An optionally substituted aryl or aryloxy group having from 2 to 30 carbon atoms, or an optionally substituted heteroaryl or heteroaryloxy group.

Preferred alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s- Cyclohexyl, n-octyl, n-decyl, n-undecyl, n-dodecyl, dodecanyl, trifluoro-methyl , Perfluoro-n-butyl, 2,2,2-trifluoroethyl, perfluorooctyl, perfluoro-hexyl and the like.

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

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

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

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

The aryl and heteroaryl groups may be monocyclic or polycyclic. That is to say they contain one ring (e.g. phenyl), two or more rings which can also be fused (e.g. naphthyl), two or more rings which can be covalently bonded (e.g. biphenyl) . ≪ / RTI > The heteroaryl group preferably contains at least one heteroatom selected from O, N, S and Se.

Particularly preferred are mono-, bi- or tricyclic aryl groups containing 6 to 25 carbon atoms and optionally mono-, bi- and trisubstituted mono-, di- or trisubstituted aryl groups having 5 to 25 ring atoms, Or a tricyclic heteroaryl group. Also preferred are 5-, 6- or 7-membered aryl and heteroaryl groups, wherein one or more CH groups may also be replaced by N, S or O in such a way that O and / or S atoms are not directly connected to each other .

Preferred aryl groups are, for example, phenyl, biphenyl, terphenyl, [1,1 ': 3', 1 "] terphenyl-2'-yl, naphthyl, anthracene, binaphthyl, Dihydrofuran, chrysene, perylene, tetracene, pentacene, benzo-pyrene, fluorene, indene, indenofluorene, spirobifluorene, and the like.

Preferred heteroaryl groups are, for example, 5-membered rings such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophen, oxa Sol, isoxazole, 1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1 , 3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 6 - a cyclic ring such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5- Tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, or condensing groups such as indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, Benzothiazole, benzothiazole, benzothiazole, benzothiazole, benzothiazole, benzothiazole, benzothiazole, benzothiazole, benzothiazole, benzothiazole, benzothiazole, benzothiazole, , This Benzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, benzoisoquinoline, acridine, Phenanthroline, thieno [2,3b] - thiophene, benzothiophene, benzothiophene, benzothiophene, benzothiophene, Thieno [3,2b] thiophene, dithienothiophene, isobenzo-thio-pen, dibenzothiophene, benzothiadiazothiophene, or a combination of these groups.

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

The (non-aromatic) alicyclic and heterocyclic groups both include a saturated ring, i.e. only including a single bond, and a partially unsaturated ring, i.e., also including multiple bonds. The heterocyclic ring preferably contains at least one heteroatom selected from Si, O, N, S and Se.

The (non-aromatic) alicyclic and heterocyclic groups may be monocyclic (e.g., cyclohexane) having only one ring, or polycyclic (including, for example, decahydro-naphthalene or bicyclooctane) . Particularly preferred is given as a saturated group. Preferred are also given as mono-, bi- or tri-cyclic groups containing from 5 to 25 ring atoms, optionally containing fused rings and optionally substituted. Also preferred is given as a 5-, 6-, 7- or 8-membered carbocyclic group, wherein one or more carbon atoms may also be replaced by Si and / or one or more CH groups may be replaced by N and / Or one or more non-adjacent CH ₂ groups may be replaced by -O- and / or -S-.

Preferred alicyclic and heterocyclic groups include, for example, 5-membered groups such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran, pyrrolidine, 6-membered groups such as cyclohexane, silica, cyclohexene, tetrahydropyran, Such as tetrahydrothiopyran, 1,3-dioxane, 1,3-dithiane, piperidine, 7-membered groups such as cycloheptane, and fused groups such as tetrahydronaphthalene, decahydronaphthalene, [1.1.1] -pentane-l, 3-diyl, bicyclo [2.2.2] octane- 1,4-diyl, spiro- [3.3] -heptane-2,6-diyl, octahydro- , 7-methanediyl-2,5-diyl.

Preferred substituents are selected from the group consisting of, for example, a solubility-promoting group such as alkyl or alkoxy, an electron-withdrawing group such as fluorine, nitro or nitrile, or a substituent for increasing the glass transition temperature (Tg) , In particular a bulky group, such as t-butyl or an optionally substituted aryl group.

Herein after also referred to as preferred substituents "L" is, F, Cl, Br, I , -CN, -NO 2, -NCO, -NCS, -OCN, -SCN, -C (= O) N (R _{^{x) 2, -C (= O}} ) Y 1, -C (= O) R x, -N (R x) 2, each having 1 to 25 carbon atoms, linear or branched alkyl, alkoxy, alkyl carbonyl Alkyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, wherein one or more H atoms may optionally be replaced by F or Cl, optionally substituted silyl having 1 to 20 silicon atoms, or 6 To < RTI ID = 0.0 > 25, < / RTI > preferably 6 to 15 carbon atoms,

Wherein R ^x is H, F, Cl, CN, or a straight, branched or cyclic alkyl having 1 to 25 carbon atoms, wherein one or more non-adjacent CH ₂ groups are optionally replaced by O- and / or S- May be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, Optionally substituted with F, Cl, P- or P-Sp-,

Y ¹ represents halogen.

"Unsubstituted silyl or aryl" is preferably, ^{halogen, -CN, R 0, -OR 0} , -CO-R 0, -CO-OR 0, -O-CO-R 0 or -O-CO- OR ⁰ , wherein R ⁰ represents H or alkyl having 1 to 20 carbon atoms.

Particularly preferred substituents L are selected from the group consisting of F, Cl, CN, NO ₂ , CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , COCH ₃ , COC ₂ H ₅ , COOCH ₃ , COOC ₂ H ₅ , CF ₃ , OCF ₃ , OCHF ₂ , OC ₂ F ₅ , and also phenyl.

는 바람직하게는

이고, 이때 L은 상기 기재된 의미 중 하나를 갖는다.

Is preferably

, Wherein L has one of the meanings given above.

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

, CH₂=CW²-(O)_k3-, CW¹=CH-CO-(O)_k3-, CW¹=CH-CO-NH-, CH₂=CW¹-CO-NH-, CH₃-CH=CH-O-, (CH₂=CH)₂CH-OCO-, (CH₂=CH-CH₂)₂CH-OCO-, (CH₂=CH)₂CH-O-, (CH₂=CH-CH₂)₂N-, (CH₂=CH-CH₂)₂N-CO-, HO-CW²W³-, HS-CW²W³-, HW²N-, HO-CW²W³-NH-, CH₂=CW¹-CO-NH-, CH₂=CH-(COO)_k1-Phe-(O)_k2-, CH₂=CH-(CO)_k1-Phe-(O)_k2-, Phe-CH=CH-, HOOC-, OCN- 및 W⁴W⁵W⁶Si-로 이루어진 군으로부터 선택되고,Preferred groups P are CH ₂ ═CW ¹ -CO-O-, CH ₂ ═CW ¹ -CO-,

^{_{, CH 2 = CW 2 - (}} O) k3 -, CW 1 = CH-CO- (O) k3 -, CW 1 = CH-CO-NH-, CH 2 = CW 1 -CO-NH-, CH 3 - CH = CH-O-, (CH 2 = CH) 2 CH-OCO-, (CH 2 = CH-CH 2) 2 CH-OCO-, (CH 2 = CH) 2 CH-O-, (CH 2 = _{CH-CH 2) 2 N-,} (CH 2 = CH-CH 2) 2 N-CO-, HO-CW 2 W 3 -, HS-CW 2 W 3 -, HW 2 N-, HO-CW 2 W _{^{3 -NH-, CH 2 = CW 1}} -CO-NH-, CH 2 = CH- (COO) k1 -Phe- (O) k2 -, CH 2 = CH- (CO) k1 -Phe- (O) k2 -, Phe-CH = CH-, HOOC-, OCN- and W ⁴ W ⁵ W ⁶ Si-,

Wherein W ¹ represents H, F, Cl, CN, CF ₃ , phenyl or alkyl having 1 to 5 carbon atoms, in particular H, F, Cl or CH ₃ ; W ² and W ³ are each, independently of one another, , H or alkyl having 1 to 5 carbon atoms, in particular H, methyl, ethyl or n-propyl, and W ⁴ , W ⁵ and W ⁶ are each, independently of one another, Cl, And W ⁷ and W ⁸ each independently represent H, Cl or an alkyl having 1 to 5 carbon atoms, and Phe represents an alkyl having 1 to 5 carbon atoms, excluding P-Sp- Phenylene which is optionally substituted with one or more radicals L as defined above, k ₁ , k ₂ and k ₃ independently of one another represent 0 or 1, k ₃ preferably represents 1 , and k ₄ represents an integer of 1 to 10.

, CH₂=CW²-O-, CH₂=CW²-, CW¹=CH-CO-(O)_k3-, CW¹=CH-CO-NH-, CH₂=CW¹-CO-NH-, (CH₂=CH)₂CH-OCO-, (CH₂=CH-CH₂)₂CH-OCO-, (CH₂=CH)₂CH-O-, (CH₂=CH-CH₂)₂N-, (CH₂=CH-CH₂)₂N-CO-, CH₂=CW¹-CO-NH-, CH₂=CH-(COO)_k1-Phe-(O)_k2-, CH₂=CH-(CO)_k1-Phe-(O)_k2-, Phe-CH=CH- 및 W⁴W⁵W⁶Si-로 이루어진 군으로부터 선택되고,A highly preferred group P is CH ₂ ═CW ¹ -CO-O-, CH ₂ ═CW ¹ -CO-,

^{_{, CH 2 = CW 2 -O-,}} CH 2 = CW 2 -, CW 1 = CH-CO- (O) k3 -, CW 1 = CH-CO-NH-, CH 2 = CW 1 -CO-NH- _{, (CH 2 = CH) 2} CH-OCO-, (CH 2 = CH-CH 2) 2 CH-OCO-, (CH 2 = CH) 2 CH-O-, (CH 2 = CH-CH 2) 2 _{N-, (CH 2 = CH-} CH 2) 2 N-CO-, CH 2 = CW 1 -CO-NH-, CH 2 = CH- (COO) k1 -Phe- (O) k2 -, CH 2 = is selected from, the group consisting of Phe-CH = CH- and ^{W 4 W 5 W 6 Si-,} - CH- (CO) k1 -Phe- (O) k2

Wherein W ¹ represents H, F, Cl, CN, CF ₃ , phenyl or alkyl having 1 to 5 carbon atoms, in particular H, F, Cl or CH ₃ ; W ² and W ³ are each, independently of one another, , H or alkyl having 1 to 5 carbon atoms, in particular H, methyl, ethyl or n-propyl, and W ⁴ , W ⁵ and W ⁶ are each, independently of one another, Cl, W ⁷ and W ⁸ each independently of one another represent H, Cl or an alkyl having 1 to 5 carbon atoms, Phe represents 1,4-phenylene, k ₁ , k ₂ and k ₃ independently represent 0 or 1, k ₃ preferably represents 1, and k ₄ represents an integer of 1 to 10.

