Liquid crystal medium

Abstract

The invention relates to a liquid crystal (LC) material as defined in claim 1, preferably having a negative dielectric anisotropy, and to the use thereof for optical, electro-optical and electronic purposes, for example in energy-saving LC displays, in particular displays of the PS-VA type.

Description

Technical Field

[0001] This invention relates to liquid crystal (LC) media comprising one, two or more polymerizable compounds; to the use of said LC media for optical, electro-optical and electronic purposes, particularly in LC displays, especially in PSA (polymer-stabilized alignment) or SA (self-alignment) mode LC displays; to PSA or SA mode LC displays comprising said LC media; to methods for manufacturing LC displays, particularly energy-efficient LC displays, using said LC media; and to methods for producing energy-efficient LC displays. Background Technology

[0002] The proliferation of 8K and gaming monitors has led to increased demand for LC display (LCD) panels with higher refresh rates, and consequently, for LC media with faster response times. Many of these LCD panels use polymer-stabilized (PS) or polymer-stabilized alignment (PSA) modes, such as PS-VA (vertically aligned), PS-IPS (in-plane switching), or PS-FFS (edge ​​field switching) modes or their derivatives, or self-aligned (SA) modes such as SA-VA, which are polymer-stabilized.

[0003] In PS or PSA mode, a small amount, typically 0.1-1%, of one or more polymerizable mesocrystalline compounds (also known as RM (reactive mesocrystalline)) is added to the LC medium. After the LC medium is filled into the display, the RM is then polymerized in situ via UV photopolymerization while a voltage is applied to the electrodes of the display. This creates a small tilt angle in the LC molecules of the LC medium, which is stabilized by the polymerized RM. The UV polymerization method (also known as the "PSA method") is typically carried out in two steps: a first UV exposure step ("UV1 step"), in which a voltage is applied to create the tilt angle, and a second UV exposure step ("UV2 step"), in which no voltage is applied, to complete the RM polymerization.

[0004] In SA-VA mode, the alignment layer is omitted from the display. Instead, a small amount, typically 0.1–2.5%, of self-aligning (SA) additive is added to the LC medium. This initiates the desired alignment, such as vertical or planar alignment, in situ via a self-assembly mechanism. SA additives typically contain an organic mesocrystalline core group with one or more polar anchoring groups, such as hydroxyl, carboxyl, amino, or thiol groups, attached thereto. These groups interact with the substrate surface, leading to additive alignment on the substrate surface and inducing the desired alignment within the LC molecules. SA additives may also contain one or more polymerizable groups, which can be polymerized under conditions similar to the RM used in the PSA method. In addition to SA additives, the LC medium may also contain one or more RMs.

[0005] One approach to reducing the response time of LC media to PSA mode is, for example, by using alkenyl compounds as components of the LC host mixture. However, this can lead to reduced reliability of the mixture when exposed to the UV light required for polymerizing RM additives, which is believed to be due to the reaction of the alkenyl compound with the polyimide in the alignment layer, particularly problematic when using shorter UV wavelengths less than 320 nm. Therefore, there is a trend towards using longer UV wavelengths for PSA methods.

[0006] The use of UV-LED lamps in the PSA process is also recommended because they exhibit lower energy consumption, longer lifetime, and more efficient light energy transfer to the LC medium due to their narrower emission peaks, which allows for reduced UV intensity and / or UV irradiation time. This can shorten cycle time and save energy and production costs. Currently available UV lamps have higher wavelength emission, for example, at 365 nm.

[0007] Therefore, polymerizable LC media that enable RM to be effectively polymerized at longer UV wavelengths are also needed.

[0008] Another issue in PSA display production is the presence or removal of residual unreacted polymerized reductant (RM), particularly after polymerization steps that create tilt in the display. For example, this type of unreacted RM can adversely affect display performance, such as by polymerizing in an uncontrolled manner during post-display operation.

[0009] Therefore, in existing PSA displays, additional image sticking caused by the presence of unpolymerized resonant membranes (RMs) is commonly observed. Uncontrolled polymerization of residual RMs is triggered by ambient ultraviolet light or backlighting. In switching display areas, this changes the tilt angle after multiple addressing cycles. Consequently, the transmittance in switching areas may vary, while it remains constant in non-switching areas.

