TW201940675A - Liquid-crystal display - Google Patents

Abstract

The present invention relates to a method of manufacturing a liquid crystal display (LCD) of the polymer stabilized ultra fast (PS-UF) twisted nematic (TN) mode, to an LCD obtained by this method and to an LC medium used therein.

Description

LCD Monitor

The present invention relates to a method for manufacturing a liquid crystal display (LCD) having a polymer stabilized (PS) twisted nematic (TN) mode, an LCD obtained by the method, and an LC medium used therein.

LCDs currently in use have a variety of good characteristics, such as low weight, flatness, and wide viewing angles. However, the response time of current technologically advanced LCDs is often not fast enough, and therefore poses obstacles to their implementation in a variety of novel applications such as gaming and virtual reality (VR). In order to enable color sequence technology, a response time of approximately 1 ms is required. If such a fast response time can be achieved, the LCD can become a low power consumption technology, thereby extending the battery pack life of mobile devices. LCD manufacturers of LCDs therefore invest a lot of effort to shorten LCD response time.

However, so far, no viable solution has been issued for LCD modes with ultra-fast response times that are also suitable for mass production. For example, currently used LCD modes, such as TN, Multi-domain Vertical Arrangement (MVA), Coplanar Switching (IPS), and Fringe Field Switching (FFS) modes, cannot fully meet the fast response time and high speed due to their unit configuration. Transmission requirements. To achieve this, a new LCD mode is needed.

Recently, a solution to this problem has been proposed, which achieves a fast response time by using a short-pitch TN LCD. The TN LCD is doped with a chiral nematic LC material to achieve a shorter spiral pitch (p) of twisted nematic LC molecules, thereby achieving a shorter decay response time (t _d ).

However, when the ratio d / p of the element gap (d) to the helical pitch (p) is greater than 0.5, the 270 ° super twisted nematic (STN) LC director configuration is more energy-efficient than the short pitch length of 90 ° TN The LC director configuration is more stable, while the 90 ° TN configuration becomes unstable and transitions to a 270 ° STN configuration. Therefore, it is necessary to maintain a short pitch of d / p> 0.5, but at the same time maintain the TN LC configuration required to achieve fast switching time.

In the literature, it is reported that the 270 ° STN configuration can be changed to a 90 ° TN configuration by applying a voltage, and the 90 ° TN configuration can then be stabilized by photopolymerization, such as by forming in an LC medium Polymer network structure, see K. Takatoh et al., "Fast-response twisted nematic liquid crystals with ultrashort pitch liquid crystalline materials", Liq. Cryst. 2012 , 39 , 715-720. It was also reported that the 90 ° TN configuration can be stabilized by forming polymer walls in LC media, see IDW 2014, LCT1-2, "Polymer-Wall Stabilization of Ultra-Short-Pitch TN-LCDs". However, the stabilized TN LCD as described therein has a lower transmittance and / or a lower contrast ratio and requires a higher driving voltage than a conventional unstable TN LCD.

Therefore, the object of the present invention is to provide a method for manufacturing a TN LCD, which has a fast response time, especially a fast off or decay time (t _d ), while still maintaining a 90 ° TN LC director configuration and simultaneously achieving One or more of a low driving voltage, a high contrast ratio, and a high transmittance. Another object of the present invention is to provide a TN LCD, especially a polymer stabilized (PS) TN LCD obtained by this method, which allows to achieve a fast response time and overcome the disadvantages of the prior art TN LCD and PS-TN LCD, Such as high driving voltage, low contrast ratio and low transmittance. Those skilled in the art will immediately recognize other objects of the present invention based on the following embodiments.

It has been found that these goals can be achieved by providing a method of manufacturing a TN LCD as disclosed and claimed below. In particular, it was found that by stabilizing a TN LCD with a polymer (even with a small amount of polymer) according to the method described below, a fast response time can be achieved while maintaining a 90 ° TN LC director configuration and still be achieved Low driving voltage, high contrast ratio and high transmittance. The display obtained by this method according to the present invention is hereinafter also referred to as "polymer stabilized (ultrafast) twisted nematic LCD" or "PS (-UF) -TN LCD".

The present invention relates to a liquid crystal display (LCD) having a polymer stabilized twisted nematic (PS-TN) mode. The liquid crystal display includes
a) a first substrate and a second substrate, the first substrate being provided with a first electrode layer and optionally a first alignment layer, the second substrate being provided with a second electrode layer and optionally a second alignment layer,
b) a nematic LC dielectric layer distributed between the first and second substrates, which contains a palmitic additive and has a positive dielectric anisotropy,
c) a first polarizer existing on one side of the LC layer on the back of the first substrate and a second polarizer existing on one side of the LC layer on the back of the second substrate, The polarizer is preferably oriented such that its transmission plane is at a right angle to the plane polarized light (orthogonal Nicoll),
The longitudinal axis of the LC molecules is oriented parallel or oblique to the plane of the substrate, and the LC molecules of the LC medium are spirally twisted along the axis perpendicular to the substrate at a specified distance p, and the LC medium layer has a thickness , And the ratio d / p is ≥0.5, preferably> 0.5, and is preferably 0.6 to 0.8, and the twist angle of the helical twist of the LC molecule is 60 to 120 °, preferably 80 to 100 °, and very preferably 90 °, and wherein the display further comprises a polymer layer deposited on one or both of the first and second electrodes or, if present, on one or both of the first and second alignment layers ,
The polymer layer is formed of one or more polymerizable mesogen compounds, and the concentration of the compounds contained in the LC medium is <3%, preferably 0.05 to <3%, and the LC medium has been dispensed. After the two substrates, in-situ polymerization occurs.

The invention further relates to a method for manufacturing an LCD with PS-TN mode, which comprises the following steps:
a) a first substrate and a second substrate, the first substrate being provided with a first electrode layer and optionally a first alignment layer, the second substrate being provided with a second electrode layer and optionally a second alignment layer,
Wherein the first and / or second substrate is preferably equipped with a fixing member, the fixing members are preferably a sealing material and / or a spacer, so that the first substrate and the second substrate are at a constant distance relative to each other and their Fixed when the planes are parallel to each other,
b) a nematic LC dielectric layer having positive dielectric anisotropy is distributed between the first and second substrates, so that if these layers exist, the LC medium is in contact with the first and second alignment layers,
The LC medium includes, and preferably consists of:
A) a liquid crystal component A (hereinafter also referred to as "LC host mixture"), which contains liquid crystal molecules or liquid crystal molecules, preferably composed of liquid crystal molecules or liquid crystal molecules,
B) a polymerizable component B comprising one or more polymerizable mesogen compounds (hereinafter also referred to as "reactive mesogens"), preferably consisting of these compounds,
C) one or more palmar additives, preferably selected from palmar dopants,
D) optionally one or more other additives, preferably selected from polymerization initiators, stabilizers and self-aligning additives,
The concentration of the polymerizable mesogen in the LC medium is <3%, preferably 0.05 to <3%, and the longitudinal axis of the LC molecules is oriented in parallel or obliquely with respect to the plane of the substrate, and the palmity additive induces the LC medium. The LC molecules are twisted helically at a specified distance p along an axis perpendicular to the substrate, and the LC dielectric layer has a thickness d, and the ratio d / p is ≥0.5, preferably> 0.5, and preferably 0.6 to 0.8, and The twist angle of the helical twist of the LC molecule induced by the palm additive is> 210 °, preferably 210 to 330 °, more preferably 240 to 300 °, and extremely good 270 °,
c) Applying a voltage to the first electrode and the second electrode reduces the twist angle of the spiral twist of the LC molecules to <150 °, preferably to a range of 60 to 120 °, and more preferably 80 to 100 °, Excellent at 90 °,
d) polymerizing the polymerizable mesogen of the polymerizable component B of the LC medium between the first substrate and the second substrate after the voltage is applied, preferably by exposure to UV radiation Aggregate, thereby stabilizing the torsional nematic configuration of the LC medium with the reduced torsion angle in step c), and
e) subjecting the LC medium to a second polymerization step, preferably by exposing to UV radiation without applying a voltage to the first electrode and the second electrode, thereby polymerizing any polymerizable compound that has not reacted in step d) ,
f) Optionally, a first polarizer is disposed on one side of the LC layer on the back of the first substrate and a second polarizer is disposed on one side of the LC layer on the back of the second substrate, where the polarized light The mirror is preferably oriented such that its transmission plane is at a right angle (c) to the plane polarized light (orthogonal Nicollard).

The invention further relates to an LC display obtained by a method as described above and below.

The invention further relates to an LC medium for use in an LC display, as described above and below.

Terms and definitions
As used herein, the terms "active layer" and "switchable layer" mean a layer in an electro-optical display (such as an LC display) that contains one or more molecules having a structural and optical anisotropy, such as, for example, LC Molecules, which change their orientation after an external stimulus (such as an electric or magnetic field), thereby causing the layer to change its transmittance to polarized or unpolarized light.

As used herein, the terms "twist" and "twist angle" are understood to mean an orientation in which the longitudinal axis of the LC molecules of the LC medium is substantially parallel to the plane of the nearest substrate of the display unit and follows a spiral perpendicular to the plane of the substrate The shaft is twisted.

As used herein, the terms "tilt" and "tilt angle" are understood to mean an orientation in which the longitudinal axis of the LC molecules of the LC medium forms an angle with the plane of the nearest substrate of the display unit.

As used herein, the term "director" or "LC director" is understood to mean the average direction of the long molecular axis of the LC molecule.

As used herein, the terms "reactive mesogen" and "RM" mean a compound containing a mesogen framework or a mesogen structure and one or more functional groups attached thereto, which functional groups are suitable for polymerization and are also referred to as "may Polymeric group "or" P ".

As used herein, unless otherwise stated, the term "polymerizable compound" is understood to mean a polymerizable monomer compound.

As used above and below, the LC medium contains the words "polymer obtained from polymerisation of polymerizable component B" or "polymer obtained from polymerisation of one or more polymerisable compounds" and the wording should be understood to encompass the polymer retaining portion Or fully dispersed in the LC medium; and in which the polymer precipitates from the LC medium and is on one or both of the substrates or on one or both of the alignment layers or electrode structures deposited thereon Example of forming a polymer layer.

As used herein, the term "low-molecular-weight compound" is understood to mean a compound that, as opposed to a "polymeric compound" or "polymer," acts as a monomer and / or is not prepared by a polymerization reaction.

As used herein, the term "non-polymerizable compound" is understood to mean a compound that does not contain a functional group suitable for polymerization under the conditions in which RM polymerization is typically applied.

As used herein, the term "liquid crystalline group" is known to those skilled in the art and described in the literature, and means that it substantially contributes to low molecular weight or polymeric materials due to its anisotropy of attraction and repulsion interactions. A group that generates a liquid crystal (LC) phase. The compound containing a mesogen (the mesogen) does not necessarily need to have an LC phase. The mesogen compound may also exhibit LC phase characteristics only after mixing with other compounds and / or after polymerization. Typical liquid crystal primitives are, for example, rigid rod-shaped or disc-shaped cells. An overview of terms and definitions used in connection with mesogen compounds or LC compounds is provided in Pure Appl. Chem. 2001, 73 (5), 888 and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004 , 116, 6340-6368.

As used herein, the term "spacer" (hereinafter also referred to as "Sp") is known to those skilled in the art and is described in the literature, see, for example, Pure Appl. Chem. 2001, 73 (5), 888 And C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004 , 116, 6340-6368. As used herein, the term "spacer" or "spacer" means a flexible group, such as an alkylene group, that connects a mesogen in a polymerizable mesogen to a polymerizable group.

Above and below,

Represents a trans-1,4-cyclohexyl ring, and

Represents a 1,4-phenylene ring.

Above and below, "organic group" means a carbon or hydrocarbon group.
"Carbon-based" means a monovalent or polyvalent organic group containing at least one carbon atom, which does not contain other atoms (such as -C≡C-) or optionally one or more other atoms, such as N, O, S , B, P, Si, Se, As, Te, or Ge (such as carbonyl, etc.). The term "hydrocarbyl" refers to a carbon group that additionally contains 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" means F, Cl, Br or I.

-CO-, -C (= O)-, and -C (O)-represent carbonyl groups, that is, .

The carbon or hydrocarbon group may be a saturated or unsaturated group. Unsaturated groups are, for example, aryl, alkenyl or alkynyl. A carbon or hydrocarbyl group having more than 3 C atoms may be a linear, branched, and / or cyclic group and may also contain a spiro bond or a condensed ring.

The terms "alkyl", "aryl", "heteroaryl" and the like also encompass polyvalent groups such as alkylene, aryl, heteroaryl, and the like.

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

Preferred carbon and hydrocarbon groups are optionally substituted straight, branched or cyclic alkyl, alkenyl, alkynyl, alkane having 1 to 40, preferably 1 to 20, and preferably 1 to 12 C atoms. Oxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy; optionally substituted aryl or aryloxy having 5 to 30, preferably 6 to 25 C atoms ; Or optionally substituted alkylaryl, arylalkyl, alkylaryloxy, arylalkoxy, arylcarbonyl, aryloxy having 5 to 30, preferably 6 to 25 C atoms Carbonyl, arylcarbonyloxy and aryloxycarbonyloxy, in which one or more C atoms can also be replaced by heteroatoms, these heteroatoms are preferably selected from N, O, S, Se, Te, Si and Ge .

More preferred carbon and hydrocarbon groups are C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ allyl, C ₄ -C ₂₀ alkyldienyl , C ₄ -C ₂₀ polyalkenyl, C ₆ -C ₂₀ cycloalkyl, C ₄ -C ₁₅ cycloalkenyl, C ₆ -C ₃₀ aryl, C ₆ -C ₃₀ alkylaryl, C ₆ -C ₃₀ arylalkyl, C ₆ -C ₃₀ alkylaryloxy, C ₆ -C ₃₀ arylalkoxy, 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.

More preferred carbon and hydrocarbon groups are straight, branched or cyclic alkyl groups having 1 to 20, preferably 1 to 12 C atoms, which are unsubstituted or monosubstituted by F, Cl, Br, I or CN or Multi-substituted and one or more of the non-adjacent CH ₂ groups are independently of each other in such a way that O and / or S atoms may not be directly connected to each other via -C (R _x ) = C (R _x )-,- CC-, -N (Rx)-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- substitution.

R ^x preferably represents H, F, Cl, CN, a linear, branched, or cyclic alkyl group having 1 to 25 C atoms, wherein, in addition, one or more non-adjacent C atoms may be -O- , -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, and one or more of the H atoms may be replaced by F or Cl, or it means that Substituted aryl or aryloxy groups having 6 to 30 C atoms or optionally substituted heteroaryl or heteroaryloxy groups having 2 to 30 C atoms.

Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, 2-methylbutyl, n-pentyl, Dipentyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, n-nonyl, n-decyl, n-undecyl, N-dodecyl, dodecyl, trifluoromethyl, perfluoro-n-butyl, 2,2,2-trifluoroethyl, perfluorooctyl, perfluorohexyl and the like.