로 이루어진 군으로부터 선택된다.A very particularly preferred group P is CH ₂ ═CW ¹ -CO-O-, especially CH ₂ ═CH-CO-O-, CH ₂ ═C (CH ₃ ) -CO-O- and CH ₂ ═CF-CO-O -, and also CH ₂ ═CH-O-, (CH ₂ ═CH) ₂ CH-O-CO-, (CH ₂ ═CH) ₂ CH-

≪ / RTI >

A further preferred polymerizable group P is selected from the group consisting of vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide, most preferably acrylate and methacrylate.

When the spacer group Sp is different from a single bond, it is preferably of the formula Sp "-X", so that the individual radicals P-Sp- correspond to the formula P-Sp "-X" -,

Sp "is an alkenyl group having 1 to 20, preferably 1 to 12 carbon atoms, optionally mono- or polysubstituted by F, Cl, Br, I or CN, wherein one or more non-adjacent CH the _second group is also, independently from each other, O and / or S atom in a manner that is not directly connected to each other, -O-, -S-, -NH-, -N (R 0) -, -Si (R 0 R 00 ) -, -CO-, -CO-O- , -O-CO-, -O-CO-O-, -S-CO-, -CO-S-, -N (R 00) -CO-O- , -O-CO-N (R ⁰ ) -, -N (R ⁰ ) -CO-N (R ⁰⁰ ) -, -CH═CH- or -C≡C-,

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

R ⁰ and R ⁰⁰ are each, independently of one another, H or alkyl having 1 to 20 carbon atoms,

Y ² and Y ³ each independently represent H, F, Cl or CN.

X "is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR ⁰ -, -NR ⁰ -CO-, -NR ⁰ - CO-NR < ⁰⁰ > - or a single bond.

Typical spacer groups Sp, and -Sp "-X" -, for example _{- (CH 2) p1 -,} - (CH 2 CH 2 O) q1 -CH 2 CH 2 -, -CH 2 CH 2 -S-CH 2 CH _{2 -, -CH 2 CH 2 -NH} -CH 2 CH 2 - or ^{- (SiR 0 R 00 -O)} p1 - and, at this time, and p1 is an integer from 1 to 12, q1 is an integer of 1 to 3, R ⁰ and R ⁰⁰ have the meanings indicated above.

Particularly preferred groups Sp and -Sp "-X" - is _{- (CH 2) p1 -,} - (CH 2) p1 -O-, - (CH 2) p1 -O-CO-, - (CH 2) p1 - CO-O-, or - a (CH _{2) p1} -O-CO-O-, wherein p1 and q1 have the above described meaning.

Particularly preferred groups Sp "are, in each case, straight chain, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, Ethylene, methyleneoxybutylene, ethylene thioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, ethenylene, prophenylene and buteneylene.

In the compounds of formula (S), R &^lt; a ^{> -d} preferably represents methyl or ethyl, very preferably methyl.

In the compounds of formula S, A preferably represents straight chain alkylene of 1 to 20 carbon atoms, branched alkylene of 2 to 20 carbon atoms, or cyclic alkylene of 3 to 20 carbon atoms, all of which Is optionally substituted with one or more groups L < ^{A &} gt ;.

In the compounds of the formula S, A very preferably denotes straight-chain alkylene having 1 to 20 carbon atoms or branched alkylene having 2 to 20 carbon atoms, all of which are optionally substituted with one or more groups L ^A .

Preferred substituents L ^A are selected from F and straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy each having 1 to 12 carbon atoms, wherein one or more The H atom may optionally be replaced by F or Cl.

In the first preferred embodiment of the invention, the compound of Formula S is selected from those X is H or CH _3, preferably H.

In the first preferred embodiment of the invention, the compound of Formula S is selected from those of the X ^and O, or OH, preferably O ^and.

In a first preferred embodiment of the invention the compound of formula S is selected from those wherein A is a branched alkylene having 2 to 20 carbon atoms optionally substituted with one or more groups L < ^{A &} gt ;.

Preferred compounds of formula S are selected from the following sub-formulas S1 to S4:

Wherein n1 is an integer from 2 to 12 and wherein one or more H-atoms in these radicals (CH ₂ ) _n1 are optionally substituted with methyl, ethyl, propyl, butyl, pentyl or hexyl groups.

A highly preferred compound of formula S is selected from the sub-formulas S1a to S4a:

In the first preferred embodiment of the invention, the compound of Formula S is selected from those X is H or CH _3, preferably H. Preferred compounds of the first preferred embodiment are those of formulas S1 and S4 above and sub-formulas S1a, S1b and S4a.

In a second preferred embodiment of the invention, the compound of Formula S is selected from those of the X ^and O, or OH, preferably O ^and. Preferred compounds of said second preferred embodiment are those of formulas S2 and S3 above and sub-formulas S2a, S2b, S2c and S3a. Especially preferred are the compounds of formula (S2a).

In a third preferred embodiment of the invention the compound of formula S is selected from those wherein A is optionally branched alkylene having 2 to 20 carbon atoms substituted by one or more groups L < ^{A &} gt ;. Preferred compounds of the second preferred embodiment are the compounds of formula S5 and sub-formulas S1b and S2c.

In this formula,

X is H, CH _3, OH or O ^and, preferably, H or O ^and,

R ^A is methyl, ethyl, propyl, butyl, pentyl or hexyl,

n2 is 0 or an integer of 1 to 12, preferably 0,

n3 is 0 or an integer of 1 to 12.

Preferred compounds of formula S5 are those of sub-formulas S1b and S2c.

Preferably, the ratio of the formula S or sub-formula thereof in the LC medium is from 10 to 1000 ppm, very preferably from 20 to 500 ppm.

Preferably, the LC medium comprises 1 to 5, preferably 1, 2 or 3 compounds of the formula S or sub-formulas thereof.

In another preferred embodiment of the invention, in addition to the compounds of the formula S, the LC medium comprises one or more further stabilizers, preferably those selected from the compounds of the formulas:

In the above formula, n is an integer of 1 to 6, preferably 3.

Preferably, the proportion of further stabilizers such as compounds of the formula SC in the LC medium is from 10 to 500 ppm, very preferably from 20 to 100 ppm.

The compound of formula (A) is preferably selected from the following formula (A1)

In the above formula, alkyl represents a straight-chain alkyl radical having 1 to 6 carbon atoms, and (O) represents an oxygen atom or a single bond. (O) represents an oxygen atom, and alkyl is preferably straight chain methyl, ethyl, propyl, butyl, pentyl or hexyl.

Preferably, the proportion of the compound of formula A or Al in the LC medium is from 2 to 35%, very preferably from 3 to 30%, most preferably from 5 to 25%.

Preferably, the LC medium comprises from 1 to 5, preferably 1, 2 or 3 compounds of formula A or Al.

The compound of formula (B) is preferably selected from formula (B1)

In the above formula, alkyl represents a straight-chain alkyl radical having 1 to 6 carbon atoms, and (O) represents an oxygen atom or a single bond. Very preferred are compounds of formula (B1) in which both of the radicals (O) represent an oxygen atom, and the alkyl is preferably straight-chain methyl, ethyl, propyl, butyl, pentyl or hexyl.

Preferably, the compound of formula B or B 1 in the LC medium is from 0.5 to 20%, very preferably from 1 to 15%, most preferably from 1 to 10%.

Preferably, the LC medium comprises 1 to 5, preferably 1, 2 or 3 compounds of the formula B or B1.

The compounds of formula (T) are preferably selected from the following sub-formulas T1 to T24:

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

R and R ^* preferably represent methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy or pentoxy.

Very preferred are those of the formulas T1, T2 and T3, especially those of the formulas T1 and T2.

(O) represents an oxygen atom, m is 1, 2, 3, 4 or 5, and R is preferably a linear, methyl, ethyl, propyl, butyl , Pentyl or hexyl.

Preferably, the LC medium does not comprise more than 15% of a compound of formula T or T1 to T24 or any other compound having a terphenyl group.

Preferably, the ratio of the compound of formula T or T1 to T24 or any other compound having a terphenyl group in the LC medium is from 0.5 to 15%, very preferably from 1 to 10%. In another preferred embodiment, the ratio of the compound of formula T or T1 to T24 or any other compound having a terphenyl group in the LC medium is from 5 to 15%, very preferably from 5 to 10%.

Preferably, the LC medium comprises from 1 to 5, very preferably from 1 to 2 compounds of the formula T or T1 to T24.

In an LC medium according to the invention, an LC host mixture comprising compounds of the formulas A, B and T is reacted with a stabilizer of one or more of the formula S, and preferably a polymerization Use with a gender component leads to properties favorable to the PSA display. In particular, one or more of the following advantages can be achieved:

- Excellent UV absorption even at longer wavelengths,

- Rapid and complete polymerization of RM,

In particular, the pre-emergence of a low pre-UV angle and / or a low pre-

- High UV absorption,

- increased UV stability,

- High linear stability after UV exposure,

- reduced afterimage,

- reduced ODF staining,

- high reliability and high VHR values after UV exposure and / or heat treatment,

- High birefringence,

- reduced viscosity, and

- Faster response time.

Since the LC medium according to the invention exhibits high absorption at longer UV wavelengths, it is possible to use longer UV wavelengths in the polymerization, which is advantageous for the display manufacturing process.