[0010] Therefore, in the production process of PSA displays, it is desirable for the polymerization of RM to proceed as completely as possible, and for the presence of unpolymerized RM in the display to be eliminated or reduced to a minimum. Thus, a mixture of RM and LC is needed to achieve or support efficient and complete polymerization of RM. Furthermore, controlled reaction of residual RM amounts is also desirable. It would be simpler if RM could polymerize faster and more efficiently than compounds known to date.

[0011] Another issue observed in the operation of PSA displays is the stability of the tilt angle. Therefore, the tilt angle generated during the display manufacturing process through the polymerization of RM as described above does not remain constant, but rather deteriorates after the display is subjected to voltage stress during its operation. This can negatively impact display performance, for example, by increasing black-state transmittance, thereby reducing contrast.

[0012] Therefore, the object of the present invention is to provide an improved LC medium containing RM for PSA or SA displays, and a PSA or SA display containing the thereof, which exhibits very high resistivity, high VHR, high reliability, low threshold voltage, short response time, high birefringence, good UV absorption, especially at longer UV wavelengths, preferably in the range of 340 to 380 nm, rapid and complete polymerization of RM, controlled generation of low tilt angles, high tilt angle stability after UV exposure, reduced image viscosity and ODF inhomogeneity (mura), and wherein RM exhibits high solubility in the LC bulk mixture.

[0013] It has been found that one or more of these objectives can be achieved by providing an LC medium containing one, two or more polymerizable compounds as described herein and claimed. Summary of the Invention

[0014] This invention relates to an LC dielectric having a high brightness temperature of 95°C or higher and having negative dielectric anisotropy, comprising...

[0015] a) 5-30%, preferably 7-25%, of one or more compounds of formula IIA-1.

[0016]

[0017] b) 15-45%, preferably 18-40%, of one or more compounds of formula IIA-2.

[0018]

[0019] c) 8%-30%, preferably 12-27%, of one or more compounds of formula IIB.

[0020] d) 4%-12% of one or more compounds selected from formulas IIC, IIE, and XI.

[0021]

[0022] e) Less than 1% or 0% of one or more IID compounds

[0023]

[0024] in

[0025] R 2A R 2B R 2C R 2D and R 2EThe same or different representations of H, straight-chain alkyl or alkoxy groups having 1-15 carbon atoms, straight-chain alkenyl or alkenyloxy groups having 2-15 carbon atoms, or branched alkyl, alkoxy, alkenyl, or alkenyloxy groups each having 3-15 carbon atoms, wherein one or more CH2 groups among these groups can be independently represented by each other.

[0026] -CH=CH-, -C≡C-, -CF2O-, -OCF2-, -O-, -CO-O-, or -O-CO- are substitutions where the O atoms are not directly connected to each other, and one or more of the H atoms can be replaced by halogens.

[0027] R 111 and R 112 It may represent F or Cl in the same or different ways, or have the group R. 2A One of the meanings, and preferably F or Cl, or a straight-chain alkyl group having 1-7 carbon atoms, or a straight-chain alkenyl group having 2-7 carbon atoms.

[0028] L 1 and L 2 Each can be independently represented by F, Cl, CF3, or CHF2, with F or Cl being preferred, and F being highly preferred.

[0029] X 21 X 22 X 23 X 24 X 25 X 26 X 111 X 112 and X 113 They may represent H, F, Cl, CF3, or CHF2, either the same or different.

[0030] Y represents H, F, Cl, CF3, CHF2, or CH3, preferably H or CH3, more preferably H.

[0031] Z 2 and Z 2D Each of these can independently represent a single bond, -CH2CH2-, -CH=CH-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -COO-, -OCO-, -C2F4-, -CF=CF-, or -CH=CHCH2O-.

[0032] (O) represents O or a single bond.

[0033] q represents 0, 1, or 2, and

[0034] v represents an integer from 1 to 6.

[0035] The following media are excluded:

[0036] 2.5% of compound CC-3-V1,

[0037] 10.0% of compound CC-4-V1,

[0038] 3.0% of compound CC-3-O1,

[0039] 4.0% of compound CC-3-4,

[0040] 4.0% of compound CC-3-5,

[0041] 6.0% of compound CCP-3-1,

[0042] 6.0% of compound CCP-3-3,

[0043] 4.0% of compound CCY-3-O1,

[0044] 4.0% of the compound CCY-3-O2,

[0045] 4.0% of the compound CCY-3-O3,

[0046] 4.0% of the compound CCY-4-O2,

[0047] 4.0% of compound CCY-5-O2

[0048] 10.0% of compound CPY-2-O2,

[0049] 10.0% of compound CPY-3-O2,

[0050] 6.5% of compound CY-3-O2,

[0051] 10.0% of compound CY-3-O4,

[0052] 5.0% of compound PYP-2-3, and

[0053] 3.0% of compound PYP-2-4,

[0054] Furthermore, the total concentration of preferred compounds IIA-1 and IIA-2 is in the range of 30%-65%, and / or the total concentration of preferred compounds IIB and IIC and / or IIE and / or XI is in the range of 13%-30% by weight.