Preferred alkenyl groups are, for example, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctene Base etc.

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

Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, Tertiary butoxy, 2-methylbutoxy, n-pentoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonoxy, n-decoxy, n-undecyloxy, N-dodecyloxy and the like.

Preferred amine groups are, for example, dimethylamino, methylamino, methylaniline, aniline and the like.

Aryl and heteroaryl groups can be monocyclic or polycyclic groups, that is, they can contain one ring (such as phenyl) or two or more rings, and these rings can also be fused (such as naphthyl) Either covalently bonded (such as biphenyl) or a combination containing fused and bonded rings. Heteroaryl contains one or more heteroatoms, which are preferably selected from O, N, S and Se.

Especially preferred are monocyclic, bicyclic or tricyclic aryl groups having 6 to 25 C atoms and monocyclic, bicyclic or tricyclic heteroaryl groups having 5 to 25 ring atoms, which optionally contain fused rings and optionally Was replaced. In addition, a 5-membered, 6-membered or 7-membered aryl group and a heteroaryl group are preferred, and in addition, one or more CH groups may pass through N, S or O substitution.

Preferred aryl groups are, for example, phenyl, biphenyl, bitriphenyl, [1,1 ': 3', 1 "] bitriphenyl-2'-yl, naphthyl, anthracene, binaphthyl, phenanthrene, 9,10 -Dihydro-phenanthrene, pyrene, pyrene, dihydropyrene, tritium, pyrene, fused tetrabenzene, pentacene, benzofluorene, fluorene, indene, indenefluorene, 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, selenophene, oxazole, Isoxazole, 1,2-thiazole, 1,3-thiazole, 1, 2,3-oxadiazole, 1, 2, 4-oxadiazole, 1, 2, 5-oxadiazole, 1, 3, 4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole; 6-membered 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 a condensed group such as indole, isoindole, indazine, indazole, benzimidazole, benzotriazole, Purine, naphthalimidazole, fimidazole, pyrimidazole, pyrazine imidazole, quinazoline imidazole, benzoxazole, naphthoxazole, anthraxazole, phenanthrazole, isoxazole, benzothiazole, benzo Furan, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pyridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quine Phthaloline, benzoisoquinoline, acridine, phenothiazine, phenoxazine, benzopyrazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole , Benzocarboline, phenanthroline, phenanthroline, thieno [2,3b] thiophene, thieno [3,2b] thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazole Thiothiophene, or a combination of these groups.

The aryl and heteroaryl groups mentioned above and below may also be substituted with alkyl, alkoxy, sulfanyl, fluorine, fluoroalkyl, or other aryl or heteroaryl groups.

(Non-aromatic) cycloaliphatic and heterocyclic groups encompass saturated rings, that is, rings that exclusively contain single bonds; and partially unsaturated rings, that is, rings that may also contain multiple bonds. The heterocyclic ring contains one or more heteroatoms, which are preferably selected from Si, O, N, S and Se.

(Non-aromatic) alicyclic and heterocyclic groups may be monocyclic, that is, contain only one ring (such as cyclohexane); or polycyclic, that is, contain multiple rings (such as decahydro) Naphthalene or bicyclooctane). Especially preferred is a saturated group. Further, a monocyclic, bicyclic or tricyclic group having 5 to 25 ring atoms is preferred, which optionally contains a fused ring and is optionally substituted. In addition, a 5-membered, 6-membered, 7-membered, or 8-membered carbocyclic group is preferable, in addition, one or more C atoms may be substituted by Si and / or one or more CH groups may be substituted 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 are, for example, 5-membered groups such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran, pyrrolidine; 6-membered groups such as cyclohexane, cyclohexylsilane, cyclohexene, Tetrahydropiran, tetrahydrothiopiran, 1,3-dioxane, 1,3-dithiane, piperidine; 7-membered groups such as cycloheptane; and fused groups such as tetrahydronaphthalene , Decahydronaphthalene, indane, bicyclo [1.1.1] pentane-1,3-diyl, bicyclo [2.2.2] octane-1,4-diyl, spiro [3.3] heptane-2,6 -Diyl, octahydro-4,7-methyl bridge indane-2,5-diyl.

Preferred substituents are, for example, solubility-promoting groups such as alkyl or alkoxy groups; electron-withdrawing groups such as fluorine, nitro, or nitriles; or substituents for increasing the glass transition temperature (Tg) of the polymer, in particular In other words, a bulky group, such as a third butyl group, or an optionally substituted aryl group.

Preferred substituents (hereinafter also referred to as "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 , straight or branched chain alkyl, alkoxy, alkylcarbonyl, alkoxy A carbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy group, each of which has 1 to 25 C atoms, of which one or more H atoms can be optionally substituted with the following: F or Cl, optionally substituted with 1 Silicon groups of up to 20 Si atoms, or optionally substituted aryl groups of 6 to 25 (preferably 6 to 15) C atoms,
Where R ^x indicates H, F, Cl, CN or a linear, branched or cyclic alkyl group having 1 to 25 C atoms, where one or more non-adjacent CH ₂ -groups are O- and / or S-atoms are not directly connected to each other by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, and one or more of them are replaced as appropriate. Each H atom is optionally replaced by F, Cl, P- or P-Sp-, and
Y ¹ represents halogen.

"Substituted silicon or aryl" preferably means via halogen, -CN, R ⁰ , -OR ⁰ , -CO-R ⁰ , -CO-OR ⁰ , -O-CO-R ⁰ or -O- CO-OR ⁰ substitution, where R ⁰ represents H or an alkyl group having 1 to 20 C atoms.

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

Preferably
Where L has one of the meanings specified above.

The polymerizable group P is a group suitable for a polymerization reaction (such as radical or ionic chain polymerization, addition polymerization, or polycondensation) or a polymer-like reaction (for example, addition or condensation to a polymer main chain). Particularly preferred are groups for chain polymerization, in particular, groups containing a C = C double bond or -C≡C-parameter bond, and groups suitable for ring-opening polymerization, such as an oxocyclic ring Butane or epoxy.

The preferred group P is selected from the group consisting of: 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-, where W ¹ represents H, F, Cl, CN, CF ₃ , phenyl, or one having 1 to 5 C atoms Alkyl, in particular, H, F, Cl or CH ₃ ; W ² and W ³ each independently represent H or an alkyl group having 1 to 5 C atoms, in particular, H, methyl, ethyl Or n-propyl; W ⁴ , W ^5, and W ⁶ each independently represent Cl, oxaalkyl or oxacarbonylalkyl having 1 to 5 C atoms; W ⁷ and W ⁸ each independently represent H , Cl or an alkyl group having 1 to 5 C atoms; Phe means 1,4-phenylene, which is optionally substituted with one or more groups L as defined above other than P-Sp-; k ₁ , k ₂ and k ₃ are represented independently of each other 0 or 1, k ₃ preferably represents 1, and k ₄ represents an integer of 1 to 10.

An excellent group P is selected from the group consisting of: 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 = CH- (CO) _k1 -Phe- (O) _k2- , Phe-CH = CH- and W ⁴ W ⁵ W ⁶ Si-, where W ¹ represents H, F, Cl, CN, CF _{3 ,} phenyl or An alkyl group of 1 to 5 C atoms, specifically, H, F, Cl, or CH ₃ ; W ² and W ³ each independently represent H or an alkyl group of 1 to 5 C atoms, specifically, H, methyl, ethyl, or n-propyl; W ⁴ , W ^5, and W ⁶ each independently represent Cl, an oxaalkyl group or an oxacarbonylalkyl group having 1 to 5 C atoms; W ⁷ and W ⁸ each independently represent H, Cl or an alkyl group having 1 to 5 C atoms; Phe represents 1,4-phenylene; k ₁ , k ₂ and k ₃ each independently represent 0 or 1, k ₃ It is preferable to represent 1 and k ₄ represents an integer of 1 to 10.

An extremely preferred group P is selected from the group consisting of: CH ₂ = CW ¹ -CO-O-, in particular, CH ₂ = CH-CO-O-; CH ₂ = C (CH ₃ ) -CO-O -And CH ₂ = CF-CO-O-, and CH ₂ = CH-O-, (CH ₂ = CH) ₂ CH-O-CO-, (CH ₂ = CH) ₂ CH-O-, .

More preferably, the polymerizable group P is selected from the group consisting of vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide, most preferably selected from acrylic acid. Esters and methacrylates.

If Sp is different from a single bond, it preferably has the formula Sp "-X", so that each group P-Sp- conforms to the formula P-Sp "-X"-, where
Sp "represents an alkylene group having 1 to 20, preferably 1 to 12 C atoms, which is optionally mono- or poly-substituted by F, Cl, Br, I or CN and wherein, in addition, one or more are not adjacent The CH ₂ groups can be independently of each other via -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- substitution,
"X" means -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 single bond,
R ⁰ and R ⁰⁰ each independently represent H or an alkyl group having 1 to 20 C atoms, and
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 single key.

Typical spacer groups Sp and -Sp "-X"-are, 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- , where p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R ⁰ and R ⁰⁰ has the meaning specified above.

Particularly preferred groups SP and -Sp "-X"-are-(CH ₂ ) _p1 -,-(CH ₂ ) _p1 -O-,-(CH ₂ ) _p1 -O-CO-,-(CH ₂ ) _p1 -CO-O-,-(CH ₂ ) _p1 -O-CO-O-, wherein p1 and q1 have the meanings specified above.

In each case, the particularly preferred groups Sp "are straight-chain ethylene, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Undecyl, Dodecyl, Octadecyl, Ethyloxy, Ethyl, Methyleneoxy, Butyl, Ethylthio, Ethyl-N-methyl Imine ethylene, 1-methyl alkylene, vinylene, propenyl and butenyl.

In the method according to the invention, the twisted nematic LC configuration is provided with an initial short pitch corresponding to the STN configuration, where d / p> 0.5, and the twist angle is in the range of 210 ° to 330 °, preferably 270 °.

This is achieved by adding a dopant dopant with a specific torsional force to the LC medium.

The helical twisting force or HTP of a palm dopant is a measure of its ability to induce helical twisting of a particular nematic LC medium. HTP for palm dopants is inherent and can be defined by equation (1)
HTP = (p ^. C) ^-1 (1)
Where p is the distance between the induced helical twists, and c is the concentration c of the dopant dopant in the LC medium.

It is also possible to use two or more homogeneous dopants, for example to compensate for the temperature dependence of the HTP of the individual dopants and thereby reduce the temperature dependence of the spiral spacing.

A limited voltage is then applied to the electrodes of the display during the manufacturing process. Therefore, the twist angle is reduced to a value corresponding to the TN configuration, such as 90 °.

According to K. Takatoh et al., Liq. Cryst. 2012 , 39 , 715-720, it is possible to change the LC molecule's self-twisted open state (as in the STN configuration) to a torsional bend state (as in the TN configuration). Explain that the twist angle changed from 270 ° to 90 °.

This voltage-induced TN configuration is metastable and usually relaxes to the initial STN configuration after a certain period of voltage disconnection.

In the method according to the invention, the relaxation of the twist angle from the TN-LC to the STN-LC configuration is prevented by polymerizing the polymerizable compound of component B, preferably by ultraviolet light polymerization. Although the palm dopants induce short pitches, thereby maintaining a metastable TN configuration with a "non-natural" low twist angle. Thus, the LC molecules in the LC medium are forced into a state where the natural pitch of the LC medium is lower than that specified by equation (1) above. In other words, the actual twist angle of the LC molecules does no longer correspond to the "natural" pitch of the helical twist induced by the opposing dopant and the d / p value of the display unit.

As a result of this method, significant reductions in response time can be achieved (compared to those made from similar materials, but in which the amount of palmitic dopants is reduced, so the spacing is longer and the d / p value is lower, both A display that matches the reduced twist angle).

It has been found that according to the present invention, the low torsion and beneficial effects of polymer-stabilized PS-TN LCDs (such as fast rise and decay times, high transmittance, and good contrast) can be achieved by placing only a small amount of polymerizable liquid crystals <3% This was achieved by adding the original compound to the LC medium.

It has also been found that in the PS-TN LCD according to the present invention, a considerable portion of the polymer formed from the polymerizable mesogen compound will be phase-separated from the LC medium or precipitated from the LC medium and be provided on or on the substrate or electrode. A polymer layer is formed on the alignment layer. This can be confirmed by micrometrics such as SEM or AFM, which indicates that the polymer formed is mainly accumulated at the LC layer / substrate interface. This makes it possible, in particular, to reduce the transmission loss of the LCD compared to an unstable TN LCD and to achieve a high transmission.

These are the previous techniques such as the above reports that the formation of a polymer network structure or polymer wall in LC media requires a certain minimum amount of monomers, and that the polymer network structure or polymer wall in LC media results in lower transmission Significant advantages that publications cannot anticipate.

Preferably, the LC medium used in the display according to the present invention contains
A) a liquid crystal component A, which contains mesogen molecules or liquid crystal molecules,
B) a polymerizable component B comprising one or more polymerizable mesogen compounds,
C) one or more palmar additives, preferably selected from palmar dopants,
D) optionally one or more other additives, preferably selected from stabilizers and polymerization initiators,
The concentration of the polymerizable mesogen of component B in the LC medium is 0.1 to <3% by weight.

The liquid crystal component A) in the LC medium as used in the display according to the present invention is also referred to as "LC host mixture" hereinafter, and preferably contains only LC compounds selected from non-polymerizable low molecular weight compounds.

Component A or LC host mixture in the LC medium preferably comprises one or more compounds selected from the group consisting of formulas A and B

Wherein the individual groups have the following meanings independently of each other and in each occurrence the same or different:
R ²¹ , R ³¹ are each independently an alkyl, alkoxy, oxaalkyl, or alkoxyalkyl group having 1 to 9 C atoms or an alkenyl or alkenyloxy group having 2 to 9 C atoms The above owners are fluorinated as appropriate,
X ⁰ F, Cl, a halogenated alkyl or alkoxy group having 1 to 6 C atoms, or a halogenated alkenyl or alkenyloxy group having 2 to 6 C atoms,
Z ³¹ -CH ₂ CH _2- , -CF ₂ CF _2- , -COO-, trans-CH = CH-, trans - CF = CF-, -CH ₂ O- or single bond, preferably -CH ₂ CH _2- , -COO-, trans-CH = CH- or a single bond, especially -COO-, trans-CH = CH- or a single bond,
L ²¹ , L ²² , L ³¹ , and L ³² are each independently H or F,
L ^S H or CH ₃ , wherein preferably, at least one of the two groups L ^S connected to the same benzene ring is H,
g 0, 1, 2, or 3.