The polymerizable compound is preferably selected from the following formula < RTI ID = 0.0 > (I) <

R ^a -B ¹ - (Z ^b -B ² ) _m -R ^b I

Wherein the individual radicals in each case are the same or different and each independently of one another have the following meanings:

R ^a and R ^b are, P, P-Sp-, H , F, Cl, Br, I, -CN, -NO 2, -NCO, -NCS, -OCN, -SCN, SF 5 , or 1 to 25 Wherein at least one non-adjacent CH ₂ group is also independently selected from the group consisting of -C (R ⁰ ) = C (R ² ) ₂ , in which the O and / or S atoms are not directly connected to each other, ^{R 00) -, -C≡C-, -N} (R 00) -, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- Wherein one or more H atoms may also be replaced by F, Cl, Br, I, CN, P or P-Sp- and B ¹ and / or B ² comprises a saturated carbon atom , R < ^{a >} and / or R < ^b & gt ^; may also represent a spiro-linked radical to the saturated carbon atom,

Wherein at least one of the radicals R & lt ^{; a} & gt ^; and R < ^b & gt ^; represents or contains a group P or P-

P is a polymerizable group,

Sp is a spacer group or a single bond,

B ¹ and B ² are aromatic, heteroaromatic, alicyclic or heterocyclic groups having 4 to 25 ring atoms, which may include fused rings and are unsubstituted or mono- or polysubstituted by L, And,

Z ^b is -O-, -S-, -CO-, -CO- O-, -OCO-, -O-CO-O-, -OCH 2 -, -CH 2 O-, -SCH 2 -, - _{CH 2 S-, -CF 2 O-,} -OCF 2 -, -CF 2 S-, -SCF 2 -, - (CH 2) n1 -, -CF 2 CH 2 -, -CH 2 CF 2 -, - _{(CF 2) n1 -, -CH} = CH-, -CF = CF-, -C≡C-, -CH = CH-COO-, -OCO-CH = CH-, CR 0 R 00 or a single bond ,

R ⁰ and R ⁰⁰ are H or alkyl having 1 to 12 carbon atoms,

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

n1 represents 1, 2, 3 or 4,

L is P, P-Sp-, OH, CH ₂ OH, F, Cl, Br, I, -CN, -NO ₂ , -NCO, -NCS, -OCN, R ^x ) ₂ , -C (═O) Y ¹ , -C (═O) R ^x , -N (R ^x ) ₂ , optionally substituted silyl, optionally substituted aryl , Or a straight or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxy-carbonyloxy having 1 to 25 carbon atoms, wherein one or more H atoms are also optionally replaced by F, Cl, < / RTI > P or P-Sp-,

P and Sp have the meanings indicated above,

Y ¹ represents halogen,

R ^x is selected from the group consisting of P, P-Sp-, H, halogen, straight chain, branched or cyclic alkyl having from 1 to 25 carbon atoms wherein one or more non-adjacent CH ₂ groups are also optionally replaced by O and / O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- and at least one H atom may also be replaced by F , Cl, P or P-Sp-), an optionally substituted aryl or aryloxy group having from 6 to 40 carbon atoms, or an optionally substituted heteroaryl group having from 2 to 40 carbon atoms Or a hetero-aryloxy group.

Especially preferred compounds of formula (I), B ¹ and B ² are, Each independently of the other, is selected from the group consisting of 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, 7-diyl, fluorene-2,7-diyl, coumarin, flavone, wherein one or more CH groups in these groups are also optionally replaced by N, N-dihydro-phenanthrene-2,7-diyl, anthracene- Cyclohexane-1,4-diyl, wherein one or more non-adjacent CH ₂ groups may also be replaced by O and / or S, 1,4-cyclohexylene, bicyclo- [1.1.1] -Pentane-l, 3-diyl, bicyclo [2.2.2] octane- 1,4-diyl, spiro [3.3] -heptane-2,6-diyl, piperidin- Naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indan-2,5-diyl or octahydro-4 , 7-methanediyl-2,5-diyl, wherein all of these groups may be unsubstituted or mono- or polysubstituted by L as defined above. It is selected from the features.

Particularly preferred compounds of formula I are those wherein B ¹ and B ² are each, independently of one another, 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl or naphthalene- They are things that represent work.

Highly preferred compounds of formula I are selected from the following formulas:

Wherein the individual radicals in each case are the same or different and each independently of one another have the following meanings:

P ¹ , P ² and P ³ represent vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane or epoxy group,

Sp ¹ , Sp ² and Sp ³ represent a single bond or a spacer group, and at least ^{one of the} radicals P ¹ -Sp ¹ -, P ¹ -Sp ² - and P ³ -Sp ³ - may also represent R ^aa And at least one of the radicals P ¹ -Sp ¹ -, P ² -Sp ² and P ³ -Sp ³ - present is different from R ^aa ,

R ^aa is selected from the group consisting of H, F, Cl, CN or linear or branched alkyl having from 1 to 25 carbon atoms, wherein the at least one non-adjacent CH ₂ group may also independently of one another be replaced by O and / the ^{non-connection, -C (R 0) = C} (R 00) -, -C≡C-, -N (R 0) -, -O-, -S-, -CO-, -CO-O -, -O-CO-, -O-CO-O-, wherein one or more H atoms may also be replaced by F, Cl, CN or P ¹ -Sp ¹ - Optionally mono-or multifluorinated alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkylcarbonyloxy having from 1 to 12 carbon atoms, preferably from 1 to 12 carbon atoms, Alkoxycarbonyloxy wherein said alkenyl and alkynyl radical have at least two carbon atoms and said branched radical has at least three carbon atoms,

R ⁰ and R ⁰⁰ are H, or alkyl having 1 to 12 carbon atoms,

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

X ¹ , X ² and X ³ represent -CO-O-, -O-CO- or a single bond,

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

Z ² and Z ³ represent -CO-O-, -O-CO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ - or - (CH ₂ ) _n - Wherein n is 2, 3 or 4,

L is F, Cl, CN or a straight or branched, optionally mono- or polyfluorinated alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkyl Carbonyloxy or alkoxycarbonyloxy,

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

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

s represents 0, 1, 2 or 3,

t represents 0, 1 or 2,

x represents 0 or 1;

Particularly preferred are the compounds of the formulas M2 and M13.

Further preferred are the three reactive compounds M15 to M30, especially M17, M18, M19, M22, M23, M24, M25, M29 and M30.

In the compounds of formulas M1 to M30,

는 바람직하게는

이고,group

Is preferably

ego,

In this case, L is in each case the same or different from each other, have the or meaning given below, preferably _{F, Cl, CN, NO 2} , CH 3, C 2 H 5, C (CH 3) 3 , CH (CH ₃ ) ₂ , CH ₂ CH (CH ₃ ) C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , COCH ₃ , COC ₂ H ₅ , COOCH ₃ , COOC ₂ H ₅ , CF ₃ , OCF ₃ , OCHF ₂ , OC ₂ F ₅ or P-Sp-, very preferably F, Cl, CN, CH ₃ , C ₂ H ₅ , OCH ₃ , COCH ₃ , OCF ₃ or P- is Cl, CH _3, OCH _3, COCH ₃ or OCF _3, in particular F or CH _3.

Preferred compounds of formulas M1 to M30 are those in which P ¹ , P ² and P ³ represent acrylate, methacrylate, oxetane or epoxy groups, very preferably acrylate or methacrylate groups.

Preferred compounds of the formula M1 to M30 is of the add, Sp ^1, Sp ² and Sp are those ³ is a single bond.

Additional preferred compounds are the formula M1 to M30, an Sp ^1, Sp ² and Sp is a single bond, and ^3, Sp ^1, Sp ² and Sp ³ and one of the different ones with a single bond.

Preferred compounds of the formula M1 to M30 of the added is a single bond with different groups Sp ^1, Sp ² and _{^{Sp 3 - (CH 2) s1}} -X "- represents, where s1 is 1 to 6, preferably 2, 3, 4 or 5, X "is a link to the benzene ring, -O-, -O-CO-, -CO-O, -O-CO-O- or a single bond.

Particularly preferred is a LC medium comprising one, two or three polymeric compounds of formula (I).

Preferably, the proportion of the compound of formula I in the LC medium is from 0.01 to 5%, very preferably from 0.05 to 1%, most preferably from 0.1 to 0.5%.

Combining the polymerizable compounds of formulas M1 to M30 with the compounds of formulas B, Q and T is advantageous for fast and complete polymerization, rapid generation of a stable low pretilt angle after UV exposure, high reliability after UV exposure and high high VHR values Leads to favorable behavior of the LC medium, which is achieved with refractive index. In addition, the LC medium exhibits a high absorption rate at longer UV wavelengths, and thus it is possible to use such long UV wavelengths for polymerization, which is advantageous in the display manufacturing process.

For the production of PSA displays, the polymeric compounds contained in the LC medium are polymerized or cross-linked by in situ polymerization in the LC medium between the substrates of the LC display, optionally with voltage applied to the electrodes When two or more polymerizable groups are contained).

The structure of the PSA display according to the present invention corresponds to the conventional geometric PSA display described in the prior art cited at the outset. It is preferred that the geometry without protrusions, in particular the electrodes on the color filter side, are unstructured and only the electrodes on the TFT side have slots. A particularly suitable and preferred electrode structure for PS-VA displays is described, for example, in US 2006/0066793 A1.

A preferred PSA type LC display of the present invention comprises:

A pixel electrode designating a pixel region, wherein the pixel electrode is connected to a switching element disposed in each pixel region and optionally comprises a micro-slit pattern, and optionally a first orientation layer disposed on the pixel electrode A first substrate,

A second substrate comprising a common electrode layer, which may be disposed over a second substrate facing the first substrate, and optionally a second alignment layer,

A LC medium disposed between the first and second substrates and comprising the polymerizable component A and the liquid crystal component B described above and below, wherein the polymerizable component A can also be polymerized, layer.

The first and / or second alignment layer adjusts the alignment direction of the LC molecules of the LC layer. For example, in a PS-VA display, the orientation layer is selected to give an LC molecule homeotropic (or vertical) orientation (i.e., perpendicular to the surface) or an oblique orientation. Such an orientation layer may comprise, for example, polyimide, which may also be rubbed, or may be prepared by a photo-alignment method.

The LC layer with the LC medium can be deposited between the substrates of the display by methods commonly used by the display manufacturer, such as the so-called liquid crystal drop (ODF) method. The polymerizable component of the LC medium is then polymerized, for example by UV photopolymerization. The polymerization may be carried out in one step or in two or more steps.

The PSA display may include additional elements such as a color filter, a black matrix, a passive layer, an optical retardation layer, transistor elements for addressing individual pixels, etc., all of which are well known to those skilled in the art, It can also be used without the phosphor technology.

The electrode structure may be devised by one of ordinary skill in the art depending on the particular display type. For example, in the case of a PS-VA display, by providing electrodes with slits and / or bumps or protrusions to create two, four, or more different tilt orientation directions, multi-domain orientation of LC molecules can be induced .

Upon polymerization, the polymerizable compound forms a cross-linked polymer, which causes a specific pre-tilt of the LC molecule in the LC medium. Without wishing to be bound by any particular theory, it is believed that at least a portion of the cross-linked polymer formed by the polymerizable compound will be phase-separated or deposited from the LC medium and form a polymer layer on the substrate or electrode, or an orientation layer provided thereon. Microscopic measurement data (e.g., SEM and AFM) confirm that at least a portion of the polymer formed is deposited at the LC / substrate interface.

The polymerization can be carried out in one step. It is also possible to first polymerize by applying a voltage arbitrarily to provide a pre-baked square as a first step, and then to polymerize or cross-link unreacted compounds in the first step in a second polymerization step without applying a voltage ("End curing").

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

Optionally, one or more polymerization initiators are added to the LC medium. Suitable conditions for polymerization and suitable types and amounts of initiator are known to those skilled in the art and are described in the literature. Suitable for free-radical polymerization are, for example, commercially available photoinitiators Irgacure 651 ^® , Irgacure 184 ^® , Irgacure 907 ^® , Irgacure 369 ^® or Darocure 1173 ^® (Ciba AG). When a polymerization initiator is used, its proportion is preferably 0.001 to 5% by weight, particularly preferably 0.001 to 1% by weight.