[0055] The present invention also relates to LC displays comprising the LC medium according to the present invention, particularly VA, IPS, FFS, PS-VA, PS-IPS, PS-FFS, PS-UB-FFS, or SA-VA displays. The present invention further relates to the use of the LC medium according to the present invention in said displays.

[0056] The present invention also relates to the use of the LC medium according to the invention in a PSA display, and particularly to the use of generating a tilt angle in the LC medium by in-situ polymerization of polymerizable reactive mesomorphs (RM) in the PSA display, preferably in an electric or magnetic field, in a PSA display containing the LC medium.

[0057] The present invention also relates to a method for preparing the liquid crystal medium described in the context, comprising the steps of mixing one or more compounds of formula IIA-1 and IIA-2 as defined above, as well as IIB and / or IIC and / or IIE and / or optional IID compounds, and optionally mixing with other liquid crystal compounds or additives.

[0058] This invention also relates to a method for manufacturing a liquid crystal display device, comprising at least the following steps:

[0059] - Provide a first substrate and a second substrate, at least one of which is transparent to light, and provide one electrode on each substrate, or two electrodes on one substrate.

[0060] - A sealant is formed along the end of one of the first substrate and the second substrate.

[0061] - An LC medium according to one or more of claims 1 to 11 is provided between the first substrate and the second substrate and the sealant.

[0062] - To bond the first substrate and the second substrate together to form an LC cell.

[0063] - Post-baking the sealant at a temperature of approximately 100°C to approximately 140°C for approximately 15 minutes to approximately 120 minutes.

[0064] - For example, using a temperature gradient across at least one direction of the display for non-uniform cooling.

[0065] Optionally, if present, a self-aligning liquid crystal layer is formed between the first and second substrates and the sealant by maintaining the temperature of the liquid crystal cell above the clearing point temperature of the self-aligning liquid crystal material comprising the SA compound as defined in claim 9.

[0066] - and optionally, if present, polymerizing the polymerizable compound of formula P according to claim 8 by irradiation with UV light, preferably while applying a voltage to the electrodes of the liquid crystal display device.

[0067] Surprisingly, the medium according to the invention exhibits a nematic phase over a wide temperature range and has a particularly high clearing temperature. Despite the relatively high viscosity accompanying the high clearing temperature, the medium demonstrates an improved ability to achieve uniform alignment on the substrate for vertical alignment.

[0068] Furthermore, the LC medium according to the invention is characterized by surprisingly high reliability and stability against UV or backlight, and also possesses the following advantageous properties, particularly when used in PS-VA displays:

[0069] - Excellent low-temperature stability (LTS)

[0070] - Improved contrast of the display,

[0071] - The display's high transmittance

[0072] -High clarity temperature

[0073] - High voltage retention rate

[0074] -Low rotational viscosity,

[0075] - Quick switching

[0076] - Fast response time to enable low-power LCDs that can extend the battery life of mobile devices.

[0077] - High elastic constant.

[0078] In a preferred embodiment of the invention, the medium comprises one or more compounds of formula IIA'.

[0079]

[0080] in

[0081] R 2A The group represents H, a straight-chain alkyl or alkoxy group having 1-15 carbon atoms, a straight-chain alkenyl or alkenyloxy group having 2-15 carbon atoms, or a branched alkyl, alkoxy, alkenyl, or alkenyloxy group each having 3-15 carbon atoms, wherein one or more of these CH2 groups can be independently separated from each other. -CH=CH-, -C≡C-, -CF2O-, -OCF2-, -O-, -CO-O-, or -O-CO- are substitutions where the O atoms are not directly connected to each other, and one or more of the H atoms can be replaced by halogens.

[0082] This indicates 1,4-cyclohexylene or tetrahydropyran-2,5-diyl.

[0083] L 1 and L 2 Each can be independently represented as F, Cl, CF3, or CHF2.