In the compound of the formula A and B, X ⁰ is preferably _{F, Cl, CF 3, CHF} 2, OCF 3, OCHF 2, OCFHCF 3, OCFHCHF 2, OCFHCHF 2, OCF 2 CH 3, OCF 2 CHF 2, OCF ₂ CHF ₂ 、 OCF ₂ CF ₂ CHF ₂ 、 OCF ₂ CF ₂ CHF ₂ 、 OCFHCF ₂ CF ₃ 、 OCFHCF ₂ CHF ₂ 、 OCF ₂ CF ₂ CF ₃ 、 OCF ₂ CF ₂ CClF ₂ 、 OCClFCF ₂ CF ₃ or CH = CF ₂ , preferably F or OCF ₃ , most preferably F.

In compounds of the formulae A and B and their subformulas, the ring

Better representation
,
In addition,
.

In a preferred embodiment, at least one of the compounds of formulae A and B or a subformula thereof contains at least one ring
.

In the compounds of the formulae A and B, R ²¹ and R ^{31 are} preferably selected from linear alkyl or alkoxy groups having 1, 2, 3, 4, 5, or 6 C atoms, and having 2, 3, 4 A linear alkenyl group of 5, 6, or 7 C atoms.

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

In the compound of formula B, Z ^{31 is} preferably COO, trans-CH = CH or a single bond, and most preferably COO or a single bond.

Preferably, component A) of the LC medium comprises one or more compounds of formula A selected from the group consisting of:

Wherein A ²¹ , R ²¹ , X ⁰ , L ²¹ , L ^22, and L ^S have the meanings specified in Formula A, L ²³ and L ²⁴ are each independently H or F, and X ^{0 is} preferably F. Especially preferred are compounds of formulae A1 and A2.

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


Wherein R ²¹ , X ⁰ , L ²¹ and L ²² have the meanings specified in Formula A1, L ²³ , L ²⁴ , L ²⁵ and L ²⁶ are each independently H or F, and X ^{0 is} preferably F.

More preferred are compounds of the formula A1a-A1g, wherein at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group at the para position of the fluorine atom.

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



Wherein R ^{21 is} as defined in Formula A1.

More preferred are compounds of the formula A1a1-A1g1, in which at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group at the para position of the fluorine atom.

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



Wherein R ²¹ , X ⁰ , L ²¹ and L ²² have the meanings specified in Formula A2, L ²³ , L ²⁴ , L ²⁵ and L ²⁶ are each independently H or F, and X ^{0 is} preferably F.

More preferred are compounds of formula A2a-A2l, wherein at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group at the para position of the fluorine atom.

Extremely preferred compounds of formula A2 are selected from the group consisting of:



Wherein R ²¹ and X ⁰ are as defined in Formula A2.

More preferred are compounds of the formula A2a1-A2l2, in which at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group in the para position to the fluorine atom.

Particularly preferred compounds of the formula A3 are selected from the group consisting of:

Wherein R ²¹ , X ⁰ , L ²¹ and L ²² have the meanings specified in Formula A3, and X ^{0 is} preferably F.

More preferred are compounds of formulas A3a-A3c, wherein at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group at the para position of the fluorine atom.

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

Wherein R ^{21 is} as defined in Formula A4.

More preferred is a compound of formula A4a, in which at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group at the para position of the fluorine atom.

Preferably, component A) in the LC medium comprises one or more compounds of formula B selected from the group consisting of:


Among them, g, A ³¹ , A ³² , R ³¹ , X ⁰ , L ³¹ , L ³² and L ^S have the meanings specified in Formula B, and X ^{0 is} preferably F. Especially preferred are compounds of formulae B1 and B2.

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

Wherein R ³¹ , X ⁰ , L ³¹ and L ³² have the meanings specified in Formula B1, and X ^{0 is} preferably F.

More preferred are compounds of formulas B1a-B1b, in which at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group at the para position of the fluorine atom.

Very preferred compounds of formula B1a are selected from the group consisting of the following subformulas:

Wherein R ^{31 is} as defined in Formula B1.

More preferred are compounds of formulas B1a1 to B1a6, in which at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group at the para position of the fluorine atom.

Very preferred compounds of formula B1b are selected from the group consisting of the following subformulas:

Wherein R ^{31 is} as defined in Formula B1.

More preferred are compounds of formulas B1b1 to B1b4, in which at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group in the para position to the fluorine atom.

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



Wherein R ³¹ , X ⁰ , L ³¹ and L ³² have the meanings specified in Formula B2, L ³³ , L ³⁴ , L ³⁵ and L ³⁶ are each independently H or F, and X ^{0 is} preferably F.

More preferred are compounds of formula B2a-B2l, in which at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group at the para position of the fluorine atom.

Extremely preferred compounds of formula B2 are selected from the group consisting of:

Where R ^{31 is} as defined in Formula B2.

More preferred are compounds of formula B2a1-B2a5, in which at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group at the para position of the fluorine atom.

Very preferred compounds of formula B2b are selected from the group consisting of the following subformulas:


Where R ^{31 is} as defined in Formula B2.

More preferred are compounds of the formula B2b1-B2b4, in which at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group at the para position of the fluorine atom.

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


Where R ^{31 is} as defined in Formula B2.

More preferred are compounds of formula B2c1-B2c5, wherein at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group at the para position of the fluorine atom.

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

Where R ^{31 is} as defined in Formula B2.

More preferred are compounds of formulas B2d1 and B2e1, in which at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group at the para position of the fluorine atom.

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

Where R ^{31 is} as defined in Formula B2.

More preferred are compounds of formula B2f1-B2f5, in which at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group at the para position of the fluorine atom.

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

Where R ^{31 is} as defined in Formula B2.

More preferred are compounds of the formula B2g1-B2g5, in which at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group at the para position of the fluorine atom.

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

Where R ^{31 is} as defined in Formula B2.

More preferred are compounds of the formula B2h1-B2h3, wherein at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group at the para position of the fluorine atom.

Very preferred compounds of formula B2i are selected from the group consisting of the following subformulas:

Where R ^{31 is} as defined in Formula B2.

More preferred are compounds of formulas B2i1 and B2i2, wherein at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group at the para position of the fluorine atom.

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

Where R ^{31 is} as defined in Formula B2.

More preferred are compounds of formulas B2k1 and B2k2, wherein at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group at the para position of the fluorine atom.

Very preferred compounds of formula B2l are selected from the group consisting of the following subformulas:


Where R ^{31 is} as defined in Formula B2.

More preferred are compounds of the formulae B2l1 and B2l2, in which at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group at the para position of the fluorine atom.

As an alternative to or in addition to the compounds of formula B1 and / or B2, component A) in the LC medium may also contain one or more compounds of formula B3 as defined above.

Extremely preferred compounds of formula B3 are selected from the group consisting of:

Wherein R ^{31 is} as defined in Formula B3.

More preferred are compounds of formulas B3a and B3b, in which at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group at the para position of the fluorine atom.

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

The individual groups have the following meanings:
R ⁴¹ and R ⁴² are each independently an alkyl, alkoxy, oxaalkyl, or alkoxyalkyl group having 1 to 9 C atoms or an alkenyl or alkenyloxy group having 2 to 9 C atoms The above owners are fluorinated as appropriate,
Z ⁴¹ and Z ⁴² are each independently -CH ₂ CH _2- , -COO-, trans-CH = CH-, trans-CF = CF-, -CH ₂ O-, -CF ₂ O-, -C≡ C- or single bond, preferably single bond,
h 0, 1, 2, or 3.

In the compound of formula C, R ⁴¹ and R ^{42 are} preferably selected from a linear alkyl or alkoxy group having 1, 2, 3, 4, 5, or 6 C atoms, and having 2, 3, 4, 5, A straight-chain alkenyl group of 6 or 7 C atoms.

In the compound of formula C, h is preferably 0, 1 or 2.

In the compound of formula C, Z ⁴¹ and Z ^{42 are} preferably selected from COO, trans-CH = CH, and a single bond, and are preferably selected from COO and a single bond.

Preferred compounds of formula C are selected from the group consisting of:



Where f is 0 or 1, and R ⁴¹ and R ⁴² have the meanings specified in formula C, and preferably each independently represent an alkyl group, an alkoxy group, a fluorinated alkyl group or a group having 1 to 7 C atoms. Fluorinated alkoxy, or alkenyl, alkenyl, alkoxyalkyl or fluorinated alkenyl having 2 to 7 C atoms.

Excellent are compounds of formulae C1, C4, C5 and C9.

Preferred compounds of formula C are selected from the group consisting of:

Wherein alkyl and alkyl * each independently represent a straight-chain alkyl group having 1 to 6 C atoms.

Especially preferred is a compound of formula C1a, most preferably one selected from the following subformulas:

Among them, propyl, butyl and pentyl are linear groups.

Most preferred are compounds of formula C1a1.

In another preferred embodiment of the present invention, in addition to the compounds of formula A and / or B and / or C, component A) in the LC medium also contains one or more compounds of formula D

Wherein A ⁴¹ , A ⁴² , Z ⁴¹ , Z ⁴² , R ⁴¹ , R ⁴² and h have one of the meanings specified in formula C or one of the preferred meanings specified above.

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

Among them, R ⁴¹ and R ⁴² have the meanings specified in Formula D and preferably represent an alkyl group.

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


Wherein alkyl and alkyl * each independently represent a linear alkyl group having 1 to 6 C atoms, and alkenyl represents a linear alkenyl group having 2 to 7 C atoms, 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 best compound of formula D is selected from the group consisting of:

In another preferred embodiment of the present invention, in addition to the compounds of formula A and / or B, component A) in the LC medium also contains one or more compounds of formula E containing alkenyl groups.

The individual groups have the following meanings, which are the same or different and independent of each other at each occurrence:
R ^A1 has an alkenyl group of 2 to 9 C atoms, or if at least one of rings X, Y, and Z represents cyclohexenyl, it is also one of the meanings of R ^A2 ,
R ^A2 has an alkyl group of 1 to 12 C atoms, in addition, one or two non-adjacent CH ₂ groups can make O atoms not directly connected to each other via -O-, -CH = CH-,- CO-, -OCO- or -COO- replacement,
x 1 or 2.

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

Preferred compounds of formula E are selected from the following subformulas:


Wherein alkyl and alkyl * each independently represent a linear alkyl group having 1 to 6 C atoms, and alkenyl and alkenyl * each independently represent a linear alkenyl group having 2 to 7 C atoms. alkenyl and alkenyl * preferably represent 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- .

Excellent compounds of formula E are selected from the following subformulas:

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 preferred compounds of formula E are selected from the following subformulas:

Most preferred are compounds of formula E1a2, E1a5, E6a1 and E6a2.

In another preferred embodiment of the present invention, in addition to the compounds of formula A and / or B, component A) in the LC medium also contains one or more compounds of formula F

Wherein the individual groups have the following meanings independently of each other and in each occurrence the same or different:
R ^{21 is} each independently an alkyl, alkoxy, oxaalkyl, or alkoxyalkyl group having 1 to 9 C atoms or an alkenyl or alkenyloxy group having 2 to 9 C atoms, each The owner is fluorinated as appropriate,
X ⁰ F, Cl, a halogenated alkyl or alkoxy group having 1 to 6 C atoms, or a halogenated alkenyl or alkenyloxy group having 2 to 6 C atoms,
Z ²¹ -CH ₂ CH _2- , -CF ₂ CF _2- , -COO-, trans-CH = CH-, trans-CF = CF-, -CH ₂ O-, -CF ₂ O-, -C≡C -Or a single bond, preferably -CF ₂ O-,
L ²¹ , L ²² , L ²³ , and L ²⁴ are each independently H or F,
L ^S H or CH ₃ , wherein preferably, at least one of the two groups L ^S connected to the same benzene ring is H,
g 0, 1, 2, or 3.

In compounds of formula F and its subformulas, the ring

Better representation
,
In addition
.

In a preferred embodiment, at least one of the compounds of formula F or its subformula contains at least one ring
.

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

Wherein R ²¹ , X ⁰ , L ²¹ and L ²² have the meanings specified in Formula F, L ²⁵ to L ²⁸ are each independently H or F, and X ^{0 is} preferably F.

Extremely preferred compounds of the formula F1-F3 are selected from the group consisting of:

Wherein R ^{21 is} as defined in Formula F1.

More preferred are compounds of the formulae F1-F3 and F1a-F3b, in which at least one of the benzene rings substituted with fluorine is additionally substituted with a methyl group at the para position of the fluorine atom.

The proportion of the compounds of formula A and B in the LC host mixture is preferably 2 to 60%, most preferably 3 to 45%, and most preferably 4 to 35%.

The proportion of the compounds of the formulae C and D in the LC host mixture is preferably 2 to 70%, very preferably 5 to 65%, and most preferably 10 to 60%.

The proportion of the compound of formula E in the LC host mixture is preferably 5 to 50%, and very preferably 5 to 35%.

The proportion of the compound of formula F in the LC host mixture is preferably 2 to 30%, and very preferably 5 to 20%.

Preferred embodiments of the present invention are listed below, including any combination thereof.
a) Component A or LC host mixture comprises one or more compounds of formula A and / or B having high positive dielectric anisotropy, preferably having Δε> 15.
b) Component A or LC host mixture contains one or more compounds selected from the group consisting of: A1a2 (CCQU), A1b1 (ACQU), A1d1 (PUQU), A1f1 (GUQU), A2a1 (APUQU), A2h1 ( CDUQU), A2l1 (DUUQU), A2l2 (DGUQU), A2k1 (PGUQU), B2g2 (PGU), B2i1 (CPGU), B2h3 (CCGU), B2k1 (PPGU), B2l1 (DPGU), F1a (GUQGU). The proportion of these compounds in the LC host mixture is preferably 4 to 40%, and most preferably 5 to 35%.
c) Component A or LC host mixture contains one or more compounds selected from the group consisting of formulas C1 (CCH), C4 (PCH), C5 (CCP), C7 (BCH), C9 (CBC), and D2 ( PGP), preferably C1a (CCH-nm), C4b (PCH-nOm), C5b (CCP-nOm), C7b (BCH-nOm), C9b (CBC-nmF), D2a (PGP-nm), and D2b ( PGP-n-mV). The proportion of these compounds in the LC host mixture is preferably 5 to 60%, and very preferably 8 to 50%.
d) The LC host mixture comprises one or more compounds selected from the group consisting of formulae E1 (CC-alkenyl), E3 (PP-alkenyl) and E6 (CCP-alkenyl), preferably E1a (CC- n-Vm), E3a (PP-n-kVm), and E6a (CCP-Vn-m), preferably E1a2 (CC-3-V), E1a5 (CC-3-V1), E3a1 (PP-3- V), E3a3 (PP-1-2V1), and E6a1 (CCP-V-1). The proportion of these compounds in the LC host mixture is preferably 5 to 750%, and very preferably 10 to 65%.

Preferably, the proportion of LC component A) in the LC medium is 95% to <100%, preferably 95% to 97%, and most preferably 96% to 99%.