The polymerisable compounds according to the invention are also suitable for polymerization without an initiator, which is accompanied by a considerable advantage such as less material cost and less contamination of the LC medium, especially by the possible residual amount of initiator or its degradation products. The polymerization can therefore also be carried out without the addition of an initiator. Thus, in a preferred embodiment, the LC medium does not comprise a polymerization initiator.

The LC medium may also comprise one or more stabilizers, for example, to prevent unwanted spontaneous polymerization of the RM during storage or transport steps. Suitable types and amounts of stabilizers are known to those skilled in the art and are described in the literature. Especially suitable are, for example, Irganox (Irganox ^®) series (Ciba AG), for example, say that a commercially obtainable stabilizer from Knox ^® 1076. When a stabilizer is used, the ratio thereof based on the total amount of RM or the polymerizable component (component A) is preferably 10 to 500,000 ppm, particularly preferably 50 to 50,000 ppm.

The polymeric compounds of formula I show particularly good UV absorption in the process of preparing PSA displays comprising at least one of the following characteristics and are therefore particularly suitable for such processes:

- exposing the polymerizable medium to UV light in a two-step manner in the display (e.g., a first UV exposure step ("UV-1 step") to generate the tilt angle and a second UV exposure step -2 step ")),

- exposing the polymeric media in the display to UV light in a display generated by a power saving UV lamp (also known as a "green UV lamp") (these lamps have relatively high absorption spectra of 300 to 380 nm) Can be characterized by a low intensity (typical UV1 lamp of 1/100 to 1/10), preferably used in UV2 stage, but also optionally in UVl stage if it is necessary to avoid high intensity) , And

Exposure of the polymeric medium to UV light generated by UV lamps in a display with a radiation spectrum which is converted to a longer wavelength, preferably 340 nm or more, in order to avoid short UV light exposure in the PS-VA process To do.

By using both lower intensity and UV conversion to longer wavelengths, it protects the organic layer from damage that may be caused by UV light.

Preferred embodiments of the present invention are directed to a method of making a PSA display as described above and below comprising at least one of the following features:

Exposing the polymerizable medium to UV light in a two-step manner in the display (e.g., a first UV exposure step ("UV-1 step") to generate the tilt angle and a second UV exposure step -2 step ")),

By means of a UV lamp having a strength of 0.5 mW / cm ² to 10 mW / cm ² in the wavelength range of 300 to 380 nm, which is preferably used in the UV ² stage and optionally also in the UV 1 stage Exposure to the generated UV light, and

Exposing the polymeric LC medium to UV light having a wavelength of 340 nm or more, preferably 400 nm or less.

The preferred method is to use a UV lamp that is substantially transmissive to UV light with each desired wavelength and substantially blocks light having each undesired wavelength, / RTI &gt; and / or a cut-off filter. For example, if irradiation with UV light of wavelength lambda of 300-400 nm is desired, the UV exposure may be performed using a broadband filter that is substantially transmissive at a wavelength of 300 nm < lambda &lt; 400 nm. If it is desired to irradiate with UV light of wavelength? Greater than 340 nm, UV exposure may be performed using a cutoff filter that is substantially transmissive to wavelength? Of greater than 340 nm.

By "substantially transmissive" is meant that the filter passes a substantial portion, preferably 50% or more, of the incident light of the desired wavelength. By "substantially blocking" is meant that the filter does not pass a substantial portion of the incident light of the unwanted wavelength, preferably not more than 50%. "Desired (undesired) wavelength" means a wavelength within (outside of) a given lambda value range, for example, in the case of a bandpass filter, and a wavelength in excess of (less than) a given lambda value in the case of a cutoff filter.

This preferred method enables the manufacture of displays using longer UV wavelengths, thereby reducing or even avoiding the dangerous and deleterious effects of short UV light components.

The UV irradiation energy is generally 6 to 100 J depending on production process conditions.

Preferably the LC medium according to the invention consists essentially of the polymeric component A) and LC component B) (or LC host mixture) described above and below. However, the LC medium may additionally include, but is not limited to, comonomers, chiral dopants, polymerization initiators, inhibitors, stabilizers, surfactants, wetting agents, lubricants, dispersants, hydrophobing agents, adhesives, flow improvers, defoamers, , One or more additional ingredients or additives selected from the list including diluents, reaction diluents, adjuvants, colorants, dyes, pigments and nanoparticles.

Preferred is a LC medium in which the polymerizable component A) is exclusively composed of polymeric compounds of formula (I).

In another preferred embodiment, the polymerizable component A) comprises at least one further polymerizable compound ("comonomer") selected from polymerizable compounds of formula I, preferably RM.

Preferably, the proportion of the polymerizable component A) in the LC medium is greater than 0 and less than 5%, very preferably greater than 0 and less than 1%, most preferably between 0.01 and 0.5%.

Preferably, the ratio of LC component B) in the LC medium is less than 95 to 100%, very preferably less than 99 to 100%.

Suitable and preferred mesogenic comonomers may be selected from Table D below.

The LC medium according to the invention comprises an LC host mixture comprising at least one, preferably at least two, LC compounds selected from the LC component B), or a low molecular weight compound which is non-polymeric, as well as the polymeric component A) . These LC compounds are selected to be stable and / or unreactive in the polymerization reaction under the conditions applied to the polymerization of the polymerizable compounds.

Examples of these compounds are the compounds of the above-mentioned formulas (A), (B) and (T).

Preferred is the LC component B), or the LC host mixture has a nematic LC phase, preferably a LC medium with no chiral liquid crystal phase.

Also preferred are achicular compounds of formula (I) wherein the compounds of component A and / or B are given as LC media exclusively selected from the group consisting of non-chiral compounds.

The LC component B), or the LC host mixture, is preferably a nematic LC mixture.

The LC medium and LC component B) or LC host mixture according to the invention preferably have a negative dielectric anisotropy.

In a preferred embodiment of the present invention, the LC component B), or the LC host mixture of the LC medium, comprises a compound of formula A, as well as one or more additional mesogenic or LC compounds comprising straight chain, branched or cyclic alkenyl groups (Hereinafter also referred to as an "alkenyl compound"), wherein the alkenyl group is stable to polymerization under the conditions used for the polymerization of the rosin compound contained in the LC medium.

These additional alkenyl compounds are preferably selected from the following formulas AN and AY:

Wherein the individual radicals in each case are the same or different and each independently of one another have the following meanings:

는

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를 나타내고,

Lt; / RTI &gt;

는

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를 나타내고,

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는

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를 나타내고,

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R ^A1 represents alkenyl having 2 to 9 carbon atoms or, when at least one of rings X, Y and Z represents cyclohexenyl, it also represents one of the meanings of R ^A2 ,

R ^A2 is an alkyl having from 1 to 12 carbon atoms wherein one or two non-adjacent CH ₂ groups may also be replaced by -O-, -CH = CH-, -CO-, -OCO- or -COO-), &lt; / RTI &gt;

Z ^x is -CH ₂ CH ₂ -, -CH═CH-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -CO-O-, _{-C 2 F 4 -, -CF =} CF-, -CH = CH-CH 2 O-, or single bond, preferably a single bond,

L ^{1 -4} represents H, F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F or CHF ₂ H, preferably H, F or Cl,

x represents 1 or 2,

z represents 0 or 1;

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

Further preferred compounds of the formulas AN and AY are those wherein L ¹ and L ² represent F or one of L ¹ and L ² represents F and the other represents Cl and L ³ and L ⁴ represent F , One of L &lt; ³ &gt; and L &lt; ⁴ &gt; represents F and the other represents Cl.

The compounds of formula AN are preferably selected from the sub-formulas AN1 to AN12:

Wherein alkyl and alkyl ^* each independently of one another represent a straight-chain alkyl radical having 1 to 6 carbon atoms, and alkenyl and alkenyl ^* are each, independently of one another, a straight-chain radical having 2 to 7 carbon atoms Represents an alkenyl radical. Alkenyl and alkenyl ^* are preferably CH ₂ ═CH-, CH ₂ ═CHCH ₂ CH ₂ -, CH ₃ -CH═CH-, CH ₃ -CH ₂ -CH═CH-, CH ₃ - (CH ₂ ) ₂ -CH = CH-, CH ₃ - (CH ₂ ) ₃ -CH = CH- or CH ₃ -CH = CH- (CH ₂ ) ₂ -.

Highly preferred compounds of formula AN are selected from the sub-formulas AN1a to AN6a:

Wherein m represents 1, 2, 3, 4, 5 or 6, i represents 0, 1, 2 or 3, and R ^b1 represents H, CH ₃ or C ₂ H ₅ .

Very particularly preferred compounds of the formula AN are selected from the sub-formulas AN1a1 to AN1a5:

Most preferred are compounds of formula AN1a2 and AN1a5.

The compounds of formula (AY) are preferably selected from the sub-formulas (AY1 to AY28)

Wherein alkyl and alkyl ^* each independently of one another represent a straight-chain alkyl radical having 1 to 6 carbon atoms, and alkenyl and alkenyl ^* are each, independently of one another, a straight-chain radical having 2 to 7 carbon atoms Represents an alkenyl radical. Alkenyl and alkenyl ^* are preferably CH ₂ ═CH-, CH ₂ ═CHCH ₂ CH ₂ -, CH ₃ -CH═CH-, CH ₃ -CH ₂ -CH═CH-, CH ₃ - (CH ₂ ) ₂ -CH = CH-, CH ₃ - (CH ₂ ) ₃ -CH = CH- or CH ₃ -CH = CH- (CH ₂ ) ₂ -.

A highly preferred compound of formula AY is selected from the sub-formulas AY5a to AY11a:

Wherein m and n represent, independently of each other, 1, 2, 3, 4, 5 or 6 and the alkenyl is CH ₂ ═CH-, CH ₂ ═CHCH ₂ CH ₂ -, CH ₃ -CH═CH -, CH ₃ -CH ₂ -CH═CH-, CH ₃ - (CH ₂ ) ₂ -CH═CH-, CH ₃ - (CH ₂ ) ₃ -CH═CH- or CH ₃ -CH═CH- ₂ ) ₂ -.

The LC medium is preferably a compound containing a terminal vinyloxy group (-O-CH = CH ₂ ), especially a compound of the formula AN or AY wherein R ^A1 or R ^A2 is a terminal vinyloxy group (-O-CH = CH ₂ ) Or does not include a compound of the formula (I).

Preferably, the LC medium comprises an LC component B), or an LC host mixture, based on a compound having negative dielectric anisotropy. These LC media are particularly suitable for use in PS-VA and PS-UB-FFS displays. Particularly preferred embodiments of such LC media are those of a) to z)

a) a LC medium comprising one or more compounds of the formula CY and / or PY:

In this formula,

a represents 1 or 2,

b represents 0 or 1,

는

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를 나타내고,

The

or

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

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

L ^{1 -4} each independently represent F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F or CHF ₂ .