[0084] Y represents H, F, Cl, CF3, CHF2, or CH3, preferably H or CH3, more preferably H.

[0085] Z 2 This indicates -CH2CH2-, -CH=CH-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -COO-, -OCO-, -C2F4-, -CF=CF-, or -CH=CHCH2O-, preferably -CH2O-.

[0086] p represents 0, 1, or 2, and

[0087] v represents an integer from 1 to 6.

[0088] In a preferred embodiment of the invention, the medium comprises one or more compounds of formula IIB'.

[0089]

[0090] in

[0091] R 2B The group represents H, a straight-chain alkyl or alkoxy group having 1-15 carbon atoms, a straight-chain alkenyl or alkenyloxy group having 2-15 carbon atoms, or a branched alkyl, alkoxy, alkenyl, or alkenyloxy group each having 3-15 carbon atoms, wherein one or more of these CH2 groups can be independently separated from each other. -CH=CH-, -C≡C-, -CF2O-, -OCF2-, -O-, -CO-O-, or -O-CO- are substitutions where the O atoms are not directly connected to each other, and one or more of the H atoms can be replaced by halogens.

[0092] L 1 and L 2 Each can be independently represented as F, Cl, CF3, or CHF2.

[0093] X represents H or F, with H being preferred.

[0094] Y represents H, F, Cl, CF3, CHF2, or CH3, preferably H or CH3, more preferably H.

[0095] Z B This indicates -CH2CH2-, -CH=CH-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -COO-, -OCO-, -C2F4-, -CF=CF-, or -CH=CHCH2O-.

[0096] (O) represents O or a single bond.

[0097] p is 0 or 1, preferably 0, and

[0098] v is an integer from 1 to 6.

[0099] Preferred compounds of formulas IIA-1, IIA-2, IIA', IIB, IIB', IIC and IID are shown below:

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112] Where parameter a represents 1 or 2, alkyl and alkyl * Each of these terms independently represents a straight-chain alkyl group having 1-6 carbon atoms, and alkenyl and alkenyl *Each of these symbols independently represents a straight-chain alkenyl group with 2-6 carbon atoms, and (O) represents an oxygen atom or a single bond. alkenyl and alkenyl * The preferred representations are CH2=CH-, CH2=CHCH2CH2-, CH3-CH=CH-, CH3-CH2-CH=CH-, CH3-(CH2)2-CH=CH-, CH3-(CH2)3-CH=CH-, or CH3-CH=CH-(CH2)2-.

[0113] Compounds of formula IID-4 and IID-10 are highly preferred, wherein (O) specifically represents O.

[0114] The most preferred IID compounds are selected from the following sub-formulas:

[0115]

[0116]

[0117]

[0118]

[0119]

[0120] In a preferred embodiment, the medium comprises one or more compounds of formula IID-10a.

[0121]

[0122] The groups and parameters that appear have the meanings given in Equation IID above, and

[0123] R 2 express , where r is 0, 1, 2, 3, 4, 5 or 6, and s is 1, 2 or 3.

[0124] The preferred compounds of formula IID-10a are compounds IID-10a-1 to IID-10a-14.

[0125]

[0126]

[0127]

[0128] The preferred medium according to the invention comprises at least one compound of formula IIC-1.

[0129]

[0130] Among them alkyl and alkyl * It has the above meaning.

[0131] Specifically, the medium comprises one or more compounds selected from the following formulas: IIA-1-2

[0132]

[0133] Alternatively, preferably, in addition to compounds of formulas IIA-1-2-1 to IIA-1-2-5, the medium also comprises one or more compounds of formulas IIA-1-2a-1 to IIA-1-2a-5:

[0134]

[0135]

[0136] Specifically, the medium comprises one or more compounds selected from the formula IIA-2-2:

[0137]

[0138] Alternatively, preferably, in addition to compounds of formulas IIA-2-2-1 to IIA-2-2-5, the medium also comprises one or more compounds of formulas IIA-2-2a-1 to IIA-2-2a-5:

[0139]

[0140] Specifically, the medium comprises one or more compounds selected from the following formula IIB-2:

[0141]

[0142]

[0143] Alternatively, preferably, in addition to compounds of formulas IIB-10-1 to IIB-10-5, the medium also comprises one or more compounds of formulas IIB-10a-1 to IIB-10a-5:

[0144]

[0145] Alternatively, preferably, in addition to the compound of formula IIC-1, the medium also comprises one or more compounds of formulas IIC-1a-1 and IIC-1a-2.