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

The polymerizable mesogen of the polymerizable component B in the LC medium is preferably selected from Formula I
R^a -B¹ -(Z^b -B² )_m -R^b I
The individual groups in each case have the following meanings which are the same or different and independent of each other:
R^a And R^b P, P-Sp-, H, F, Cl, Br, I, -CN, -NO₂ , -NCO, -NCS, -OCN, -SCN, SF₅ Or a straight or branched chain alkyl group having 1 to 25 C atoms, in addition, one or more non-adjacent CH₂ The radicals can each independently pass through -C (R in a manner such that O and / or S atoms are not directly connected to each other.⁰ ) = C (R⁰⁰ )-, -C≡C-, -N (R⁰⁰ )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, and in addition, one or more H atoms may be replaced by F, Cl, Br, I, CN, P, or P-Sp-substitution, where B¹ And / or B² Contains saturated C atoms, then R^a And / or R^b It can also represent a group spliced to this saturated C atom,
Where the group R^a And R^b At least one of them represents or contains a group P or P-Sp-,
P polymerizable group,
Sp spacer or single bond,
B¹ And B² Aromatic, heteroaromatic, alicyclic or heterocyclic groups, preferably having 4 to 25 ring atoms, which may also contain fused rings and which are unsubstituted or mono- or polysubstituted by L,
Z^b -O-, -S-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH₂ -, -CH₂ O-, -SCH₂ -, -CH₂ S-, -CF₂ O-, -OCF₂ -, -CF₂ S-, -SCF₂ -,-(CH₂ )_n1 -, -CF₂ CH₂ -, -CH₂ CF₂ -,-(CF₂ )_n1 -, -CH = CH-, -CF = CF-, -C≡C-, -CH = CH-COO-, -OCO-CH = CH-, CR⁰ R⁰⁰ Or a single key,
R⁰ And R⁰⁰ Each independently represent H or an alkyl group having 1 to 12 C atoms,
m is 0, 1, 2, 3, or 4,
n1 means 1, 2, 3, or 4,
L means P, P-Sp-, OH, CH₂ OH, F, Cl, Br, I, -CN, -NO₂ , -NCO, -NCS, -OCN, -SCN, -C (= O) N (R^x )₂ , -C (= O) Y¹ , -C (= O) R^x , -N (R^x )₂ , Optionally substituted silyl, optionally substituted aryl having 6 to 20 C atoms, or straight or branched chain alkyl, alkoxy, alkylcarbonyl, having 1 to 25 C atoms, Alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, wherein, in addition, one or more H atoms may be replaced by F, Cl, P or P-Sp-
P and Sp have the meanings specified above,
Y¹ For halogen,
R^x Stands for P, P-Sp-, H, halogen, straight chain, branched chain or cycloalkyl group having 1 to 25 C atoms, in addition, one or more non-adjacent CH₂ The group can be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- in a way that O and / or S atoms are not directly connected to each other. And wherein, in addition, one or more H atoms may be replaced by F, Cl, P, or P-Sp-; optionally substituted aryl or aryloxy groups having 6 to 40 C atoms, or optionally Substituted heteroaryl or heteroaryloxy groups having 2 to 40 C atoms.

Particularly preferred compounds of the formula I are those in which B ¹ and B ² each independently represent 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene -2,6-diyl, phenanthrene-2,7-diyl, 9,10-dihydro-phenanthrene-2,7-diyl, anthracene-2,7-diyl, pyrene-2,7-diyl , Coumarin, flavones, in addition, one or more of these groups in the CH group may be replaced by N; cyclohexane-1,4-diyl, in addition, in addition, one or more non-adjacent CH ₂ groups can be replaced by O and / or S; 1,4-cyclohexenyl, bicyclo [1.1.1] pentane-1,3-diyl, bicyclo [2.2.2] octane-1,4 -Diyl, spiro [3.3] heptane-2,6-diyl, piperidine-1,4-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene -2,6-diyl, indan-2,5-diyl, or octahydro-4,7-methyl bridge indan-2,5-diyl, all of which may be unsubstituted or as above Single or multiple substitutions of L as defined herein.

Particularly preferred compounds of formula I are those in which B ¹ and B ² each independently represent 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl or naphthalene-2,6- The two bases.

Excellent compounds of formula I are selected from the formula:





The individual groups in each case have the following meanings which are the same or different and independent of each other:
P ¹ , P ² , P ³ vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane or epoxy,
Sp ¹ , Sp ² , Sp ³ single bond or spacer group, in addition, one or more of the groups P ¹ -Sp ^1- , P ¹ -Sp ² -and P ³ -Sp ³ -can represent R ^aa with the proviso that there is a group of ^{P 1 -Sp 1 -, P 2} -Sp 2 and P ³ -Sp ³ - in at least one of R ^aa with different
R ^aa H, F, Cl, CN or a straight or branched chain alkyl group having 1 to 25 C atoms, wherein, in addition, one or more non-adjacent CH ₂ groups may each independently of one another such that O and / Or S atoms are not directly connected to each other via-(R ⁰ ) = C (R ⁰⁰ )-, -C≡C-, -N (R ⁰ )-, -O-, -S-, -CO-,- CO-O-, -O-CO-, -O-CO-O-, and in addition, one or more H atoms may be replaced by F, Cl, CN or P ¹ -Sp ^1- ; particularly preferred Straight or branched, optionally mono- or polyfluorinated alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or Alkoxycarbonyloxy (where alkenyl and alkynyl have at least two C atoms and branched chain groups have at least three C atoms),
R ⁰ , R ⁰⁰ H or an alkyl group having 1 to 12 C atoms,
R ^y and R ^z H, F, CH ₃ or CF ₃ ,
X ¹ , X ² , X ³ -CO-O-, -O-CO- or single bond,
Z ¹ -O-, -CO-, -C (R ^y R ^z )-or -CF ₂ CF _2- ,
Z ² , Z ³ -CO-O-, -O-CO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF ₂ -or-(CH ₂ ) _n- , where n is 2, 3 or 4,
LF, Cl, CN, or optionally monofluorinated or polyfluorinated, linear or branched alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, having 1 to 12 C atoms , Alkylcarbonyloxy or alkoxycarbonyloxy;
L ', L "H, F or Cl,
r 0, 1, 2, 3, or 4,
s 0, 1, 2, or 3,
t 0, 1, or 2,
x 0 or 1.

Excellent formula M2, M10 and M13 compound, in particular containing exactly two polymerizable groups P ¹ and P ² of the two reactive compound.

More preferred are compounds selected from formulas M15 to M31, in particular compounds selected from formulas M17, M18, M19, M22, M23, M24, M25, M26, M30 and M31, especially containing exactly three polymerizable groups A tri-reactive compound of P ¹ , P ² and / or P ³ .

In compounds of formulas M1 to M31, the group
Where L has the same or different one of the meanings specified above or below on each occurrence, and is 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-, preferably F, Cl, CN, CH ₃ , C ₂ H ₅ , OCH ₃ , COCH ₃ , OCF ₃ or P-Sp-, more preferably F, Cl , CH ₃ , OCH ₃ , COCH ₃ or OCF ₃ , especially F or CH ₃ .

Preferred compounds of the formulas M1 to M30 are those in which P ¹ , P ² and P ³ represent an acrylate, a methacrylate, an oxetane or an epoxy group, and an excellent acrylate or methacrylate group. And so on.

More preferred compounds of the formulae M1 to M31 are those in which Sp ¹ , Sp ² and Sp ³ are single bonds.

More preferably, the compounds of formulas M1 to M31 are ones in which one of Sp ¹ , Sp ² and Sp ³ is a single bond and the other of Sp ¹ , Sp ² and Sp ³ is different from a single bond.

More preferred compounds of formulas M1 to M31 are those in which their groups Sp ¹ , Sp ² and Sp ³ which are different from the single bond represent-(CH ₂ ) _s1 -X "-, where s1 is an integer from 1 to 6, It is preferably 2, 3, 4 or 5, and X "is a bond to a benzene ring and is -O-, -O-CO-, -CO-O, -O-CO-O- or a single bond.

More preferred compounds of formula I are those selected from the group consisting of formulas RM-1 to RM-131 in Table D below, specifically, selected from the group consisting of: formulas RM-1, RM-4, RM-8, RM-17, RM-19, RM-35, RM-37, RM-39, RM-40, RM-41, RM-48, RM-51, RM-52, RM-54, RM- 57, RM-64, RM-74, RM-76, RM-88, RM-91, RM-102, RM-103, RM-109, RM-117, RM-120, RM-121 and RM-122.

Especially preferred are LC media containing one, two or three polymerizable compounds of formula I.

Further preferred are LC media in which the polymerizable component B) exclusively consists of a polymerizable compound of the formula I.

In another preferred embodiment, in addition to or as an alternative to the polymerizable compounds of formula I according to the preferred subformulas and subgroups as described above, component B) also contains one or more polymerizable mesogens The mesogen compounds contain one or more polymerizable groups and one or more polar anchor groups selected from, for example, hydroxyl, carboxyl, amine or thiol groups. These compounds can act as self-alignment (SA) additives and are suitable for use in SA mode displays according to the present invention. This type of suitable and preferred polymerizable mesogens SA additive selected from Formula I or a compound of M1 to M31, wherein at least one group ^{B 1, B 2, R a} , R b, R x, L, Sp, Sp 1 , Sp ² , Sp ³ or ^Raa is substituted with a hydroxyl, carboxyl, amine or thiol group, preferably with a hydroxyl group. More preferred polymerizable mesogen SA additives of this type are selected from the formulae SA-9 to SA-34 in Table E.

Preferably, the proportion of the polymerizable compound of component B) in the LC medium is 0.05% to <3%, more preferably 0.1% to 2.8%, very preferably 0.1% to 2.5%, and most preferably 0.2% to 2.2 %. In another preferred embodiment, the proportion of the polymerizable compound of component B) in the LC medium is <1.7%, more preferably 0.1 to 1.0%, very preferably 0.1 to 0.8%, and most preferably 0.1 to 0.5% .

In addition to components A and B, the LC medium preferably contains component C, which contains one or more optically active compounds preferably selected from a palmitic dopant.

The helical twisting force and amount of the dopant in the LC medium are preferably selected so that the ratio d / p of the display according to the present invention is ≥0.5, preferably 0.5 to 1.2, more preferably 0.55 to 1.0, and most preferably 0.6 to 0.8.

The ratio of the palm dopant in the LC medium is preferably 0.01 to 6%, very preferably 0.05 to 3%, and even more preferably 0.1 to 0.5%.

Suitable and preferred palmitic dopants are mentioned in Table B below. Preferred palmitic dopants are selected from R- or S-1011, R- or S-2011, R- or S-3011, R- or S-4011, or R- or S-5011, for example.

Preferably, the twist angle of the helical twist induced in the LC medium by the palm dopant (before voltage is applied) is 210 ° to 330 °, more preferably 240 ° to 300 °, and most preferably 270 °.

Preferably, the pitch of the helical twist induced by the palm dopant in the LC medium is 2 to 10 μm, and most preferably 3 to 6 μm.

Preferably, the ratio d / p of the display according to the present invention is ≥0.5, preferably 0.5 to 1.2, more preferably 0.55 to 1.0, and most preferably 0.6 to 0.8.

In another preferred embodiment, the LC medium contains one or more polymerization initiators.

Suitable polymerization conditions and suitable types and amounts of initiators are known to those skilled in the art and are described in the literature. Suitable for free-radical polymerization are, for example, commercially available light initiators Irgacure651®, Irgacure184®, Irgacure907®, Irgacure369® or Darocure1173® (Ciba AG).

If a polymerization initiator is added to the LC medium, the proportion is preferably 0.001 to 1% by weight, and particularly preferably 0.001 to 0.5% by weight.

In another preferred embodiment, the LC medium does not contain a polymerization initiator.

In another preferred embodiment, the LC medium contains one or more stabilizers. The use of stabilizers can prevent unwanted spontaneous polymerization of RM, such as during storage or transportation.

Suitable types and amounts of stabilizers are known to those skilled in the art and are described in the literature.

LC media according to the present invention may for example comprise one or more UV stabilizers, such as Tinuvin ^® series of Ciba Chemicals, Tinuvin ^® 770, or IRGANOX series such as Irganox® 1076 (all who obtains from BASF). Other suitable and preferred stabilizers are those selected from Table C below.

If a stabilizer is used, the ratio is preferably 10 to 500,000 ppm, and particularly preferably 50 to 50,000 ppm, based on the total amount of RM or polymerizable component (component A).

The LC medium according to the present invention may also contain other additives, such as selected from the list including (but not limited to) the following: antioxidants, free radical scavengers, defoamers, wetting agents, lubricants, dispersants, hydrophobic agents, adhesion Agents, flow improvers, deaerators, diluents, reactive diluents, auxiliaries, colorants, dyes, pigments and nano particles.

In addition, it is possible to add, for example, 0 to 15% by weight of a multicolor dye, a conductive salt (preferably 4-hexyloxybenzoate ethyl dimethyl lauryl ammonium, Complex salt of tetrabutylammonium phenylborate or crown ether) (see, eg, Haller et al., Mol. Cryst. Liq. Cryst. 24 , 249-258 (1973)), or to modify dielectric anisotropy, viscosity And / or nematic phase aligned substance. Substances 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.

In a preferred embodiment, the LC medium comprises, preferably consists of:
A) a liquid crystal component A comprising one or more compounds selected from the formulae A and B or sub-formulas as defined above, one or more compounds selected from the formulas C and D or sub-formulas as defined above , And optionally one or more compounds of formula E or a subformula thereof as defined above,
B) a polymerizable component B, which comprises one or more polymerizable liquid crystal protolyl compounds of the formula I as defined above, preferably selected from the formulas M1-M31, very preferably selected from Table D,
C) one or more palmitious additives, preferably selected from palmitic dopants, and most preferably selected from Table B,
D) one or more other additives as appropriate, preferably selected from polymerization initiators, stabilizers, which are excellently selected from Table C; and self-aligning additives, which are excellently selected from Table E,
The concentration of the polymerizable mesogen in the LC medium is 0.05 to <3%, and the concentration of the palm additive is selected such that the twist angle induced in the LC medium is> 210 °, preferably 210 to 330. °, more preferably 240 to 300 °, and very preferably 270 °.

In another preferred embodiment, the LC medium comprises, preferably consists of:
A) a liquid crystal component A comprising one or more compounds selected from the formulae A and B or sub-formulas as defined above, one or more compounds selected from the formulas C and D or sub-formulas as defined above , And optionally one or more compounds of formula E or a subformula thereof as defined above,
B) a polymerizable component B, which comprises one or more polymerizable liquid crystal protolyl compounds of the formula I as defined above, preferably selected from the formulas M1-M31, very preferably selected from Table D,
C) one or more palmitious additives, preferably selected from palmitic dopants, and most preferably selected from Table B,
D) one or more other additives as appropriate, preferably selected from polymerization initiators, stabilizers, which are excellently selected from Table C; and self-aligning additives, which are excellently selected from Table E,
The concentration of the polymerizable mesogen in the LC medium is 0.05 to <3%, and the concentration of the palm additive is selected so that the helix pitch induced in the LC medium is 2 μm to 10 μm, which is very preferably 3 μm to 6 μm.