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

The compounds of formula CY are preferably selected from the group consisting of the sub-formulas CY1 to CY33:

Wherein a represents 1 or 2, alkyl and alkyl ^* each independently of one another represent a straight chain alkyl radical having 1 to 6 carbon atoms and alkenyl represents straight chain alkenyl having 2 to 6 carbon atoms, (O) represents an oxygen atom or a single bond. Alkenyl preferably _{CH 2 = CH-, CH 2 =} CHCH 2 CH 2 -, CH 3 -CH = CH-, CH 3 -CH 2 -CH = CH-, CH 3 - (CH 2) 2 -CH = _{CH-, CH 3 - (CH 2} ) 3 -CH = CH- or _{CH 3 -CH = CH- (CH 2} ) 2 - represents a.

The compounds of formula PY are preferably selected from the group consisting of the following sub-formulas PY1 to PY20:

Wherein alkyl and alkyl ^* each, independently of one another, denote a straight-chain alkyl radical having 1 to 6 carbon atoms, alkenyl denotes a straight-chain alkenyl radical having 2 to 6 carbon atoms, (O) Atom or a single bond. Alkenyl preferably _{CH 2 = CH-, CH 2 =} CHCH 2 CH 2 -, CH 3 -CH = CH-, CH 3 -CH 2 -CH = CH-, CH 3 - (CH 2) 2 -CH = _{CH-, CH 3 - (CH 2} ) 3 -CH = CH- or _{CH 3 -CH = CH- (CH 2} ) 2 - represents a.

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

In this formula,

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

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

The compounds of the formula ZK are preferably selected from the group consisting of the sub-formulas ZK1 to ZK10:

Wherein alkyl and alkyl ^* each independently of one another denote a straight chain alkyl radical having 1 to 6 carbon atoms and alkenyl denotes a straight chain alkenyl radical having 2 to 6 carbon atoms. Alkenyl preferably _{CH 2 = CH-, CH 2 =} CHCH 2 CH 2 -, CH 3 -CH = CH-, CH 3 -CH 2 -CH = CH-, CH 3 - (CH 2) 2 -CH = _{CH-, CH 3 - (CH 2} ) 3 -CH = CH- or _{CH 3 -CH = CH- (CH 2} ) 2 - represents a.

Particularly preferred is a compound of the formula ZK1.

Particularly preferred compounds of formula ZK are selected from the sub-formulas ZK1a to ZK1c:

Wherein the propyl, butyl and pentyl groups are straight chain groups.

Most preferred is a compound of formula ZK1a.

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

Wherein the individual radicals in each case are the same or different and each independently of one another have the following meanings:

R ⁵ and R ⁶ are each, independently of one another, alkyl having 1 to 12 carbon atoms, in which one or two non-adjacent CH ₂ groups are also optionally replaced by -O-, CH = CH-, -CO-, -OCO- or -COO-), preferably alkyl or alkoxy having 1 to 6 carbon atoms,

는

를 나타내고,

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는

를 나타내고,

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e represents 1 or 2;

The compounds of formula DK are preferably selected from the group consisting of the sub-formulas DK1 to DK12:

Wherein alkyl and alkyl ^* each independently of one another denote a straight-chain alkyl radical having 1 to 6 carbon atoms and alkenyl denotes a straight-chain alkenyl radical having 2 to 6 carbon atoms. Alkenyl preferably _{CH 2 = CH-, CH 2 =} CHCH 2 CH 2 -, CH 3 -CH = CH-, CH 3 -CH 2 -CH = CH-, CH 3 - (CH 2) 2 -CH = _{CH-, CH 3 - (CH 2} ) 3 -CH = CH- or _{CH 3 -CH = CH- (CH 2} ) 2 - represents a.

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

In this formula,

는

The

를 나타내고,

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(At least one ring F is different from cyclohexylene),

f represents 1 or 2,

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

Z ^x represents -CH ₂ CH ₂ -, -CH═CH-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -CO-O-, -O- _{-C 2 F 4 -, -CF =} CF-, -CH = CH-CH 2 O- or a single bond, preferably represents a single bond.

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

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

The compounds of formula LY are preferably selected from the group consisting of the sub-formulas LY1 to LY24:

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

e) a LC medium further comprising at least one compound selected from the group consisting of the following formulas G1 to G4:

Wherein alkyl represents C _{1 -6} -alkyl, L ^x represents H or F, and X represents F, Cl, OCF ₃ , OCHF ₂ or OCH = CF ₂ . Particularly preferred are compounds of formula (G1) wherein X represents F.

f) a LC medium further comprising at least one compound selected from the group consisting of the following formulas Y1 to Y15:

Wherein R &lt; ⁵ &gt; is Alkyl has one of the meanings given above for R ¹ , alkyl represents C _{1 -6} -alkyl, d represents 0 or 1, and z and m each independently represent an integer of 1 to 6. In these compounds R ⁵ is particularly preferably a C _{1 -6-alkyl} or -alkoxy or C _{2 -6-alkenyl,} and, d is preferably 1. The LC medium according to the invention preferably comprises at least 5% by weight of one or more compounds of the above-mentioned formula.

g) a LC medium further comprising at least one biphenyl compound selected from the group consisting of the following formulas B1 to B3:

Wherein alkyl and alkyl ^* each independently of one another represent a straight-chain alkyl radical having from 1 to 6 carbon atoms, and alkenyl and alkenyl ^* are each, independently of one another, a straight-chain radical having 2 to 6 carbon atoms Represents an alkenyl radical. Alkenyl and alkenyl ^* is preferably _{CH 2 = CH-, CH 2 =} CHCH 2 CH 2 -, CH 3 -CH = CH-, CH 3 -CH 2 -CH = CH-, CH 3 - (CH ₂ ) ₂ -CH = CH-, CH ₃ - (CH ₂ ) ₃ -CH = CH- or CH ₃ -CH = CH- (CH ₂ ) ₂ -.

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

Compounds of formula (B2) are particularly preferred.

The compounds of the formulas B1 to B3 are preferably selected from the group consisting of the sub-formulas B1a to B2c:

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

h) a LC medium further comprising one or more compounds of the following formula O1 to O11:

Wherein R ¹ and R ² have the meanings as described above and preferably each independently of the other represent straight chain alkyl having 1 to 6 carbon atoms or straight chain alkenyl having 2 to 6 carbon atoms.

Preferred media comprise at least one compound selected from the following formulas O1, O3 and O4.

i) a LC medium further comprising one or more compounds of the formula (F1), preferably in an amount of more than 3% by weight, in particular of 5% by weight or more, very particularly preferably of 5 to 30%

In this formula,

는

The

를 나타내고,

Lt; / RTI &gt;

R ⁹ is H, CH _3, C ₂ H _5, or represents a nC ₃ H _7, (F) denotes any fluorine substituents, q denotes 1, 2 or 3, R ⁷ means described for R ¹ / RTI &gt;

Particularly preferred compounds of formula (FI) are selected from the group consisting of the sub-formulas Fll to Fl8:

In the above formula, R ⁷ preferably represents straight chain alkyl, and R ⁹ represents CH ₃ , C ₂ H ₅ or nC ₃ H ₇ . Particularly preferred are compounds of the formulas FI1, FI2 and FI3.

k) a LC medium further comprising at least one compound selected from the group consisting of the following formulas VK1 to VK4:

Wherein R ⁸ has ^one of the meanings given for R ¹ and alkyl represents a straight chain alkyl radical having 1 to 6 carbon atoms.

l) a LC medium further comprising at least one compound comprising a tetrahydronaphthyl or naphthyl unit selected from the group consisting of the following formulas N1 to N10:

In this formula,

R ¹⁰ and R ¹¹ are each, independently of one another, alkyl having 1 to 12 carbon atoms, in which one or two non-adjacent CH ₂ groups are also optionally replaced by -O-, CH 2, CH = CH-, -CO-, -OCO- or -COO-), preferably alkyl or alkoxy having 1 to 6 carbon atoms, and R ¹⁰ and R ¹¹ are preferably Straight-chain alkyl or alkoxy having 6 to 6 carbon atoms, or straight-chain alkenyl having 2 to 6 carbon atoms,

Z ¹ and Z ² are each independently of one _{another, -C 2 H 4 -, -CH} = CH-, - (CH 2) 4 -, - (CH 2) 3 O-, -O (CH 2) 3 - _{, -CH = CH-CH 2 CH} 2 -, -CH 2 CH 2 CH = CH-, -CH 2 O-, -OCH 2 -, -CO-O-, -O-CO-, -C 2 F 4 -, -CF = CF-, -CF = CH-, -CH = CF-, -CH ₂ - or a single bond.

m) one or more difluorodibenzochroms and / or chlorobenzenes of the following formulas BC to RC, preferably in an amount of 3 to 20% by weight, in particular 3 to 15% by weight,

In this formula,

R ¹¹ and R ¹² each independently of one another have one of the meanings given for R ¹¹ ,

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

Z ^m is -C ₂ H ₄ -, -CH ₂ O-, -OCH ₂ -, -CO-O- or -O-CO-,

c is 0, 1 or 2;

Particularly preferred compounds of the formulas BC, CR and RC are selected from the group consisting of the sub-formulas BC1 to RC3:

Wherein alkyl and alkyl ^* are each, independently of each other, it represents a straight chain alkyl radical having from 1 to 6 carbon atoms, (O) is an oxygen atom or a single bond, c is 1 or 2, alkenyl and Al alkenyl ^* shows a straight-chain alkenyl radicals, each independently, having 2 to 6 carbon atoms from each other. Alkenyl and alkenyl ^* is preferably _{CH 2 = CH-, CH 2 =} CHCH 2 CH 2 -, CH 3 -CH = CH-, CH 3 -CH 2 -CH = CH-, CH 3 - (CH ₂ ) ₂ -CH = CH-, CH ₃ - (CH ₂ ) ₃ -CH = CH- or CH ₃ -CH = CH- (CH ₂ ) ₂ -.