[0146]

[0147] Wherein alkyl represents a straight-chain alkyl group having 1-7 carbon atoms, preferably 2-5 carbon atoms, and very preferably ethyl.

[0148] Preferred IIE compounds are selected from the following sub-formulas:

[0149]

[0150]

[0151]

[0152]

[0153] Where R 2E It represents a straight-chain alkyl or alkoxy group with 1-6 C atoms, (O) represents -O- or a single bond, m is 0, 1, 2, 3, 4, 5 or 6, and n is 0, 1, 2, 3 or 4.

[0154] R 2E Preferred terms include methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy, and pentoxy.

[0155] The medium according to the invention preferably comprises one or more compounds of formula III.

[0156]

[0157] in

[0158] R 31 and R 32 Each of these groups independently represents H, and is an alkyl or alkoxy group having 1 to 15 carbon atoms, wherein one or more CH2 groups are each independently represented by H. -CH=CH-, -C≡C-, -CF2O-, -OCF2-, -O-, -CO-O-, or -O-CO- are used to substitute O atoms in a way that prevents them from being directly connected to each other, and one or more H atoms can be substituted with halogens.

[0159] A 31 Each occurrence is represented independently.

[0160] a) 1,4-cyclohexeneyl or 1,4-cyclohexeneyl, wherein one or both non-adjacent CH2 groups may be replaced by -O- or -S-.

[0161] b) 1,4-Phenylidene, wherein one or both CH groups may be replaced by N, or

[0162] c) Selected from the following groups: spiro[3.3]heptane-2,6-diyl, 1,4-bicyclo[2.2.2]octylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, phenanthrene-2,7-diyl, and fluorene-2,7-diyl.

[0163] Groups a), b), and c) can be mono- or poly-substituted with halogen atoms.

[0164] n represents 0, 1, or 2, preferably 0 or 1.

[0165] Z 31 Each occurrence independently represents -CO-O-, -O-CO-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CH2-, -CH2CH2-, -(CH2)4-, -CH=CH-CH2O-, -C2F4-, -CH2CF2-, -CF2CH2-, -CF=CF-, -CH=CF-, -CF=CH-, -CH=CH-, -C≡C- or a single bond, and

[0166] L 31 and L 32 Each of these can be independently represented as F, Cl, CF3, or CHF2, preferably H or F, with F being the most preferred, and

[0167] W represents O or S.

[0168] The compounds of formula III are preferably selected from compounds of formula III-1 and / or III-2.

[0169]

[0170] The groups appearing therein have the same meaning as those given in Formula III above, and are preferably...

[0171] R 31 and R 32 Each of these is independently an alkyl, alkenyl, or alkoxy group having at most 15 carbon atoms, more preferably one or both of them representing an alkoxy group, and

[0172] L 31 and L 32 Each is preferred, represented by F.

[0173] Preferably, the compound of formula III-1 is selected from compounds of formulas III-1-1 to III-1-11, preferably formula III-1-6.

[0174]

[0175]

[0176] in

[0177] alkyl and alkyl* each independently represent a straight-chain alkyl group having 1-6 carbon atoms, alkenyl and alkenyl* each independently represent a straight-chain alkenyl group having 2-6 carbon atoms, alkoxy and alkoxy* each independently represent a straight-chain alkoxy group having 1-6 carbon atoms, and L... 31 and L 32 Each can be represented independently as F or Cl, with F being the preferred choice.

[0178] The compounds of formula III-2 are preferably selected from compounds of formulas III-2-1 to III-2-10, with formula III-2-6 being the most preferred.

[0179]

[0180]

[0181] in

[0182] alkyl and alkyl* each independently represent a straight-chain alkyl group having 1-6 carbon atoms, alkenyl and alkenyl* each independently represent a straight-chain alkenyl group having 2-6 carbon atoms, alkoxy and alkoxy* each independently represent a straight-chain alkoxy group having 1-6 carbon atoms, and L... 31 and L 32 Each can be represented independently as F or Cl, with F being the preferred choice.

[0183] Optionally, the medium comprises one or more compounds of formula IIIA-1 and / or IIIA-2.

[0184]

[0185] Where L 31 and L 32 It has the same meaning as given in Equation III, where (O) represents O or a single bond.

[0186] R IIIA Cy-C indicates an alkyl or alkenyl group or group having up to 7 carbon atoms. m H 2m+1 -,

[0187] m and n are the same or different from 0, 1, 2, 3, 4, 5 or 6, preferably 1, 2 or 3, very preferably 1.