In another preferred embodiment, the LC medium comprises one or more compounds selected from the following group or any combination thereof:
1) One or more compounds selected from the group consisting of formulas A2a1, A2k1, and B2k1. These compounds can increase dielectric anisotropy, optical anisotropy, and operating temperature.
2) One or more compounds selected from the group consisting of formula A1d1. These compounds not only increase the dielectric anisotropy and optical anisotropy, but also lower the operating temperature.
3) One or more compounds selected from the group consisting of formula A1a2. These compounds can increase the dielectric anisotropy, but lower the operating temperature.
4) One or more compounds selected from the group consisting of formulas C1a, C1b, E1a. These compounds not only reduce viscosity and adjust optical anisotropy, but also lower operating temperatures.
5) One or more compounds selected from the group consisting of formula C4b. These compounds not only reduce viscosity, but also lower operating temperatures.
6) One or more compounds selected from the group consisting of formulae C7a, D2, E6. These compounds can reduce dielectric anisotropy and operating temperature.
7) One or more palmar dopants, preferably selected from Table B, and very preferably selected from the formulas R / S-1011, R / S-2011, R / S-3011, R / S-4011, and R / S-5011. These compounds induce helical twisted structures and twist angles in layers with LC molecules.
8) One or more reactive mesogens, preferably selected from Formula I, preferably selected from Formulas M1 to M31, more preferably selected from Formulas RM-1 to RM-131 of Table D, and most preferably selected from the group consisting of : RM-1, RM-4, RM-8, RM-17, RM-19, RM-35, RM-37, RM-39, RM-40, RM-41, RM-48, RM-51, RM-52, RM-54, RM-57, RM-64, RM-74, RM-76, RM-88, RM-91, RM-102, RM-103, RM-109, RM-117, RM- 120, RM-121 and RM-122. These compounds provide polymer stability, thereby reducing the twist angle.
9) One or more stabilizers, preferably selected from Table C, very preferably selected from the formula

,
Wherein n is 1, 2, 3, 4, 5, 6, or 7, preferably 3.
10) One or more photoinitiators. These compounds initiate the polymerization of the polymerizable compounds of component B and group 8 described above.
11) One or more self-aligning additives. These compounds can omit the alignment layer.
12) One or more additives selected from the group consisting of antioxidants, UV absorbers, coloring substances, and defoamers.

The individual components of the preferred embodiment of the LC medium according to the present invention are known; or its preparation method can be easily derived from the prior art by those skilled in the relevant art because it is based on standard methods described in the literature.

It is self-evident to 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 have been replaced by corresponding isotopes (such as deuterium, etc.).

The LC medium that can be used according to the present invention is prepared in a manner known per se, for example by mixing one or more LC compounds selected from Formulas A to F or one or more compounds of the preferred embodiments described above with each other and / or with other LCs Compounds and / or additives (such as polymerizable compounds or RM) are mixed. In general, it is advantageous to dissolve the required amount of the component in a smaller amount in the component constituting the main component, and to dissolve it at a high temperature. It is also possible to mix the solutions of the components in an organic solvent (for example in acetone, chloroform or methanol) and remove the solvent again after thorough mixing, for example by distillation.

It goes without saying that, through proper selection of the components of the LC mixture according to the invention, it is also possible to achieve higher clearing points (for example above 100 ° C) at higher threshold voltages while maintaining other advantageous properties Or reach a lower clear point at a lower threshold voltage. With a correspondingly only slight increase in viscosity, it is also possible to obtain mixtures with a higher Δε and therefore a low threshold. The MLC display according to the present invention is preferably operated at the first Gooch and Tarry transmission minimum [CH Gooch and HA Tarry, Electron. Lett. 10, 2-4, 1974; CH Gooch and HA Tarry , Appl. Phys., Volume 8, 1575-1584, 1975], in addition to particularly advantageous electro-optical characteristics (such as high steepness of characteristic lines and low angular dependence of contrast (German Patent 30 22 818)) At the second minimum, at the same threshold voltage as similar displays, a lower dielectric anisotropy is sufficient. This enables the use of the mixture of the invention at a first minimum value to achieve a specific resistance value that is significantly higher than in the case of a mixture containing a cyano compound. With proper selection of the individual components and their weight ratios, those skilled in the art can use a simple and conventional method to set the birefringence necessary for a pre-specified layer thickness of an MLC display.

The LC medium and the LC main mixture of the present invention preferably have a nematic phase range of ≥80 K, excellent ≥100 K and a rotational viscosity of ≤250 mPa · s, preferably ≤200 mPa · s at 20 ° C.

The birefringence Δn of the LC medium and the LC host mixture according to the present invention at 20 ° C is preferably 0.07 to 0.15, and particularly preferably 0.08 to 0.15.

The LC medium and the LC host mixture have positive dielectric anisotropy Δε. Preferably, the LC medium and the LC host mixture have a positive dielectric anisotropy Δε of +2 to +30, particularly preferably +3 to +20 at 20 ° C and 1 kHz.

The structure of the PS-UF TN-LC display according to the present invention corresponds to the common geometry of the TN display described in the prior art as cited at the beginning.

The construction of a PS-UF TN-LC display according to the present invention using a polarizer, an electrode substrate, and a surface-treated electrode corresponds to a common design of this type of display. The term common design is roughly drawn here, and also covers all derivatives and modifications of MLC displays, in particular, including matrix display elements based on poly Si TFT or MIM.

The preferred PS-UF TN-LC display of the present invention includes:
A first substrate including a pixel electrode defining a pixel region, the pixel electrode being connected to a switching element disposed in each pixel region, and a first alignment layer disposed on the pixel electrode as appropriate,
-A second substrate comprising a common electrode layer, the common electrode layer may be disposed on an entire portion of the second substrate facing the first substrate; and a second alignment layer as appropriate,
-A nematic LC dielectric layer with positive dielectric anisotropy, which is distributed between the first substrate and the second substrate and contains a liquid crystal component A, the liquid crystal component A comprising one or more liquid crystal molecules or liquid crystal molecules, It is preferably composed of one or more mesogens or liquid crystal molecules, and further comprises component C, which contains one or more palliative additives, and optionally component D containing one or more other additives,
A polymer layer deposited on each of the first and second electrodes or, if present, on each of the first and second alignment layers, wherein the polymer layers are formed by a Or more polymerizable mesogen compounds are formed in the LC medium at a concentration of 0.1 to <3%, and after the LC medium has been distributed between the two substrates, polymerization occurs in situ,
-c) a first polarizer that exists on one side of the LC layer on the back of the first substrate and a second polarizer that exists on one side of the LC layer on the back of the second substrate, The isopolarizing lens is preferably oriented such that its transmission plane is at a right angle with respect to the plane polarized light (orthogonal Nichols).

FIG. 1 illustrates the structure of a preferred PS-UF TN-LC display according to the present invention in an off state or an unaddressed state (ie, no voltage is applied to the electrodes). The display (100) includes a first substrate (110) and a second substrate (150), each of which is equipped with an ITO electrode (115, 155) and an alignment layer (120, 160) as appropriate. It is preferably unidirectional friction and Arranged such that the rubbing direction is at a right angle; the LC medium (140) located between the two substrates, where the LC molecules are aligned in parallel or obliquely with respect to the substrate and twisted spirally along an axis perpendicular to the substrate; and the polymer layer ( 130, 170), the polymer layers are formed on the alignment layers (120, 160) by polymerizing the polymerizable mesogen compounds contained in the LC medium. The display further includes two polarizers (180, 190) sandwiching the display, arranged so that their transmission planes are 90 ° relative to each other with respect to the plane-polarized light (orthogonal Nicollard).

The invention also relates to a method for manufacturing a liquid crystal display (LCD) having a polymer stabilized twisted nematic (PS-TN) mode. The method includes the following steps:
a) A first substrate and a second substrate are provided, the first substrate is provided with a first electrode layer and optionally a first alignment layer, and the second substrate is provided with a second electrode layer and optionally a second alignment layer ,
Wherein the first and / or second substrate is preferably equipped with a fixing member, the fixing members are preferably a sealing material and / or a spacer, so that the first substrate and the second substrate are at a constant distance relative to each other and their Fixed when the planes are parallel to each other,
b) assigning a nematic LC dielectric layer with positive dielectric anisotropy between the first and second substrates, so that if these layers exist, the LC dielectric is in contact with the first and second alignment layers,
The LC medium includes, and preferably consists of:
A) a liquid crystal component A (hereinafter also referred to as "LC host mixture"), which contains liquid crystal molecules or liquid crystal molecules, preferably composed of liquid crystal molecules or liquid crystal molecules,
B) a polymerizable component B comprising one or more polymerizable mesogen compounds (hereinafter also referred to as "reactive mesogens"), preferably consisting of these compounds,
C) one or more palmar additives, preferably selected from palmar dopants,
D) optionally one or more other additives, preferably selected from polymerization initiators, stabilizers and self-aligning additives,
The ratio of the polymerizable mesogen in the LC medium is <3%, preferably 0.05 to <3%, and the longitudinal axis of the LC molecules is oriented parallel or obliquely relative to the substrate plane, and the palmity additive induces the LC medium. The LC molecules are twisted helically at a specified distance p along an axis perpendicular to the substrate, and the LC dielectric layer has a thickness d, and the ratio d / p is ≥0.5, preferably> 0.5, and preferably 0.6 to 0.8, and The twist angle of the helical twist of the LC molecule induced by the palm additive is> 210 °, preferably in the range of 210 to 330 °, more preferably 240 to 300 °, and extremely good 270 °,
c) Apply voltage to the first electrode and the second electrode, so that the twist angle of the spiral twist of the LC molecules is reduced to <150 °, preferably to a range of 60 to 120 °, and preferably 80 to 100 °, Excellent at 90 °,
d) polymerizing the polymerizable mesogen of the polymerizable component B of the LC medium between the first substrate and the second substrate after the voltage is applied, preferably by exposure to UV radiation Aggregate, thereby stabilizing the torsional nematic configuration of the LC medium with the reduced torsion angle in step c), and
e) Subjecting the LC medium to a second polymerization step as appropriate, preferably by exposing to UV radiation without applying a voltage to the first electrode and the second electrode, thereby polymerizing any polymerizable compound that has not reacted in step d) ,
f) Optionally, a first polarizer is disposed on one side of the LC layer on the back of the first substrate and a second polarizer is disposed on one side of the LC layer on the back of the second substrate, where the polarized light The mirror is preferably oriented such that its transmission plane is at a right angle with respect to the plane polarized light (orthogonal Nicolson).

The substrate used in the display according to the present invention and in step a) of the manufacturing method thereof is preferably a glass substrate. For a flexible LC display, a plastic substrate is preferably used. These plastic substrates preferably have a low birefringence. Examples of suitable and preferred plastic substrates are polycarbonate (PC), polyether fluorene (PES), polycyclic olefins (PCO), polyarylate (PAR), polyether ether ketone (PEEK), or colorless polyfluorene Amine (CPI) substrate.

At least one substrate should be transparent to the optical radiation used to polymerize the polymerizable compounds used in the method of the present invention.

In the case where the substrate is equipped with an alignment layer prepared by photopolymerization and / or photoalignment, at least one substrate should be transparent to the optical radiation used for photopolymerization or photoalignment of the alignment layer material or its precursor.

The electrode layer can be designed by those skilled in the art according to the type of individual display. In the LC display according to the present invention, the first substrate and the second substrate are each provided with an electrode layer.

More preferably, one of the first electrode layer and the second electrode layer is a pixel electrode defining a pixel region, the pixel electrode is connected to a switching element disposed in each pixel region and includes a micro slit pattern as appropriate, and the first The other of the one electrode layer and the second electrode layer is a common electrode layer, which can be disposed on the entire portion of the substrate facing the other substrate.

The first and / or second substrate may carry other layers or components, including (but not limited to) color filters, TFT arrays, black matrices, polyimide coatings, or other components typically found on display substrates.

Preferably, at least one of the first substrate and the second substrate, more preferably each substrate, is provided with an alignment layer, which is usually applied to the electrode so that it contacts the LC medium.

The first and / or second alignment layer controls the alignment direction of the LC molecules in the LC layer. In the display according to the present invention, the alignment layer is selected so that it imparts an orientation direction in which the LC molecules are parallel or slightly inclined with respect to the substrate.

A suitable and preferred alignment layer includes, for example, polyimide or consists of polyimide, which can also be rubbed or prepared by a photo-alignment method. A solution-processable alignment layer material is preferred. These materials are preferably treated as a solution in a solvent, preferably an organic solvent such as, for example, N-methylpyrrolidone, 2-butoxyethanol or γ-butyrolactone.

In a preferred embodiment, the alignment layer is formed by depositing a solution of an alignment layer material (such as, for example, polyimide or a precursor thereof, such as, for example, a polyimide precursor) on a substrate, and optionally by Exposure to heat and / or actinic radiation (such as UV radiation) causes the alignment layer material or its precursor to cure.

The alignment layer material or its precursor may be deposited on the substrate by a coating or printing method.

In the case where the solvent is used to deposit the alignment layer material, the solvent is preferably dried or evaporated after deposition. Solvent evaporation can be supported, for example, by applying heat and / or reduced pressure.

The preferred method for curing the alignment layer is thermal curing and light curing, and most preferably, light curing. Light curing is performed, for example, by exposure to UV radiation. Those skilled in the art can select suitable curing conditions based on their common sense and as described in the literature, depending on the precursor materials used. In the case of commercially available materials, suitable processing and / or curing conditions are usually provided along with the sale or sampling of the materials.

In the display according to the present invention, the alignment layer is preferably selected such that it imparts planar (or parallel) alignment to the LC molecules, that is, where the longitudinal axis of the LC molecules is parallel to the surface of the nearest substrate, and where the longitudinal axis of the LC molecules is The surface of the substrate may also be slightly inclined.

Preferably, the inclination angle of the longitudinal axis of the LC molecules located near the surface of the substrate with respect to the substrate is> 0 ° to 20 °, preferably 0.1 ° to 20 °, and most preferably 0.2 ° to 3.5 °.

In order to give the LC molecules a preferred two-dimensional alignment direction in the plane of the substrate, the alignment layer includes, for example, an alignment layer material, such as polyimide, which is unidirectionally rubbed or prepared by a photo-alignment method.

Preferably, the alignment direction or the average orientation direction (also referred to as "director") of the longitudinal axis of the LC molecules is at a right angle near the first and second substrates, that is, at an angle of 90 ° with respect to each other. More preferably, the alignment directions or LC directors near the first and second substrates are at an angle of 45 ° with respect to the edge of the substrate.