Very particular preference is given to mixtures comprising one, two or three compounds of the formula BC-2.

n) a LC medium further comprising fluorinated phenanthrene and / or dibenzofurane of one or more of the following formulas: PH or BF:

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

Particularly preferred compounds of the formula PH and BF are selected from the group consisting of the sub-formulas PH1 to BF1:

Wherein R and R ', each independently of the other, represent a straight chain alkyl or alkoxy radical having from 1 to 7 carbon atoms.

o) a LC medium further comprising one or more monocyclic compounds of the formula Y:

In this formula,

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

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

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

The compound of formula (Y) is preferably selected from the group consisting of the sub-formulas Y1 to Y10:

Wherein alkyl and alkyl ^* each independently of one another denote a straight chain alkyl radical having 1 to 6 carbon atoms and alkoxy denotes a straight chain alkoxy radical having 1 to 6 carbon atoms and alkenyl and alkenyl ^* Each independently represent a straight chain alkenyl radical having 2 to 6 carbon atoms and O represents an oxygen atom or a single bond. Alkenyl and alkenyl ^* is preferably _{CH 2 = CH-, CH 2 =} CHCH 2 CH 2 -, CH 3 -CH = CH-, CH 3 -CH 2 -CH = CH-, CH 3 - (CH ₂ ) ₂ -CH = CH-, CH ₃ - (CH ₂ ) ₃ -CH = CH- or CH ₃ -CH = CH- (CH ₂ ) ₂ -.

Particularly preferred compounds of formula Y are selected from the group consisting of the sub-formulas Y6A and Y6B:

In the above formulas, alkoxy preferably represents straight-chain alkoxy having 3, 4 or 5 carbon atoms.

p) a LC medium further comprising at least one terphenyl compound selected from the group consisting of:

In this formula,

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

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

L ^Q1 to L ^Q6 independently of one another are H or F, and at least one of L ^Q1 to L ^Q6 is F;

Preferred compounds of formula (Q) are those in which R ^Q is straight chain alkyl having 2 to 6 carbon 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 in which X ^Q represents F or OCF ₃ , very preferably F.

The compound of formula (Q) is preferably selected from the sub-formulas (Q1) or (Q2) below:

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

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

Preferably, the proportion of the compound of formula (Q) in the LC medium is from more than 0 to 5% by weight, very preferably 0.1 to 2% by weight, most preferably 0.2 to 1.5% by weight.

Preferably, the LC medium comprises 1 to 5, preferably 1 or 2 compounds of formula (Q).

The addition of the quaterphenyl compound of formula (Q) to the LC medium mixture maintains high UV absorption, allows for rapid and complete polymerization, allows for strong and fast inclination angles while reducing ODF speckles, Increases stability.

Furthermore, the addition of in the LC medium having a negative dielectric anisotropy of the formula Q having the positive dielectric anisotropy of the compound is the dielectric constant ε _|| And ε _⊥ , but in particular the high dielectric constant ε _|| , While keeping the dielectric anisotropy [Delta] e constant, thereby reducing the kick-back voltage and the afterimage.

q) a LC medium which does not comprise a compound comprising a terminal vinyloxy group (-O-CH = CH ₂ ), apart from a polymerizable compound according to the invention, in particular a compound of formula I or a sub-formula thereof and a comonomer.

r) a LC medium comprising 1 to 5, preferably 1, 2 or 3 polymeric compounds, preferably selected from polymeric compounds according to the invention, in particular compounds of formula I or sub-formulas thereof.

s), the proportion of the polymerizable compound, in particular the compound of formula I or sub-formula (s) thereof, is 0.05 to 5%, preferably 0.1 to 1%.

t) from 1 to 8, preferably from 1 to 5, compounds of the formulas CY1, CY2, PY1 and / or PY2. The proportion of these compounds in the whole mixture is preferably 5 to 60%, particularly preferably 10 to 35%. The individual contents of these compounds are preferably in each case 2 to 20%.

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

v) 1 to 10, preferably 1 to 8, compounds of the formula ZK, in particular the compounds of the formulas ZK1, ZK2 and / or ZK6. The proportion of these compounds in the whole mixture is preferably 3 to 25%, particularly preferably 5 to 45%. The individual contents of these compounds are preferably in each case 2 to 20%.

w) the proportion of compounds of the formulas CY, PY and ZK in the total mixture is more than 70%, preferably more than 80%.

x) The LC host mixture is a compound containing an alkenyl group, preferably a compound of the formula CY, PY and LY, in which one or both of R &lt; ¹ &gt; and R &lt; ² &gt; represents a straight chain alkenyl having 2 to 6 carbon atoms, , formula ZK and DK (wherein R ³ and R ⁴ represents a of the straight chain alkenyl having one or both or R ⁵ and R either ⁶ or both are from 2 to 6 carbon atoms), and by the formula B2 and B3 And more preferably at least one compound selected from the group consisting of CY15, CY16, CY24, CY32, PY15, PY16, ZK3, ZK4, DK3, DK6, B2 and B3. The concentration of these compounds in the LC host mixture is preferably from 2 to 70%, very preferably from 3 to 55%.

y) a LC medium comprising compounds selected from the formulas PY1 to PY8, very preferably one or more, preferably 1-5, compounds of the formula PY2. The proportion of these compounds in the whole LC host mixture is preferably 1 to 30%, particularly preferably 2 to 20%. The individual contents of these compounds are preferably 1 to 20% in each case.

The combination of the compounds of the above-mentioned preferred embodiments with the polymerized compounds described above provides the LC medium according to the invention with a low threshold voltage, a low rotational viscosity and a very good low temperature stability, as well as a constant high clearing point and a high HR value And permits rapid build-up of the PSA display, especially in low-angle squares. In particular, the LC medium exhibits a very short response time, especially a gray tone response time, in the PSA display as compared to the media from the prior art.

The LC medium and LC host mixture of the present invention preferably have a nematic phase range of at least 80 K, particularly preferably at least 100 K, and a rotational viscosity at 20 캜 of 250 mPa s or less, preferably 200 mPa s or less .

In a VA-type display according to the present invention, in the layer of the LC medium in the switched-off state, the molecules are oriented perpendicularly to the electrode surface (homeotropic orientation) or have a sloping homeotropic orientation. Upon application of an electric voltage, the rearrangement of the LC molecules occurs in the longitudinal molecular axis parallel to the electrode surface.

The LC media according to the invention, based on compounds with negative dielectric anisotropy, especially for use in displays of the PS-VA and PS-UB-FFS types, exhibit very low values of -0.5 to &lt; RTI ID = -10, in particular a negative dielectric anisotropy DELTA epsilon of -2.5 to -7.5.

In the LC medium according to the present invention used for displays of the PS-VA and PS-UB-FFS type, the birefringence? N is preferably less than 0.16, particularly preferably 0.06 to 0.14 and very particularly preferably 0.07 to 0.12.

The LC media according to the present invention may also comprise further additives known to those skilled in the art and described in the literature, such as polymerization initiators, inhibitors, stabilizers, surface-active ingredients or chiral dopants. They are not polymerizable or polymerizable. The polymerizable additive is thus given by the polymerizable component or component A). The non-polymerizable additive is thus given by the non-polymeric component or component B).

In a preferred embodiment, the LC medium comprises at least one chiral dopant, preferably at a concentration of from 0.01 to 1%, very preferably from 0.05 to 0.5%. The chiral dopants are preferably selected from the group consisting of the compounds from Table B below, very preferably R- or S-1011, R- or S-2011, R- or S-3011, R- or S- R- or S-5011.

In another preferred embodiment, the LC medium preferably comprises a racemate of one or more chiral dopants selected from the chiral dopants mentioned in the preceding paragraph.

Also, in the LC medium, for example, 0 to 15% by weight of a pleochroic dye, a nanoparticle, a conductive salt, preferably ethyldimethyldodecylammonium 4-hexylbenzoate, tetrabutylammoniumtetraphenyl (See, for example, Haller et al., Mol. Cryst. Liq. Cryst. 24, 249-258 (1973)) or by orienting the dielectric anisotropy, viscosity and / or nematic phase orientation It is possible to add a substance to change. Materials of this type are described, for example, in DE-A 22 09 127, 22 40 864, 23 21 632, 23 38 281, 24 50 088, 26 37 430 and 28 53 728.

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

The LC medium which can be used in accordance with the invention can be prepared in its own customary manner, for example by mixing one or more of the above-mentioned compounds with one or more polymeric compounds as defined above and optionally further liquid crystal compounds and / do. In general, the preferred amount of ingredient used in lesser amounts Advantageously, it is soluble in the ingredients that make up the major constituents at elevated temperatures. It is also possible to mix solutions of the components in an organic solvent such as acetone, chloroform or methanol, mix thoroughly and then distill, for example, to remove the solvent. The present invention also relates to a process for the preparation of the LC medium according to the invention.

It is natural for those skilled in the art that the LC medium according to the present invention may also include compounds in which, for example, H, N, O, Cl, F are replaced by corresponding isotopes such as deuterium and the like.

The following examples illustrate the present invention without limiting it. However, these examples show the preferred mixture concept with the compounds preferably used and their respective concentrations and combinations of these with each other. The embodiments also illustrate acceptable combinations of characteristics and characteristics.

The following abbreviations are used:

(n, m, and z are each, independently of each other, 1, 2, 3, 4, 5 or 6)

Table A

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

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

Table B

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

Table C shows possible stabilizers that can be applied to the LC medium according to the invention.

Table C

(Wherein n represents an integer of 1 to 12, preferably 1, 2, 3, 4, 5, 6, 7 or 8, and the terminal methyl group is not shown)

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

Table D

Table D shows exemplary compounds that can be used in the LC media according to the invention, preferably as reactive mesogen compounds.

In a preferred embodiment of the present invention, the mesogenic medium comprises at least one compound selected from the group of compounds selected from Table D. Most preferably, the LC medium is a compound selected from the following formulas RM-1 to RM-32, most preferably RM-1, RM-15 or RM-17, Comprises a compound selected from the formula &lt; RTI ID = 0.0 &gt; RM-41:

In addition, the following abbreviations and symbols are used:

V ₀ represents the threshold voltage (capacitance) [V] at 20 ° C,

n _e is the extraordinary refractive index measured at 20 캜 and 589 nm,

n _o is the normal refractive index measured at 20 ° C and 589 nm,

[Delta] n is the optical anisotropy measured at 20 [deg.] C and 589 nm,

ε _⊥ is the dielectric susceptibility perpendicular to the director at 20 ° C and 1 kHz,

is the dielectric susceptibility parallel to the director at 20 &lt; 0 & gt _; C and 1 kHz,

?? is dielectric anisotropy at 20 占 폚 and 1 kHz,

cl.p. Or T (N, I) is the isometric point [DEG C]

? ₁ is a rotational viscosity [mPa · s] measured at 20 ° C,

K ₁ is the modulus of elasticity ("splay" strain) at 20 ° C [pN]

K ₂ is the modulus of elasticity at 20 ° C ("twist" strain) [pN]

K ₃ is the modulus of elasticity at 20 ° C ("bend" strain) [pN].

Unless explicitly stated otherwise, all concentrations in the present invention are quoted in weight percent and relate to all the corresponding solid or liquid whole components without solvent.

Unless expressly stated otherwise, all temperature values described herein, such as the melting point T (C, N), the transition temperature T (S, N) from the smectic (S) to the nematic (N) T (N, I) is quoted in degrees Celsius (° C). M.p. shows the melting point and cl.p. Also, C = crystalline phase, N = nematic phase, S = smectic phase and I = isotropic phase. The numerical value between these symbols indicates the transition temperature.