[0188] Cy represents an alicyclic group having 3, 4, or 5 ring atoms, which may optionally be substituted by an alkyl or alkenyl group having up to 3 carbon atoms, or a halogen or CN, and preferably represents cyclopropyl, cyclobutyl, cyclopentyl, cyclopent-1-enyl, cyclopent-2-enyl, and cyclopent-3-enyl.

[0189] Compounds of formula IIIA-1 and / or IIIA-2 may alternatively or preferably be included in the medium in addition to compounds of formula III.

[0190] The most preferred compounds of formulas IIIA-1 and IIIA-2 are as follows:

[0191]

[0192]

[0193]

[0194] Where alkoxy represents a straight-chain alkoxy group having 1-6 carbon atoms, or alternatively –(CH2). n F, where n is 2, 3, 4, or 5, preferably C2H4F.

[0195] In a preferred embodiment of the invention, the medium comprises one or more compounds of formula III-3.

[0196]

[0197] in

[0198] R 31 R 32 The same or different representations of H, alkyl or alkoxy groups having 1 to 15 C atoms, wherein one or more CH2 groups among these groups are optionally independently of each other marked with -C≡C-, -CF2O-, -OCF2-, -CH=CH-, The O atoms can be replaced by -O-, -CO-O-, or -O-CO- in such a way that the O atoms are not directly connected to each other, and one or more of the H atoms can be replaced by halogens.

[0199] The compounds of formula III-3 are preferably selected from compounds of formulas III-3-1 to III-3-10:

[0200]

[0201]

[0202] Where R 32The alkyl group having 1 to 7 carbon atoms is preferred, ethyl, n-propyl, or n-butyl, or alternatively cyclopropylmethyl, cyclobutylmethyl, or cyclopentylmethyl, or alternatively –(CH2). n F, where n is 2, 3, 4, or 5, preferably C2H4F.

[0203] In a preferred embodiment of the invention, the medium comprises one or more compounds of formula III-4 to III-6, preferably formula III-5.

[0204]

[0205] The parameters have the meanings given above, R 31 Preferably, it represents straight-chain alkyl and R 32 Preferably, alkoxy groups are represented, each having 1 to 7 carbon atoms.

[0206] In a preferred embodiment, the medium comprises one or more compounds of formula III selected from formulas III-7 to III-9, preferably formula III-8.

[0207]

[0208] The parameters have the meanings given above, R 31 Preferably, it represents straight-chain alkyl and R 32 Preferably, alkoxy groups are represented, each having 1 to 7 carbon atoms.

[0209] In a preferred embodiment, the medium comprises one or more compounds of formula IV.

[0210]

[0211] in

[0212] R 41 This indicates an alkyl group having 1 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms, preferably a n-alkyl group, and particularly preferably having 2, 3, 4, or 5 carbon atoms.

[0213] R 42 The term refers to an alkyl group having 1 to 7 carbon atoms or an alkoxy group having 1 to 6 carbon atoms (both preferably having 2 to 5 carbon atoms), an alkenyl group having 2 to 7 carbon atoms, preferably having 2, 3 or 4 carbon atoms, more preferably vinyl or 1-propenyl, especially vinyl.

[0214] The compounds of formula IV are preferably selected from compounds of formulas IV-1 to IV-4.

[0215]

[0216] in

[0217] alkyl and alkyl', independently of each other, represent alkyl groups having 1 to 7 carbon atoms, preferably having 1 to 5 carbon atoms.

[0218] alkenyl indicates an alkenyl group having 2 to 5 carbon atoms, preferably 2 to 4 carbon atoms, and particularly preferably 2 carbon atoms.

[0219] 'alkenyl' indicates an alkenyl group having 2 to 5 carbon atoms, preferably 2 to 4 carbon atoms, particularly preferably 2 to 3 carbon atoms, and...

[0220] alkoxy means an alkoxy group having 1 to 5 carbon atoms, preferably having 2 to 4 carbon atoms.

[0221] The compounds of formula IV-1 are preferably selected from compounds of formulas IV-1-1 to IV-1-6:

[0222]

[0223]

[0224] The compounds of formula IV-2 are preferably selected from compounds of formulas IV-2-1 and IV-2-2.

[0225]

[0226] The compounds of formula IV-3 are preferably selected from compounds of formulas IV-3-1, IV-3-2 and IV-3-3.