This can be achieved, for example, by using first and second alignment layers (e.g., containing polyimide), which are all unidirectionally rubbed and arranged so that their rubbing directions are at right angles, and where the rubbing directions of the alignment layers Corresponds to the alignment direction of LC molecules. Alternatively, this can be achieved by preparing an alignment layer using linearly polarized light for optical alignment, wherein the polarization direction of the polarized light corresponds to the alignment direction of the LC molecules.

The display according to the present invention preferably includes first and second alignment layers, preferably polyimide, both of which are unidirectionally rubbed and wherein the rubbing directions are at right angles to each other.

The display according to the present invention may include other elements, such as a color filter, a black matrix, a passivation layer, an optical retardation layer, a transistor element for addressing individual pixels, etc. The above owners are familiar to those skilled in the art and can use Used without the skills of the present invention.

In step b), a nematic LC having positive dielectric anisotropy and containing components A, B, C and optionally D as described above is allocated between the first and second substrates. A dielectric layer such that if such an alignment layer is present, the LC medium is brought into contact with the first and second alignment layers.

The LC medium can be dispensed or filled onto the substrate or into the display separately using methods commonly used by display manufacturers.

The LC medium is preferably deposited on the substrate by using one of the following deposition methods: drop-on-fill (ODF), inkjet printing, spin coating, slit coating, flexographic printing, or the like.

The preferred method is inkjet printing.

Another preferred method is the ODF method, which preferably includes the following steps
b1) distributing the liquid droplet or liquid droplet array of the LC medium on the first substrate, and
b2) The second substrate is provided on the first substrate to which the LC medium droplets are distributed, preferably under a vacuum condition, so that the LC medium droplets are diffused and a continuous layer is formed between the two substrates.

The applied LC medium forms a uniform film having the thickness of the target final cell gap of the display.

Preferably, the display according to the present invention includes a fixing member that fixes the first substrate and the second substrate at a constant distance relative to each other and whose planes are parallel to each other. Preferably, the fixing member includes a sealing material and a spacer material in order to maintain a constant cell gap and an LC layer thickness.

Preferably, the first substrate and the second substrate are fixed or glued together by a fixing member (such as a sealing material) provided on the substrate (preferably in a region close to the edge of the substrate).

Preferably, before the LC medium is distributed between the first substrate and the second substrate, a sealing material is deposited on the first substrate or between the first substrate and the second substrate.

The sealing material is disposed on the first substrate or between the first substrate and the second substrate, and is preferably located in a region between the LC medium and an edge of each substrate. The sealing material is, for example, a crosslinked polymer formed from a curable polymer precursor. The sealing material is then cured, preferably after the first and second substrates are assembled to form the LC unit, but before the polymerizable compound contained in the LC medium is photopolymerized. Preferably, the sealing material is cured by exposure to heat and / or light radiation.

For example, the spacer material is composed of transparent glass or plastic beads. In a preferred embodiment, the spacer is distributed between the substrates together with the LC medium.

In another preferred embodiment, in order to maintain a constant cell gap and the thickness of the LC layer, the display contains a spacer material, such as a photo spacer, outside the LC layer (such as above a black matrix), and the LC layer does not contain a spacer material.

Suitable sealants and spacers are known to those skilled in the art and are commercially available.

In step c), a voltage is applied to the first electrode and the second electrode, so that the twist angle of the spiral twist of the LC molecules in the LC layer ranges from 210 to 330 ° (preferably 240 to 300 °, and excellent 270). °, as specified by the thickness of the LC layer and the natural helical twist induced by the palm dopant) is reduced to a range of 60 to 120 °, preferably 80 to 100 °, and extremely reduced to 90 °.

Suitable methods, conditions, parameters, and driving schemes for applying a voltage to achieve the desired twist angle and then polymer stabilization are well known to those skilled in the art or described in the literature, such as K. Takatoh et al., Liq. Cryst. 2012 , 39 (6) , 715-720, and can be used without the skills of the present invention.

The selection of the voltage and driving scheme applicable to the applied voltage also depends on the physical characteristics of the LC medium and the configuration between the LC medium and the alignment layer.

In a preferred embodiment, the applied voltage and driving scheme are selected to stabilize the TN orientation with a reduced twist angle as specified above for a specified period of time, such as several (> 1) seconds, several (> 1) ) Minutes or several (> 1) hours. This allows the polymerization step d) to be carried out after step c), ie without any time overlap.

A suitable and preferred driving scheme for applying a voltage in step c) is exemplarily depicted in Figs. 2a , 2b and 2c .

For example, a suitable and preferred driving scheme for applying a voltage in step c) includes (but is not limited to):
Apply a square wave of +20 V to -20 V and a frequency of 50 to 100 Hz,
Or apply a square wave, where the pulse height is 0 V to +20 V, the pulse width is 50 to 150 ms, preferably 100 ms, and the cycle length of one pulse is 2 to 8 s, preferably 5 s (see figure 2a ),
Or apply a square wave with a pulse height of +20 V to -20 V, where each pulse contains a positive subpulse and a negative subpulse, where the pulse width is 50 to 150 ms, preferably 100 ms, and the cycle length of a pulse is 5 to 15 s, preferably 10 s, and the sub-cycle length of a sub-pulse is 2 to 8 s, preferably 5 s (see Figure 2b )
Or apply a square wave, where the pulse height is 0 V to +30 V, the pulse width of the first pulse is 1 to 10 s, preferably 5 s, and the pulse width of the second and other pulses is 50 to 150 ms, It is preferably 100 ms, with a pause between pulses of 10 to 40 s, preferably 30 s (see Figure 2c ).

In step d), the polymerizable compound of the polymerizable component B contained in the LC medium is polymerized or crosslinked by in situ polymerization of the LC medium between the LC display substrates (if the compound contains two Or more polymerizable groups), optionally applying a voltage to the electrodes simultaneously for at least a portion of the polymerization process time. In step e) as appropriate, the polymerizable compound that has not fully reacted in step d) is polymerized or crosslinked by in situ polymerization without applying a voltage.

In steps d) and e), the polymerizable compound of the polymerizable component B is preferably polymerized by photopolymerization, and most preferably by UV photopolymerization.

After the polymerizable compound is polymerized, a polymer or a crosslinked polymer that reduces the twist angle of LC molecules in the LC medium is formed. Without wishing to be bound by a particular theory, most of the polymers obtained from polymerizable compounds will phase separate from or precipitate from the LC medium and form a polymer layer on a substrate or electrode or an alignment layer disposed thereon. Microscopy data (such as SEM and AFM) have confirmed that the polymer mainly accumulates at the LC layer / substrate interface.

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

The polymerization can be carried out in one step (step d) or in two or more steps (steps d and e or a repetition thereof), as described above and below. Step d) is also referred to as "UV1" step hereinafter and step e) is also referred to as "UV2" step hereinafter.

In a preferred embodiment of the present invention, the method for manufacturing a display includes one or more of the following features:
-The polymerizable LC medium is exposed to UV light in a two-step process, including a first UV exposure step (step d or UV1) performed at the same time or after (preferably after) applying a voltage to the electrode, and further includes a second UV exposure Step (step e or UV2) to complete the polymerization without applying a voltage to the electrode,
-The polymerizable LC medium is preferably exposed in the UV2 step and optionally in the UV1 step by UV light generated by the UV lamp, and has a wavelength range of 300-380 nm, preferably 0.5 mW / cm ² to 30 mW / cm ² , more preferably 1 to 20 mW / cm ² ,
-Expose the polymerizable LC medium to UV light having a wavelength of 340 nm or more and preferably 400 nm or less.

The method of this preferred embodiment can be performed, for example, by using a desired UV lamp or by using a band-pass filter and / or a cut-off filter, which filters are substantially transmissive to UV light having a respective desired wavelength And substantially block light having respective undesired wavelengths. For example, when it is necessary to irradiate with UV light having a wavelength λ of 300-400 nm, UV exposure can be performed using a broadband pass filter with a transmission wavelength substantially 300 nm <λ <400 nm. When it is necessary to irradiate with UV light having a wavelength λ exceeding 365 nm, UV exposure can be performed using a cut-off filter having a transmission wavelength λ> 365 nm substantially.

"Substantially transmissive" means that the filter transmits a substantial portion, preferably at least 50% of the intensity, of incident light having a desired wavelength. "Substantially blocking" means that the filter does not transmit a substantial portion, preferably at least 50% intensity, of incident light at an undesired wavelength. "Expected (undesired) wavelength" means, for example, a wavelength within (outside) a specified range of λ in the case of a band-pass filter, and a designation higher (below) λ in the case of a cut-off filter Value of the wavelength.

The method of this preferred embodiment enables the display to be manufactured by using longer UV wavelengths, thereby reducing or even avoiding the dangerous and harmful effects of shorter UV light components.

The polymer obtained by polymerizing the polymerizable compound of component B of the LC medium preferably forms a layer on one or both of the substrates or on an alignment layer or an electrode structure deposited thereon.

Preferably, the polymerizable compound of the polymerizable component B is polymerized at least during a part of the polymerization process, preferably while the voltage is applied during the step UV1 as described above, so as to stabilize the reduction and torsion. However, after applying the voltage in step c), it is also possible to achieve the desired reduced torsional orientation by carrying out the polymerization and preferably the UV1 process step.

Therefore, in a preferred embodiment of the present invention, step d) (UV1) of polymerizing the polymerizable compound of the polymerizable component B is performed simultaneously with step c) of applying a voltage, or step d) is performed so that it is the same as step c) at least partially overlap.

In another preferred embodiment of the present invention, step d) (UV1) of polymerizing the polymerizable compound of polymerizable component B is performed after step c) of applying a voltage.

In a preferred embodiment, the display according to the present invention does not contain a polyimide alignment layer. In another preferred embodiment, the display according to the present invention includes a polyimide alignment layer on one or both of the substrates.

In another preferred embodiment, the LC medium according to the present invention contains a self-aligning (SA) additive, preferably at a concentration of 0.1 to 2.5%. The LC medium according to this preferred embodiment is particularly suitable for polymer-stabilized SA (PS-SA) displays.

The preferred SA additive for this preferred embodiment is selected from compounds containing a mesogen and a linear or branched alkyl side chain. The linear or branched alkyl side chain is selected from one or more selected from the group consisting of hydroxyl and carboxyl. , Amine or thiol-based polar anchoring groups.

More preferred SA additives contain one or more polymerizable groups optionally connected to the mesogen via a spacer group. These polymerizable SA additives can be polymerized in an LC medium under conditions similar to those used for the polymerizable compound of the polymerizable component B.

In another preferred embodiment, the LC medium or polymer stabilized SA-VA or SA-FFS display according to the present invention contains one or more self-aligning additives selected from Table E below.

Above and below, any SA additives (such as those of the formulae SA-9 to SA-34 in Table E) contained in LC media containing mesogen and one or more polymerizable groups should be understood Part of polymerizable component B. The preferred composition and concentration ranges specified above and below for the polymerizable component B and its ingredients are therefore understood as including RMs that are not SA additives and RMs that are SA additives and contain one or more polar anchoring groups The anchoring groups are selected from, for example, hydroxyl, carboxyl, amine or thiol groups.

The following examples are intended to explain the invention without limiting it. Above and below, percentage data represent weight percent; all temperatures are expressed in degrees Celsius.

table A
In Table A, m and n are independently integers 1 to 12, preferably 1, 2, 3, 4, 5, or 6, and k is 0, 1, 2, 3, 4, 5, or 6, and ( O) C_m H_{2m + 1} Means C_m H_{2m + 1} Or OC_m H_{2m + 1} .

Especially preferred are liquid crystal mixtures containing at least one, two, three, four or more compounds selected from Table A.

Table B indicates possible dopants which are usually added to the mixture according to the invention. The mixture preferably contains 0 to 10% by weight, in particular 0.001 to 5% by weight and particularly preferably 0.001 to 3% by weight of dopants.
Table B

table C
The stabilizers mentioned below may be added to the mixture according to the invention in an amount of, for example, 0 to 10% by weight.

table D
Table D shows illustrative reactive mesogen compounds that can be used in LC media according to the present invention.

In a preferred embodiment, the mixture according to the invention comprises one or more polymerizable compounds, preferably selected from polymerizable compounds of the formula RM-1 to RM-140. Among them, compounds RM-1, RM-4, RM-8, RM-17, RM-19, RM-35, RM-37, RM-39, RM-40, RM-41, RM-48, RM-51 , RM-52, RM-54, RM-57, RM-64, RM-74, RM-76, RM-88, RM-91 RM-102, RM-103, RM-109, RM-117, RM- 120, RM-121 and RM-122 are particularly preferred.

table E
Table E shows a self-aligning additive for vertical alignment, which can be used in the LC media of SA-VA and SA-FFS displays according to the invention together with the polymerizable compound of Formula I:

In a preferred embodiment, the LC media, SA-VA and SA-FFS displays according to the present invention comprise one or more SA additives selected from the formulas SA-1 to SA-34.

Examples
The following examples explain the invention without limiting it. However, it demonstrates to those skilled in the art the concept of a better mixture and the better used compounds and their respective concentrations and their combinations with each other. In addition, examples illustrate the available properties and combinations of properties.

In addition, the following abbreviations and symbols are used:
t- _off , t _d , τ- _off Off or decay time at 20 ° C [ms]
t _ON, t _r, τ _{is turned} on or at increased temperature is 20 ℃ time [ms]
d LC thickness of cell gap or switchable LC layer [μm]
V ₀ , V _th Threshold voltage at 20 ° C, capacitance [V]
V _op operating voltage [V]
n _e Abnormal refractive index at 20 ° C and 589 nm,
n _o ordinary refractive index at 20 ° C and 589 nm,
Δn Optical anisotropy at 20 ° C and 589 nm,
ε _⊥ the dielectric permittivity perpendicular to the director at 20 ° C and 1 kHz,
ε || The dielectric permittivity parallel to the director at 20 ° C and 1 kHz,
Δε dielectric anisotropy at 20 ° C and 1 kHz,
cl.p., T (N, I) Clear point [℃],
γ ₁ Rotational viscosity [mPa · s] at 20 ℃,
K ₁ elastic constant, "open" deformation at 20 ° C [pN];
K ₂ elastic constant, "torsional" deformation at 20 ° C [pN],
K ₃ elastic constant, "bending" deformation [pN] at 20 ° C.

Unless explicitly stated otherwise, all parameters and values specified above and below refer to a temperature of 20 ° C.

Unless stated otherwise, all concentrations and proportions in this application are quoted as weight percentages, and refer to the corresponding whole mixtures containing all solid or liquid crystal components without solvents.

Unless stated otherwise, in this application such as the melting point T (C, N), the smectic phase (S) to the nematic phase (N) transfer T (S, N) and the clear point T (N, I) All temperature values indicated are quoted in degrees Celsius (° C). M.p. indicates melting point, cl.p. = clear point. In addition, C = crystalline state, N = nematic phase, S = smectic phase and I = isotropic phase. The information between these symbols indicates the transition temperature.