All physical properties are described in "Merck Liquid Crystals, Physical Properties of Liquid Crystals ", Status Nov. 1997, Merck KGaA, Germany], and a temperature of 20 ° C is applied and Δn is determined at 589 nm and Δε is determined at 1 kHz unless otherwise noted in each case.

The term "threshold voltage" in the present invention relates to a capacitive threshold voltage (V ₀ ), also known as a Freedericks threshold, unless explicitly stated otherwise. In an embodiment, the optical threshold voltage can also typically be quoted with a 10% relative contrast (V ₁₀ ).

Unless otherwise stated, the methods of polymerizing the polymerizable compounds in the PSA displays described above and below are carried out at a temperature at which the LC medium shows a liquid phase, preferably a nematic phase, and most preferably at room temperature do.

Unless otherwise stated, a method of making a test cell and measuring its electro-optic and other properties is performed herein below or similarly.

The display used for the measurement of the capacitive threshold voltage consists of two plane-parallel glass outer plates with an electrode layer inside and a rubbed polyimide alignment layer on top with a spacing of 25 μm, It affects the tropic edge orientation.

The display or test cell, which is used for the measurement of the tilt angle, consists of two surface-parallel glass outer plates spaced apart by 4 μm with an electrode layer inside and a rubbed polyimide alignment layer on top, The mid layer rubs against each other and affects the homeotropic edge orientation of the liquid crystal molecules.

The polymerizable compound is polymerized by irradiation with UVA light of a defined intensity for a prespecified time in the display or test cell by a voltage (often 10 V to 30 V cross current, 1 kHz) applied simultaneously to the display. In the examples, unless otherwise stated, metal halide lamps or high pressure mercury lamps and 50 mW / cm ² intensity are used for the polymerization. The intensity is measured using a standard UVA meter (Hoenle UV-meter high resolution with UVA sensor).

The inclination angle is determined by a crystal rotation experiment (Otronic-Melchus TBA-105). A lower value (i.e. a larger deviation from a 90 DEG angle) corresponds to a larger slope here.

The VHR values were measured as follows: 0.3% polymeric monomeric compound was added to the LC host mixture and the resulting mixture was introduced into a VA-VHR test cell containing a non-rubbed VA-polyimide orientation layer. Unless otherwise stated, the LC-layer thickness d is approximately 6 [mu] m. VHR values are measured before and after UV exposure at 1 V, 60 Hz, and 64 μs pulses (measurement instrument: Autronic-Melchus VHRM-105).

Example  One

The nematic LC host mixture N1 was formulated as follows.

Usage Example  A

The polymerizable mixture was prepared by adding the reactive mesogen M1 to the nematic LC host mixture N1 at a concentration of 0.3% by weight and further adding stabilizers of the formula S1a or S1b, or prior art stabilizers SC at various concentrations .

The composition of the polymerizable mixture is shown in Table 1 below.

Table 1 - Polymerizable  Mixture composition

The VHR values of the polymerizable mixture are measured before and after UV exposure for 80 minutes at 20 DEG C or 60 DEG C, respectively, using fluorescent UV lamp type C (305 nm to 355 nm).

The VHR values of the polymer blend are shown in Table 1 below.

Table 2 - VHR  value

From Table 2 it can be seen that the compounds P1 to P6 according to the invention containing stabilizers of the formula S1a or S1b show significantly higher VHR values after UV exposure comparable to the mixture CP1 containing only the stabilizer SC .

Each of the polymerizable mixture and the polymerizable comparative mixture according to the present invention is each injected into a VA e / o test cell. The test cell includes a VA-polyimide alignment layer (JALS-2096-R1) rubbed antiparallel. The LC-layer thickness d is approximately 4 [mu] m.

(% By weight) of non-polymerized RM in the test cell by HPLC after polymerization in a test cell using fluorescent UV lamp type C (305 nm to 355 nm) at 60 ° C for 80 minutes to determine the polymerization rate, ). For this purpose, the polymerized mixture is then rinsed from the test cell and measured using MEK (methyl ethyl ketone).

The residual concentrations of RM in the mixture after 80 minutes of irradiation are shown in Table 3 below.

Table 3 - Residual monomer content

From Table 3 it can be seen that the mixtures P1 to P6 according to the invention comprising the stabilizers of the formula S1a or S1b show a rapid polymerization with a low amount of residual RM comparable to the stabilizer-free mixture CP1 of the formula S1a or S1b Can be confirmed.

Crystalline rotation experiment (Autronic - Melchers TBA-105). After UV irradiation (6J) of 50 mW / cm &lt; ² &gt; for 120 seconds, measure the pretilt angle.

Table 4 shows the pretilt angles.

Table 4 - Square

From Table 4, it can be seen that the mixtures P1 to P6 according to the invention containing the stabilizers of the formula S1a or S1b show a pretilt angle occurrence comparable to the stabilizer-free mixture CP1 of the formula S1a or S1b.

The results show that the polymeric mixture according to the invention comprising a stabilizer of the formula S exhibits improved reliability to high VHR values after UV exposure compared to a polymeric mixture having known stabilizers from the prior art Also shows that addition of the stabilizer of the above formula (S) does not adversely affect other properties such as pre-squareness and fast and complete polymerization.

Usage Example  B

0.3% by weight of reactive mesogen M1 is added to the nematic LC host mixture N1 to prepare a comparative polymerizable mixture CP2.

A polymerizable mixture P7 according to the invention is prepared by adding 0.3% by weight of reactive mesogen M1 and 100 ppm of a stabilizer of formula S2a to the nematic LC host mixture N1.

The VHR values of the polymerizable mixture are measured before and after UV exposure at 20 [deg.] C or 60 [deg.] C for 80 minutes each using fluorescent UV lamp type C (305 nm to 355 nm).

The VHR values of the polymerizable mixture are shown in Table 5 below.

Table 5 - VHR  value

From Table 5 it can be seen that the mixture P7 according to the invention containing the stabilizer of the formula S2a exhibits a higher VHR value after UV exposure compared to the stabilizer-free mixture CP2.

Each of the polymerizable mixture and the polymerizable comparative mixture according to the present invention is each inserted into a VA e / o test cell. The test cell includes a VA-polyimide alignment layer (JALS-2096-R1) rubbed in antiparallel. The LC-layer thickness d is about 4 [mu] m.

(% By weight) of the non-polymerized RM in the test cell by HPLC after polymerization in a test cell using fluorescent UV lamp type C (305 nm to 355 nm) at 60 ° C for 80 minutes, . The polymerized mixture is then rinsed from the test cell and measured using MEK (methyl ethyl ketone).

The residual concentrations of RM in the mixture after 80 minutes of irradiation are shown in Table 6 below.

Table 6 - Residual monomer content

From Table 6 it can be seen that the mixture P7 according to the invention containing the stabilizer of the formula S2a exhibits fast polymerization with a low residual RM comparable to the stabilizer-free mixture CP2.

The pre-baked square before and after the UV irradiation was measured using a high-pressure Hg lamp (20J) of 50 mW / cm ² for 400 seconds by a crystal rotation experiment (Otronic-Melchus TBA-105).

Table 7 shows the pretilt angles.

Table 7 - Square

From Table 7 it can be seen that the mixture P7 according to the invention containing the stabilizer of the formula S2a exhibits a pretilt angle development comparable to the mixture CP2.

The results show that the polymerizable mixture according to the invention comprising a stabilizer of the formula S exhibits improved reliability to high VHR values after UV exposure, The characteristics are not negatively affected.

Claims (20)

Polymerizable component A) comprising at least one polymerizable compound, and
A liquid crystal component B) comprising at least one mesogenic or liquid crystalline compound comprising at least one compound of formula A, and at least one compound of formula B, and at least one compound of formula T:

Wherein the individual radicals in each case are the same or different and each independently of the other have the following meanings:
R ¹ , R ² and R ^Q represent alkyl, alkoxy, oxaalkyl or alkoxyalkyl of 1 to 9 carbon atoms or alkenyl or alkenyloxy of 2 to 9 carbon atoms, all of which are optionally substituted Fluorinated,
X ^Q represents F, Cl, halogenated alkyl or alkoxy having 1 to 6 carbon atoms or halogenated alkenyl or alkenyloxy having 2 to 6 carbon atoms,
L ¹ and L ² represent F or Cl,
L ^Q1 to L ^Q6 represent H, F or Cl, at least one of L ^Q1 to L ^Q6 is F or Cl,
L ^T1 to L ^T6 represent H, F or Cl, and at least one of L ^T1 to L ^T6 is F or Cl,
(LC) medium comprising at least one compound selected from the following formula (S): &lt; EMI ID =

[In the above formula,
R ^{a -d} independently of one another denote straight-chain or branched-chain alkyl having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, very preferably 1 to 4 carbon atoms,
X represents H, CH _3, OH or O ^and,
A represents a linear, branched or cyclic alkylene having from 1 to 20 carbon atoms which is optionally substituted. The method according to claim 1,
Wherein the compound of formula S is selected from the sub-formulas S1 to S5:

[In the above formula,
X represents H, CH _3, OH or O ^and,
R ^A represents methyl, ethyl, propyl, butyl, pentyl or hexyl,
n1 is an integer of 2 to 12,
n2 is 0 or an integer of 1 to 12, preferably 0,
n3 is 0 or an integer of 1 to 12,
In formula S1 to S4, a radical (CH ₂₎ one or more H- atom in _n1 it is optionally replaced with methyl, ethyl, propyl, butyl, pentyl or hexyl. 3. The method according to claim 1 or 2,
Wherein the compound of formula S is selected from the sub-formulas S1a to S4a:

. 4. The method according to any one of claims 1 to 3,
Wherein the compound of formula A is selected from the sub-formula &lt; RTI ID = 0.0 &gt; A1 &lt; / RTI &

In the above formula, alkyl represents a straight-chain alkyl radical having 1 to 6 carbon atoms, and (O) represents an oxygen atom or a single bond. 5. The method according to any one of claims 1 to 4,
Characterized in that the compound of formula (B) is selected from the following formula (B1):

In the above formula, alkyl represents a straight-chain alkyl radical having 1 to 6 carbon atoms, and (O) represents an oxygen atom or a single bond. 6. The method according to any one of claims 1 to 5,
Wherein the compound of formula (T) is selected from the group consisting of the following formulas (T1) to (T24):

Wherein R represents a straight chain alkyl or alkoxy radical having 1 to 7 carbon atoms, R ^* represents a straight chain alkenyl having 2 to 7 carbon atoms, (O) represents an oxygen atom or a single bond, m represents an integer of 1 to 6; 7. The method according to any one of claims 1 to 6,
Lt; RTI ID = 0.0 &gt; formula I &lt; / RTI &gt;