[0227]

[0228]

[0229] Wherein alkyl has the meaning defined above, and wherein compounds of formula I are excluded from formula IV-3-2.

[0230] The compounds of formula IV-3-1, IV-3-2 and IV-3-3 are preferably selected from the following compounds:

[0231]

[0232]

[0233] Very preferably, the medium according to the invention comprises a compound of formula IV-4, particularly compounds selected from formulas IV-4-1 to IV-4-3.

[0234]

[0235] The liquid crystal medium preferably further comprises one or more compounds of formula IVa.

[0236]

[0237] in

[0238] R 41 and R 42 Each of these independently represents a straight-chain alkyl, alkoxy, alkenyl, alkoxyalkyl, or alkoxy group having up to 12 carbon atoms.

[0239] express or ,

[0240] Z 4 The following represent single bonds: -CH2CH2-, -CH=CH-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -COO-, -OCO-, -C2F4-, -C4H8-, -CF=CF-.

[0241] Preferred compounds of formula IVa are shown below:

[0242]

[0243] in

[0244] Alkyl and alkyl* each independently represent straight-chain alkyl groups having 1 to 6 carbon atoms.

[0245] The medium according to the invention preferably comprises at least one compound of formula IVa-1 and / or formula IVa-2.

[0246] The proportion of the IVa compound in the whole mixture is preferably less than 5% by weight, and very preferably less than 2% by weight.

[0247] Preferably, the medium comprises one or more compounds of formula IVb-1 to IVb-4, more preferably compounds of formula IVb-1 to IVb-3.

[0248]

[0249]

[0250] in

[0251] alkyl and alkyl* each independently represent straight-chain alkyl groups having 1 to 6 carbon atoms, and

[0252] alkenyl and alkenyl* each independently represent straight-chain alkenyl groups having 2 to 6 carbon atoms.

[0253] Of the compounds of formulas IVb-1 to IVb-3, the compound of formula IVb-2 is particularly preferred.

[0254] The preferred biphenyl is

[0255]

[0256] Wherein alkyl* represents an alkyl group having 1 to 6 carbon atoms and preferably represents n-propyl. The media according to the invention particularly preferably comprise one or more compounds of formula IVb-1-1 and / or IVb-2-3.

[0257] In a preferred embodiment, the medium according to the invention comprises one or more compounds of formula V.

[0258]

[0259] in

[0260] R 51 R 52 Independently representing an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkoxyalkyl, alkenyl, or alkenoxy group having 2 to 7 carbon atoms.

[0261] and The same or different, indicating , or ,

[0262] Z 51 Z 52 Each independently represents -CH2-CH2-, -CH2-O-, -CH=CH-, -C≡C-, -COO- or a single bond, and

[0263] n is 1 or 2,

[0264] Among them, the compounds with the exclusion formula CL.

[0265] The compounds of formula V are preferably selected from compounds of formulas V-1, V-2 and V-3:

[0266]

[0267] The groups appearing therein have the meanings given above for formula V.

[0268] The compounds of formula V-1 are preferably selected from compounds of formulas Vl-1 to Vl-8;

[0269] Compounds of formula V-2 are preferably selected from compounds of formulas V-2-1 to V-2-4; and

[0270] Compounds of formula V-3 are preferably selected from compounds of formulas V-3-1 to V-3-7:

[0271]

[0272]

[0273]

[0274] Where R 51 and R 52 It has the meaning shown in Equation V above.

[0275] R 51 and R 52 Preferably, each of the terms represents a straight-chain alkyl group having 1 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms, and each is independent of the other.

[0276] The most preferred compounds of formula V-2-1 are selected from compounds of formula V-2-1a to V-2-1g.

[0277]

[0278]

[0279] The most preferred compounds of formula V-2-2 are selected from compounds of formula V-2-2a to V-2-2i.

[0280]

[0281] Preferably, the medium according to the invention comprises one or more compounds of the formula CL.

[0282]

[0283] in

[0284] R L The symbol represents H, a straight-chain or branched alkyl or alkoxy group having 1 to 15 carbon atoms, or a straight-chain or branched alkenyl group having 2 to 15 carbon atoms, wherein one or more CH2 groups of these groups can be independently separated from each other. The following halogens are used to replace the oxygen atoms: -C≡C-, -CF₂O-, -OCF₂-, -CH=CH-, -O-, -CO-O-, or -O-CO-, such that the oxygen atoms are not directly connected to each other, and in addition, one or more hydrogen atoms may be replaced by halogens.