Unless otherwise specifically indicated in each case, all physical properties have been measured in accordance with "Merck Liquid Crystals, Physical Properties of Liquid Crystals", Status November 1997, Merck KGaA, Germany, and are applicable to temperatures of 20 ° C, And Δn was measured at 589 nm and Δε was measured at 1 kHz.

In the present invention, the term “threshold voltage (V _th , V ₀ )” refers to a capacitance threshold value (V ₀ ), and is also referred to as a Freedericks threshold (Freedericks threshold), unless explicitly indicated otherwise. In an example, the optical threshold may also be quoted as a 10% relative contrast ratio (V ₁₀ ).

The term “operating voltage (V _op )” in the present invention refers to a voltage specified in accordance with 2 × V ₁₀ and then selects a larger multiple below 0.5 V. For example, if V ₁₀ = 4.8 V, then V _op = 10 V; if V ₁₀ = 5.2 V, then V _op = 10.5 V; if V ₁₀ = 5.6 V, then V _op = 11.5 V.

Unless otherwise stated, the polymerization method for polymerizable compounds in polymer-stabilized displays as described above and below is performed at a temperature at which the LC medium exhibits a liquid crystal phase (preferably a nematic phase), and preferably Performed at room temperature (also abbreviated as "RT").

Unless otherwise stated, methods of preparing test cells and measuring their electro-optical and other characteristics are performed by methods as described below or similar thereto.

Examples 1
The nematic LC host mixture N1 is formulated as follows:

Mixture A1 was prepared by adding 2.75% p-dopant dopant S-4011 to LC host mixture N1. The distance between the mixtures induced by the palm dopant was 5 microns.

Mixture B1 was prepared by adding 0.39% palmitic dopant S-4011 to the LC host mixture N1. The distance between the mixtures induced by the palm dopant was 35 microns.

The mixture PS-A1 was prepared by adding 1.5% RM-51, 0.5% RM-1, and 1% Irgacure® 651 (total RM concentration) to the mixture A1. The distance between the mixtures induced by the palm dopant was 5 microns.

TN Test cell manufacturing
A TN test unit was prepared, comprising two polished SL glass substrates (Corning, thickness 1.1 mm), which was equipped with an ITO electrode layer (200 A thickness, 10 Ohm / sq, 1 cm × 1 cm); the directions of friction were 0 °, respectively And 90 ° rubbed polyimide alignment layer (JSR AL3046); spacers to achieve a cell gap of 3.14 microns; and a sealant (XN-1500, available from Mitsubishi Chemicals).

Each of the mixtures N1, B1, and PS-A1 was filled into a test unit.

PS-TN Test cell manufacturing
The test unit using the mixture PS-A1 was subjected to a two-step UV curing method, in which a voltage was applied to the electrode in the first step and no voltage was applied in the second UV step.

UV step 1 (UV1):
Fe / I lamp with 365 nm filter and UV intensity of 4.0 mW / cm² ; With UV power detector Ushio UIT-250, UVD-S365; electric field (seeFigure 2a ): Pulse 5 s / cycle, pulse height 18 V, pulse width 100 ms. Irradiation time is 300 s.

UV step 2 (UV2):
Toshiba C-type fluorescent lamp, green UV, no 365 nm filter, UV intensity 0.5 mW / cm ² , with UV power detector Ushio UIT-250, UVD-S365, irradiation time 60 minutes.

Twist angle
Measurement of twist angle with AxoStep-Mueller matrix imaging polarimeter (brand: Axometrics)

In the test unit using the palmar doped mixture B1, the twist angle was measured to be -90.5 °, which corresponds to the TN configuration, as expected from a low d / p value of 0.09.

In a test unit using a palm-doped polymer-stabilized mixture PS-A1, the twist angle was measured as -90.8 °, which also corresponds to the TN configuration, but significantly lower than the high d / p according to 0.62 The expected twist angle. This can be explained by the fact that the aggregation of the RM under an applied voltage stabilizes the abnormally low torsion angle.

This proves that it is possible to produce a polymer-stabilized TN mode display with a high d / p value but a low twist angle using the method according to the present invention.

E / O efficacy , Response time
An LCD evaluation system (LCD-5200, Otsuka electronics Co., Ltd) was used to measure the electro-optical performance (transmittance vs. voltage) and response time of the test unit.

In addition, use the following equation to calculate the response time of individual mixtures

Wherein τ is the decay time _OFF, γ ₁ is the rotational viscosity, d is the cell gap, p is the helical pitch, and K _11, K ₂₂ and K ₃₃ are open, the torsional and bending deformation of the elastic constant.

Figure 3 shows the e / o curve of a test unit using host mixture N1 (a), palmitically doped mixture B1 (b), and palmitized polymer-stabilized mixture PS-A1 (c). It can be seen that in the test unit using the mixture PS-A1, the V / T curve is shifted to high voltage due to the short distance and polymer stabilization effect, because the voltage necessary to overcome the orientation force of the surface polymer is higher than that used Test unit doped with host mixture N1 and test unit using mixture B1 with lower d / p value. It can also be seen that the polymer-stabilized mixture PS-A1 maintains high transmittance and contrast ratio, which is an advantage over PS-TN displays as reported in the prior art.

Figures 4a-c show tests using an undoped host mixture N1 ( Figure 4a ), a palm-doped mixture B1 ( Figure 4b ), and a polymer-stabilized palm-doped mixture PS-A1 ( Figure 4c ). Units measured e / o curves at 0 ° C, 10 ° C, 25 ° C, 35 ° C, and 50 ° C (right to left). It can be seen that as the temperature increases, the e / o curve shifts to a lower voltage. It can also be seen that test units using the polymer-stabilized mixture PS-A1 exhibit significantly smaller e / o curve shifts than test units using the polymer-stabilized mixtures N1 and B1.

Table 1 shows the calculated response times.
table 1 - Calculated response time
t_d Decrease (from N1 to PS-A1): 39%

It can be seen that when the d / p ratio changes from 0 to 0.63, the t _{d is} expected to decrease by 39%.

Table 2 shows the measured response times.
table 2 - Measured response time
t_d Decrease (from N1 to PS-A1): 38%

It can be seen that from mixture N1 to mixture PS-A1, the response times t _r , t _d and t _r + t _{d are} significantly reduced.

It can also be seen that the measured decrease (38%) of the decay time t _d is almost the same as the calculated value (39%). The small difference can be explained by the fact that polymer stabilization will affect the operating voltage, and the operating voltage of the polymer-stabilized mixture can still be optimized to further reduce the calculated response time and the measured response time. Difference.

Examples 2
Mixture A2 was prepared by adding 2.75% p-dopant dopant S-4011 to the LC host mixture N1. The distance between the mixtures induced by the palm dopant was 5 microns.

The mixture PS-A2 was prepared by adding 2.0% RM-51 and 1% Irgacure® 651 (concentration to RM) to the mixture A2. The distance between the mixtures induced by the palm dopant was 5 microns.

Mixture B2 was prepared by adding 1.0% p-dopant dopant S-4011 to the LC host mixture N1. The distance between the mixtures induced by the palm dopant was 13.7 microns.

Mixture C2 was prepared by adding 0.39% palmitic dopant S-4011 to the LC host mixture N1. The distance between the mixtures induced by the palm dopant was 35 microns.

TN , PS-TN Test cell manufacturing
A TN test unit using mixtures N1, B2, and C2 and a PS-TN test unit using mixture PS-A2 were prepared as described in Example 1.

E / O Performance, response time
The electro-optical performance (transmittance vs. voltage) and response time of the test unit were measured as described in Example 1.

Figure 5 shows (from left to right) a test unit using an undoped host mixture N1, a palm-doped mixture B2, a palm-doped mixture C2, and a palm-doped polymer-stabilized mixture PS-A2. E / o curve. It can be seen that in the test unit using the mixture PS-A2, the V / T curve shifts to a higher voltage than the test unit using the main mixture N1 and the test units using the lower d / p mixtures B2 and C2. As discussed in Example 1. It can also be seen that the polymer-stabilized mixture PS-A2 maintains high transmittance and contrast ratio, which is an advantage over PS-TN displays as reported in the prior art.

Table 3 shows the measured response times.
table 3- Response time
t_d Decrease (from N1 to PS-A2): 51%

It can be seen that from the mixture N1 to the mixture PS-A2, the response times t _d and t _r + t _{d are} significantly reduced.

Examples 3
Mixture A3 was prepared by adding 0.25% para-dopant R-5011 to the LC host mixture N1. The distance between the mixtures induced by the palm dopant was 5 microns.

The mixture PS-A3 was prepared by adding 1.5% RM-91, 0.5% RM-1, and 1% Irgacure® 651 (total RM concentration) to the mixture A3. The distance between the mixtures induced by the palm dopant was 5 microns.

Mixture B3 was prepared by adding 0.035% p-dopant R-5011 to the LC host mixture N1. The distance between the mixtures induced by the palm dopant was 35 microns.

Mixture C3 was prepared by adding 0.09% palmitic dopant R-5011 to the LC host mixture N1. The distance between the mixtures induced by the palm dopant was 13.6 microns.

TN test cell manufacturing <br/> A TN test cell using a mixture of N1, B3 and C3 was prepared as described in Example 1, but with a cell gap of 2.95 microns.

PS-TN Test cell manufacturing
The test unit using the mixture PS-A3 was subjected to a two-step UV curing method in which a voltage was applied to the electrode in the first step and no voltage was applied in the second UV step.

UV step 1 (UV1):
Toshiba C-type fluorescent lamp, green UV, using 365 filter, UV intensity 0.5 mW / cm ² , using UV power detector Ushio UIT-250, UVD-S365; electric field (see Figure 2b ): each pulse contains a positive Pulse and one negative pulse, 10 s / cycle, pulse height +/- 18 V, pulse width 100 ms. Irradiation time is 600 s.

UV step 2 (UV2):
The lamp and UV intensity are the same as used in step UV1, but without filter, the irradiation time is 60 min.

E / O efficacy ,Response time
The electro-optical performance (transmittance vs. voltage) and response time of the test unit were measured as described in Example 1.

Figure 6 Demonstration (from left to right) The test unit using un-doped host mixture N1, palm-doped mixture B3, palm-doped mixture C3, and palm-doped polymer-stabilized mixture PS-A3 is at 25 E / o curve measured at ℃. It can be seen that in the test unit using the mixture PS-A3, the V / T curve is shifted to a higher voltage due to the short distance and the polymer stabilization effect, for the reasons discussed in Examples 1 and 2. It can also be seen that the mixture PS-A3 maintains a high transmittance and contrast ratio, which is an advantage over PS-TN displays as reported in the prior art.

Table 4 shows the measured response times.
table 4- Response time

It can be seen that from the mixture N1 to the mixture PS-A3, the response times t _d and t _r + t _{d are} significantly reduced.

Examples 4
Mixture A4 was prepared by adding 0.25% para-dopant R-5011 to the LC host mixture N1. The distance between the mixtures induced by the palm dopant was 5 microns.

The mixture PS-A4 was prepared by adding 1.5% RM-51, 0.5% RM-1, and 1% Irgacure® 651 (total RM concentration) to the mixture A4. The distance between the mixtures induced by the palm dopant was 5 microns.

Mixture B4 was prepared by adding 0.035% p-dopant R-5011 to the LC host mixture N1. The distance between the mixtures induced by the palm dopant was 35 microns.

TN , PS-TN Test cell manufacturing
A TN test unit using the mixture N1 and B4 and a PS-TN test unit using the mixture PS-A4 were prepared as described in Example 3.

E / O Performance, response time
The electro-optical performance (transmittance vs. voltage) and response time of the test unit were measured as described in Example 1.

FIG. 7 shows (from left to right) e / o curves of a test unit using an undoped host mixture N1, a palm-doped mixture B4, and a palm-doped polymer-stabilized mixture PS-A4. It can be seen that in the test unit using the mixture PS-A4, the V / T curve is shifted to a higher voltage due to the short distance and the polymer stabilization effect. The reason is as discussed in Examples 1 and 2. It can also be seen that the mixture PS-A4 maintains a high transmittance and contrast ratio, which is an advantage over PS-TN displays as reported in the prior art.

Table 5 shows the measured response times.
table 5- Response time
t_d Decrease (from N1 to PS-A4): 37%

It can be seen that from mixture N1 to mixture PS-A4, the response times t _d and t _r + t _{d are} significantly reduced.

Examples 5
Mixture A5 was prepared by adding 0.25% para-dopant R-5011 to the LC host mixture N1. The distance between the mixtures induced by the palm dopant was 5 microns.

The mixture PS-A5 was prepared by adding 1.5% RM-51, 0.5% RM-1, and 1% Irgacure® 651 (total RM concentration) to the mixture A5. The distance between the mixtures induced by the palm dopant was 5 microns.

Mixture B5 was prepared by adding 0.035% p-dopant R-5011 to the LC host mixture N1. The distance between the mixtures induced by the palm dopant was 35 microns.

TN , PS-TN Test cell manufacturing
A TN test unit using the mixture N1 and B5 and a PS-TN test unit using the mixture PS-A5 were prepared as described in Example 3.

E / O performance, response time
The electro-optical performance (transmittance vs. voltage) and response time of the test unit were measured as described in Example 1.

FIG. 8 shows (from left to right) e / o curves of a test cell using an undoped host mixture N1, a palm-doped mixture B5, and a palm-doped polymer stabilized mixture PS-A5. It can be seen that in the test unit using the mixture PS-A4, the V / T curve is shifted to a higher voltage due to the short distance and the polymer stabilization effect. The reason is as discussed in Examples 1 and 2. It can also be seen that the mixture PS-A5 maintains a high transmittance and contrast ratio, which is an advantage over PS-TN displays as reported in the prior art.

Table 6 shows the measured response times.
table 6- Response time
t_d Decrease (from N1 to PS-A5): 38%

It can be seen that from the mixture N1 to the mixture PS-A5, the response times t _d and t _r + t _{d are} significantly reduced.

The above results show that the method of the present invention can manufacture a PS-UF TN-LCD, which has a high d / p value while maintaining a 90 ° TN configuration, and can achieve a fast response time, especially a fast decay time, and an e / o curve. Low temperature dependence, while maintaining a reasonably low drive voltage, high contrast ratio, and high transmittance.

100‧‧‧ Display

110‧‧‧first substrate

115‧‧‧ITO electrode

120‧‧‧Alignment layer

130‧‧‧ polymer layer

140‧‧‧LC medium

150‧‧‧second substrate

155‧‧‧ITO electrode

160‧‧‧Alignment layer

170‧‧‧ polymer layer

180‧‧‧Polarizer

190‧‧‧Polarizer

FIG. 1 illustrates the structure of a PS-UF TN-LC display according to the present invention, exemplarily and schematically.

Figures 2a-c exemplarily show a suitable and preferred driving process for applying a voltage in step c) of the method of the invention.