Wherein the individual radicals in each case are the same or different and each independently of one another have the following meanings:
R ^a and R ^b are, P, P-Sp-, H , F, Cl, Br, I, -CN, -NO 2, -NCO, -NCS, -OCN, -SCN, SF 5 , or 1 to 25 Wherein at least one non-adjacent CH ₂ group is also independently selected from the group consisting of -C (R ⁰ ) = C (R ² ) ₂ , in which the O and / or S atoms are not directly connected to each other, ^{R 00) -, -C≡C-, -N} (R 00) -, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- Wherein one or more H atoms may also be replaced by F, Cl, Br, I, CN, P or P-Sp- and B ¹ and / or B ² comprises a saturated carbon atom , R &lt; ^{a &gt;} and / or R &lt; ^b & gt ^; may also represent a spiro-linked radical to the saturated carbon atom,
Wherein at least one of the radicals R & lt ^{; a} & gt ^; and R &lt; ^b & gt ^; represents or contains a group P or P-
P is a polymerizable group,
Sp is a spacer group or a single bond,
B ¹ and B ² are aromatic, heteroaromatic, alicyclic or heterocyclic groups having 4 to 25 ring atoms, which may include fused rings and are unsubstituted or mono- or polysubstituted by L, And,
Z ^b is -O-, -S-, -CO-, -CO- O-, -OCO-, -O-CO-O-, -OCH 2 -, -CH 2 O-, -SCH 2 -, - _{CH 2 S-, -CF 2 O-,} -OCF 2 -, -CF 2 S-, -SCF 2 -, - (CH 2) n1 -, -CF 2 CH 2 -, -CH 2 CF 2 -, - _{(CF 2) n1 -, -CH} = CH-, -CF = CF-, -C≡C-, -CH = CH-COO-, -OCO-CH = CH-, CR 0 R 00 or a single bond ,
R ⁰ and R ⁰⁰ are H or alkyl having 1 to 12 carbon atoms,
m represents 0, 1, 2, 3 or 4,
n1 represents 1, 2, 3 or 4,
L is P, P-Sp-, OH, CH ₂ OH, F, Cl, Br, I, -CN, -NO ₂ , -NCO, -NCS, -OCN, R ^x ) ₂ , -C (═O) Y ¹ , -C (═O) R ^x , -N (R ^x ) ₂ , optionally substituted silyl, optionally substituted aryl , Or a straight or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxy-carbonyloxy having 1 to 25 carbon atoms, wherein one or more H atoms are also optionally replaced by F, Cl, &lt; / RTI &gt; P or P-Sp-,
Y ¹ represents halogen,
R ^x is selected from the group consisting of P, P-Sp-, H, halogen, straight chain, branched or cyclic alkyl having from 1 to 25 carbon atoms wherein one or more non-adjacent CH ₂ groups are also optionally replaced by O and / O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- and at least one H atom may also be replaced by F , Cl, P or P-Sp-), an optionally substituted aryl or aryloxy group having from 6 to 40 carbon atoms, or an optionally substituted heteroaryl group having from 2 to 40 carbon atoms Or a hetero-aryloxy group. 8. The method according to any one of claims 1 to 7,
Wherein the polymerizable compound is selected from compounds of formula I as defined in claim 7, wherein B ¹ and B ² are each, independently of one another, 1,4-phenylene, 1,3-phenylene, naphthalene- Diyl, naphthalene-2,6-diyl, phenanthrene-2,7-diyl, 9,10-dihydro-phenanthrene-2,7-diyl, anthracene- -2,7-diyl, coumarin, flavone wherein one or more CH groups in these groups may also be replaced by N, cyclohexane-1,4-diyl wherein one or more non-adjacent CH ₂ groups are Cyclohexylene, bicyclo- [1.1.1] -pentane-1,3-diyl, bicyclo [2.2.2] octane-1, which may also be substituted by O and / or S, , 4-diyl, spiro [3.3] -heptane-2,6-diyl, piperidine- 1,4-diyl, decahydro-naphthalene-2,6-diyl, Dioctyl-4,7-methanediyl-2,5-diyl, wherein the moieties may be unsubstituted or substituted with one or more moieties selected from the group consisting of -tetrahydronaphthalene-2,6-diyl, Wherein all groups may be unsubstituted or mono- or polysubstituted by L as defined in claim 7. 9. The method according to any one of claims 1 to 8,
Wherein the polymerizable compound is selected from the following formulas M1 to M30: liquid crystal medium:

Wherein the individual radicals in each case are the same or different and each independently of one another have the following meanings:
P ¹ , P ² and P ³ represent vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane or epoxy group,
Sp ¹ , Sp ² and Sp ³ represent a single bond or a spacer group, and at least ^{one of the} radicals P ¹ -Sp ¹ -, P ¹ -Sp ² - and P ³ -Sp ³ - may also represent R ^aa And at least one of the radicals P ¹ -Sp ¹ -, P ² -Sp ² and P ³ -Sp ³ - present is different from R ^aa ,
R ^aa is selected from the group consisting of H, F, Cl, CN or linear or branched alkyl having from 1 to 25 carbon atoms, wherein the at least one non-adjacent CH ₂ group may also independently of one another be replaced by O and / the ^{non-connection, -C (R 0) = C} (R 00) -, -C≡C-, -N (R 0) -, -O-, -S-, -CO-, -CO-O -, -O-CO-, -O-CO-O-, wherein one or more H atoms may also be replaced by F, Cl, CN or P ¹ -Sp ¹ - Optionally mono-or multifluorinated alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkylcarbonyloxy having from 1 to 12 carbon atoms, preferably from 1 to 12 carbon atoms, Alkoxycarbonyloxy wherein said alkenyl and alkynyl radical have at least two carbon atoms and said branched radical has at least three carbon atoms,
R ⁰ and R ⁰⁰ are H, or alkyl having 1 to 12 carbon atoms,
R ^y and R ^z represent H, F, CH ₃ or CF ₃ ,
X ¹ , X ² and X ³ represent -CO-O-, -O-CO- or a single bond,
Z ¹ represents -O-, -CO-, -C (R ^y R ^z ) - or -CF ₂ CF ₂ -
Z ² and Z ³ represent -CO-O-, -O-CO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ - or - (CH ₂ ) _n - Wherein n is 2, 3 or 4,
L is F, Cl, CN or a straight or branched, optionally mono- or polyfluorinated alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkyl Carbonyloxy or alkoxycarbonyloxy,
L 'and L "represent H, F or Cl,
r represents 0, 1, 2, 3 or 4,
s represents 0, 1, 2 or 3,
t represents 0, 1 or 2,
x represents 0 or 1; 10. The method according to any one of claims 1 to 9,
Wherein the polymerizable compound is selected from the following formulas M1 and M2:

Wherein P ¹ , P ² , Sp ¹ , Sp ² , L and r are as defined in claim 8. 11. The method according to any one of claims 1 to 10,
A liquid crystal medium characterized by comprising at least one compound selected from the following formulas AN and AY:

Wherein the individual radicals in each case are the same or different and each independently of one another have the following meanings:

The

or

Lt; / RTI &gt;

The

or

Lt; / RTI &gt;

The

or

Lt; / RTI &gt;
R ^A1 represents alkenyl having 2 to 9 carbon atoms or, when at least one of rings X, Y and Z represents cyclohexenyl, it also represents one of the meanings of R ^A2 ,
R ^A2 represents alkyl having 1 to 12 carbon atoms, wherein one or two non-adjacent CH ₂ groups may also be replaced by -O-, -CH = CH-, - CO-, -OCO- or -COO-,
Z ^x is -CH ₂ CH ₂ -, -CH═CH-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -CO-O-, _{-C 2 F 4 -, -CF =} CF-, -CH = CH-CH 2 O-, or single bond, preferably a single bond,
L ^{1 -4} represents H, F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F or CHF ₂ H,
x represents 1 or 2,
z represents 0 or 1; 12. The method according to any one of claims 1 to 11,
A liquid crystal medium characterized by comprising at least one compound selected from the following formulas CY and PY:

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

The

or

Lt; / RTI &gt;
R ¹ and R ² represent alkyl having 1 to 12 carbon atoms wherein one or two non-adjacent CH ₂ groups may also be replaced by -O-, -CH = CH -, -CO-, -O-CO- or -CO-O-,
Z ^x is _{-CH = CH-, -CH 2 O-,} -OCH 2 -, -CF 2 O-, -OCF 2 -, -O-, -CH 2 -, -CH 2 CH 2 - or a single bond And,
L ^{1 -4} each independently represents F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F or CHF ₂ . 13. The method according to any one of claims 1 to 12,
A liquid crystal medium characterized in that it comprises at least one compound selected from the following formulas ZK and DK:

Wherein the individual radicals in each case are the same or different and each independently of one another have the following meanings:

The

or

Lt; / RTI &gt;

The

or

Lt; / RTI &gt;

The

or

Lt; / RTI &gt;
R ³ and R ⁴ are each, independently of one another, alkyl having 1 to 12 carbon atoms, in which one or two non-adjacent CH ₂ groups are also optionally replaced by -O- , -CH = CH-, -CO-, -O-CO- or -CO-O-,
Z ^y represents -CH ₂ CH ₂ -, -CH═CH-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -C ₂ F ₄ -, -CF = CF- or a single bond,
R ⁵ and R ⁶ are each, independently of one another, alkyl having 1 to 12 carbon atoms, in which one or two non-adjacent CH ₂ groups are also optionally replaced by -O-, CH = CH-, -CO-, -OCO- or -COO-), preferably alkyl or alkoxy having 1 to 6 carbon atoms,
e represents 1 or 2; 14. The method according to any one of claims 1 to 13,
Wherein the polymerizable compound is polymerized. An LC display comprising a LC medium as defined in any one of claims 1 to 13. 16. The method of claim 15,
LC display with PSA type display. 17. The method of claim 16,
LC display with PS-VA, PS-IPS or PS-UB-FFS display. 18. The method according to claim 16 or 17,
12. A method of manufacturing a liquid crystal display panel, comprising the steps of: providing a substrate having at least one of two substrates that are light transmissive, two electrodes provided on each substrate or only one of the two substrates, Characterized in that the layer of the LC medium as defined in claim 1, wherein the polymerizable compound is polymerized between the substrates of the display. A method of manufacturing an LC display according to claim 18, comprising providing the LC medium defined in any one of claims 1 to 11 between substrates of a display and polymerizing the polymerizable compound. At least one compound of formula A as defined in claim 1 or 4, at least one compound of formula B as defined in claim 1 or 5, and at least one compound of formula T as defined in claim 1 or 6, The compound is at least one compound of formula S as defined in any of claims 1, 2 or 3 and at least one polymerizable compound as defined in any of claims 1 and 7 to 10, 13. A process as claimed in any one of claims 1 to 11, optionally comprising admixing with further LC compounds and / or additives.