Figure 3 shows the transmittance versus voltage curve of a display test unit containing a mixture according to Example 1 of the present invention.

Figures 4a-c show a graph containing a voltage with respect to the transmittance of the display unit to test mixtures of one embodiment of the invention at different temperatures.

FIG. 5 shows the transmittance versus voltage curve of a display test unit containing a mixture according to Example 2 of the present invention.

Figure 6 shows the transmittance versus voltage curve of a display test unit containing a mixture according to Example 3 of the present invention.

FIG. 7 shows the transmittance versus voltage curve of a display test unit containing a mixture according to Example 4 of the present invention.

FIG. 8 shows the transmittance versus voltage curve of a display test unit containing a mixture according to Example 5 of the present invention.

Claims (19)

An LC display including a) a first substrate and a second substrate, the first substrate being equipped with a first electrode layer and optionally a first alignment layer, the second substrate being equipped with a second electrode layer and optionally a second alignment layer, b) a nematic LC dielectric layer distributed between the first and second substrates, the LC dielectric layer contains a palmitic additive and has a positive dielectric anisotropy, c) a first polarizer existing on the side of the first substrate opposite to the LC layer and a second polarizer existing on the side of the second substrate opposite to the LC layer, etc. The polarizer is preferably oriented such that its transmission plane is at a right angle to the plane polarized light (orthogonal Nicoll), The longitudinal axes of the LC molecules are oriented parallel or oblique to the planes of the substrates, and the pair of palm additives induce the LC molecules in the LC medium along the axis perpendicular to the substrates with a specified distance p A spiral twist, The LC dielectric layer has a thickness d, and the ratio d / p is ≧ 0.5, preferably ≧ 0.5, and most preferably 0.6 to 0.8. The twist angle of the spiral twist of the LC molecules is 60 to 120 °, preferably 80 to 100 °, and most preferably 90 °, and Wherein the display further includes a polymer layer deposited on one or both of the first and second electrodes or, if present, on one or both of the first and second alignment layers, The polymer layer is formed of one or more polymerizable mesogen compounds, and the concentration of the compounds in the LC medium is <3%, preferably 0.05 to <3%, and the LC medium has been distributed After the two substrates, in-situ polymerization occurs. The display of claim 1, wherein the twist angle of the spiral twist of the LC molecules between the first substrate and the second substrate is 80 ° to 100 °. The display as claimed in claim 1, wherein the ratio d / p of the distance p between the layer thickness d of the LC medium and the spiral twist induced by the pair of palm additives is 0.6 to 0.8. The display of claim 1, wherein the longitudinal axis of the LC molecules in the LC medium on the surface of each substrate exhibits an inclination angle of> 0 ° to 20 ° with respect to the substrate. The display of claim 1, wherein the first and second substrates are provided with fixing members that fix the first and second substrates at a constant distance from each other and whose planes are parallel to each other. The display of claim 1, wherein the LC medium comprises one or more compounds selected from the group consisting of: Wherein the individual groups have the following meanings independently of each other and in each occurrence the same or different: R ²¹ , R ³¹ are each independently an alkyl, alkoxy, oxaalkyl, or alkoxyalkyl group having 1 to 9 C atoms or an alkenyl or alkenyloxy group having 2 to 9 C atoms The above owner is optionally fluorinated, X ⁰ F, Cl, a halogenated alkyl or alkoxy group having 1 to 6 C atoms, or a halogenated alkenyl or alkenyloxy group having 2 to 6 C atoms , Z ³¹ -CH ₂ CH _2- , -CF ₂ CF _2- , -COO-, trans-CH = CH-, trans-CF = CF-, -CH ₂ O- or single bond, preferably -CH ₂ CH _2- , -COO-, trans-CH = CH- or a single bond, particularly preferably -COO-, trans-CH = CH- or a single bond, L ²¹ , L ²² , L ³¹ , L ³² are independent of each other Each is H or F, L ^S H or CH ₃ , g 0, 1, 2 or 3. The display of any one of claims 1 to 6, wherein the LC medium comprises one or more compounds selected from the following formula: The individual groups have the following meanings: R ⁴¹ and R ⁴² are each independently an alkyl, alkoxy, oxaalkyl, or alkoxyalkyl group having 1 to 9 C atoms or an alkenyl or alkenyloxy group having 2 to 9 C atoms The above owners are fluorinated as appropriate, and Z ⁴¹ and Z ⁴² are independently -CH ₂ CH _2- , -COO-, trans-CH = CH-, trans-CF = CF-, -CH ₂ O -, -CF ₂ O-, -C≡C- or a single bond, preferably a single bond, h 0, 1, 2 or 3. The display of any one of claims 1 to 6, wherein the LC medium comprises one or more compounds selected from the following formula: The individual groups have the following meanings, which are the same or different and independent of each other at each occurrence: R ^A1 having 2-9 C atoms in the alkenyl group, or a ring if X, Y and Z represents at least one of the cyclohexenyl, it is also one of the meanings of R ^A2, R ^A2 having 1 to 12 C Atomic alkyl groups, in addition, one or two non-adjacent CH ₂ groups can make O atoms not directly connected to each other via -O-, -CH = CH-, -CO-, -OCO-, or- COO-permutation, x 1 or 2. The display device of any one of claims 1 to 6, wherein the polymerizable mesogen compounds are selected from the formula I R ^a -B ^1- (Z ^b -B ² ) _m -R ^b I where individual groups are present each time The same or different and independent of each other have the following meanings: R ^a and R ^b P, P-Sp-, H, F, Cl, Br, I, -CN, -NO ₂ , -NCO, -NCS,- OCN, -SCN, SF ₅ or a straight or branched chain alkyl group having 1 to 25 C atoms, wherein, in addition, one or more non-adjacent CH ₂ groups may each independently of one another such that O and / or S The way that the atoms are not directly connected to each other via -C (R ⁰ ) = C (R ⁰⁰ )-, -C≡C-, -N (R ⁰⁰ )-, -O-, -S-, -CO-, -CO -O-, -O-CO-, -O-CO-O- substitution, and wherein additionally, one or more H atoms may be substituted with F, Cl, Br, I, CN, P, or P-Sp-, where when B ¹ and / or B ² containing saturated C atom, then R ^a and / or R ^b may represent a group screwed to this saturated C atoms, wherein these radicals R ^a and R ^b represents at least one of the Or contains a group P or P-Sp-, a P polymerizable group, a Sp spacer or a single bond, a B ¹ and B ² aromatic group, a heteroaromatic group, an alicyclic group or a heterocyclic group, preferably having 4 to 25 Ring atoms, which may also contain fused rings and which is unsubstituted or mono- or polysubstituted by ^{L, Z b -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 single bond, R ⁰ and R ⁰⁰ H or alkyl having 1 to 12 C atoms, m 0, 1, 2, 3 or 4 , N1 1, 2, 3, or 4, LP, P-Sp-, OH, CH ₂ OH, F, Cl, Br, I, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C (= O) N (R ^x ) ₂ 、 -C (= O) Y ¹ 、 -C (= O) R ^x 、 -N (R ^x ) ₂ Substituted aryl groups having 6 to 20 C atoms, or straight or branched chain alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxy groups having 1 to 25 C atoms Carbonyloxy, wherein, in addition, one or more H atoms may be replaced by F, Cl, P or P-Sp-, Y ¹ halogen, R ^x P, P-Sp-, H, halogen, having 1 to 25 C atom straight chain, branched chain or cyclic alkyl group Wherein Additionally, one or more non-adjacent CH ₂ groups may be such that O and / or S atoms are not linked directly to one another by -O -, - S -, - CO -, - CO-O -, - O -CO-, -O-CO-O- substitution, and in addition, one or more H atoms may be substituted with F, Cl, P, or P-Sp-; optionally substituted with 6 to 40 C atoms Aryl or aryloxy, or optionally substituted heteroaryl or heteroaryloxy having 2 to 40 C atoms. The display of any one of claims 1 to 6, wherein the polymerizable mesogen compounds are selected from the following formula: The individual groups are the same or different and independent of each other each time they have the following meanings: P ¹ , P ² , P ³ vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate , Oxetane or epoxy groups, Sp ¹ , Sp ² , Sp ³ single bonds or spacers, wherein in addition, the groups P ¹ -Sp ^1- , P ¹ -Sp ² -and P ³ -Sp ^3- may also be represented in one or more of R ^aa, with the proviso that the presence of such groups ^{P 1 -Sp 1 -, P 2} -Sp 2 and P ³ -Sp ³ - in at least one of R ^aa with different R ^aa H, F, Cl, CN or a straight or branched chain alkyl group having 1 to 25 C atoms, wherein, in addition, one or more non-adjacent CH ₂ groups can each independently of one another such that O and / Or S atoms are not directly connected to each other via -C (R ⁰ ) = C (R ⁰⁰ )-, -C≡C-, -N (R ⁰ )-, -O-, -S-, -CO- , -CO-O-, -O-CO-, -O-CO-O-, and in addition, one or more H atoms may be replaced by F, Cl, CN, or P ¹ -Sp ^1- ; especially It is preferably a straight or branched chain having 1 to 12 C atoms, optionally mono- or polyfluorinated alkyl, alkoxy, alkenyl, alkynyl, Alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, wherein the alkenyl and alkynyl groups have at least two C atoms and the branched chain groups have at least three C atoms, R ⁰ , R ⁰⁰ H or an alkyl group having 1 to 12 C atoms, R ^y and R ^z H, F, CH ₃ or CF ₃ , X ¹ , X ² , X ³ -CO-O-, -O-CO -Or single bond, Z ¹ -O-, -CO-, -C (R ^y R ^z )-or -CF ₂ CF _2- , Z ² , Z ³ -CO-O-, -O-CO-,- CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF ₂ -or-(CH ₂ ) _n- , where n is 2, 3 or 4, LF, Cl, CN, or has 1 to 12 C atom straight or branched, optionally monofluorinated or polyfluorinated alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyl Oxygen; L ', L "H, F or Cl, r 0, 1, 2, 3 or 4, s 0, 1, 2 or 3, t 0, 1 or 2, x 0 or 1. The display of any one of claims 1 to 6, wherein the polymerizable mesogen compounds are polymerized by UV photopolymerization. The display of any one of claims 1 to 6, wherein the LC medium comprises one or more pairs of palmar dopants. The display of any one of claims 1 to 6, wherein the LC medium comprises one or more additives selected from the group consisting of a photoinitiator, a stabilizer, and a self-aligning additive. A method of manufacturing a display as claimed in any one of claims 1 to 13, comprising the following steps a) Provide a first substrate and a second substrate, the first substrate is equipped with a first electrode layer and optionally a first alignment layer, and the second substrate is equipped with a second electrode layer and optionally a second alignment layer , Wherein the first and / or second substrate is preferably equipped with a fixing member, the fixing member is preferably a sealing material and / or a spacer, which makes the first and second substrates at a constant distance relative to each other and its Fixed when the planes are parallel to each other, b) distributing a nematic LC medium having positive dielectric anisotropy between the first and second substrates, so that if these layers exist, the LC medium is in contact with the first and second alignment layers, The LC medium includes, and preferably consists of: A) a liquid crystal component A, which contains liquid crystal molecules or liquid crystal molecules, preferably composed of liquid crystal molecules or liquid crystal molecules, B) a polymerizable component B comprising one or more polymerizable mesogen compounds, preferably consisting of one or more polymerizable mesogen compounds, C) one or more palmar additives, preferably selected from palmar dopants, D) optionally one or more other additives, preferably selected from polymerization initiators, stabilizers and self-aligning additives, Wherein the ratio of the polymerizable mesogen compounds in the LC medium is <3%, preferably 0.05 to <3%, and The longitudinal axes of the LC molecules are oriented parallel or oblique to the planes of the substrates, and the pair of palm additives induce the LC molecules in the LC medium along the axis perpendicular to the substrates with a specified distance p A spiral twist, and Wherein the LC dielectric layer has a thickness d, and the ratio d / p is ≥0.5, preferably> 0.5, and most preferably 0.6 to 0.8, and The twist angle of the helical twist of the LC molecules induced by the pair of palm additives is> 210 °, preferably 210 to 330 °, more preferably 240 to 300 °, and extremely good 270 °, c) The voltage is applied to the first electrode and the second electrode, so that the twist angle of the helical twist of the LC molecules is reduced to <150 °, preferably to a range of 60 to 120 °, and more preferably 80 to 100 °, excellent 90 °, d) polymerizing the polymerizable mesogen compounds of the polymerizable component B of the LC medium between the first substrate and the second substrate after the voltage is applied, preferably by Polymerization occurs by exposure to UV radiation, thereby stabilizing the twisted nematic configuration of the LC medium having a reduced twist angle in step c), and e) optionally subjecting the LC medium to a second polymerization step, preferably by exposing to UV radiation without applying a voltage to the first and second electrodes, thereby allowing any polymerizable compound that has not reacted in step d) polymerization. The method of claim 14, wherein the twist angle of the helical twist of the LC molecules between the first substrate and the second substrate is 240 ° to 300 ° before the voltage is applied in step c), and in step c The voltage in) is 80 ° to 100 °. The method of claim 14 or 15, wherein component A of the LC medium comprises one or more compounds as defined in any one of claims 6, 7, and 8. The method of claim 14 or 15, wherein the polymerizable mesogen compounds of component B of the LC medium are as defined in claim 9 or 10. An LC medium containing A) a liquid crystal component A comprising one or more compounds selected from the formulas A and B as defined in claim 6, one or more compounds selected from the formulas C and D as defined in claim 7, and optionally The presence of one or more compounds of formula E as defined in claim 8, B) a polymerizable component B comprising one or more polymerizable mesogens of formula I as defined in claim 9; C) one or more palmar additives, preferably selected from palmar dopants, D) optionally one or more other additives, preferably selected from polymerization initiators, stabilizers and self-aligning additives, Wherein the concentration of the polymerizable mesogen compounds of component B of the LC medium is 0.05 to <3%, and The concentration of the palmitic additives is selected so that the twist angle induced in the LC medium is> 210 °, preferably 210 to 330 °, more preferably 240 to 300 °, and extremely good 270 °. An LC medium containing A) a liquid crystal component A comprising one or more compounds selected from the formulas A and B as defined in claim 6, one or more compounds selected from the formulas C and D as defined in claim 7, and optionally The presence of one or more compounds of formula E as defined in claim 8, B) a polymerizable component B comprising one or more polymerizable mesogens of formula I as defined in claim 9; C) one or more palmar additives, preferably selected from palmar dopants, D) optionally one or more other additives, preferably selected from polymerization initiators, stabilizers and self-aligning additives, Wherein the concentration of the polymerizable mesogen compounds in the LC medium is 0.05 to <3%, and The concentration of the palmitic additives is selected so that the spiral pitch induced in the LC medium is 2 to 10 μm, and preferably 3 to 6 μm.