[0285] X L This indicates that F, Cl, CN, CHF2, CF3, OCF3, or similarly or differently, have R L One of the meanings,

[0286] Y L It represents H, F, Cl, or CH3.

[0287] The compounds of formula CL are preferably selected from compounds of formula CL-1, CL-2 and CL-3.

[0288]

[0289] in

[0290] R L1 and R L2 The same or different have the meanings given above for Formula I, and preferably represent alkyl or alkenyl groups having 1-7 C atoms or 2-7 C atoms, wherein the CH2 group can be replaced by cyclopropane-1,2-diyl, and R L2 Alternatively, it can represent an alkoxy group having 1 to 5 carbon atoms.

[0291] The most preferred CL compounds are selected from compounds of formulas CL-3-1 to CL-3-12:

[0292]

[0293]

[0294] In a particularly preferred embodiment, the medium according to the invention comprises compound CL-3-1 or CLP-3-3.

[0295] In a preferred embodiment of the invention, the medium further comprises one or more compounds of formula VI.

[0296]

[0297] in

[0298] R 61 and R 62 The groups represent H, F, straight-chain alkyl or alkoxy groups having 1 to 15 carbon atoms, straight-chain alkenyl or alkenyloxy groups having 2 to 15 carbon atoms, or branched alkyl, alkoxy, alkenyl, or alkenyloxy groups each having 3 to 15 carbon atoms, wherein one or more CH2 groups among these groups can be independently separated from each other. The H atoms can be replaced by -C≡C-, -CF₂O-, -OCF₂-, -CH=CH-, -O-, -CO-O-, or -O-CO- in such a way that the O atoms are not directly connected to each other, and one or more of the H atoms can be replaced by halogens.

[0299] X 61 X 62 X 63 X64 X 65 and X 66 H or F may be represented in the same or different ways, with X being preferred. 61 X 62 X 63 X 64 X 65 and X 66 At least one of them represents F, more preferably X. 61 X 62 X 63 X 64 X 65 and X 66 At least two of them represent F;

[0300] Z 61 and Z 62 One of them represents CH2CH2, and Z 61 and Z 62 Another representation of a single bond is in the symbol.

[0301]

[0302] The groups appearing therein have the meanings given in Formula VI.

[0303] The compounds of this formula are preferably selected from formulas VI-1-1 to VI-1-15, with formula VI-1-1 being the most preferred:

[0304]

[0305]

[0306]

[0307] Where R 6 (O) represents a straight-chain alkyl or alkoxy group having 1 to 6 C atoms, (O) represents -O- or a single bond, and m is 0, 1, 2, 3, 4, 5 or 6 and n is 0, 1, 2, 3 or 4.

[0308] R preferably represents methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy, or pentoxy.

[0309] In a preferred embodiment of the invention, the medium further comprises one or more compounds of formulas VII-1 to VII-9.

[0310]

[0311]

[0312] in

[0313] R 7 This indicates a straight-chain alkyl or alkoxy group having 1 to 6 carbon atoms, or a straight-chain alkenyl group having 2 to 6 carbon atoms.

[0314] w is an integer from 1 to 6.

[0315] Preferably, the medium according to the invention comprises one or more compounds of formula VIII:

[0316]

[0317] in

[0318] R 81 and R 82 The same or different groups may represent H, halogen, CN, SCN, a straight-chain alkyl or alkoxy group having 1 to 15 carbon atoms, a straight-chain alkenyl or alkenyloxy group having 2 to 15 carbon atoms, or a branched alkyl, alkoxy, alkenyl, or alkenyloxy group having 3 to 15 carbon atoms, wherein one or more CH2 groups of these groups may be independently converted to carbon. -C≡C-, -CF₂O-, -OCF₂-, -CH=CH-, are replaced by -O-, -CO-O-, or -O-CO- in a manner that prevents the O atoms from being directly connected to each other, and one or more of the H atoms may be replaced by halogens.

[0319] A 0 A 81 , and A 82 Each of these represents phenylene-1,4-diyl, wherein one or two CH groups may be replaced by N and one or more H atoms may be replaced by halogen, CN, CH3, CHF2, CH2F, CF3, OCH3, OCHF2 or OCF3, cyclohexane-1,4-diyl, wherein one or two non-adjacent CH2 groups may be replaced by O and / or S and one or more H atoms may be replaced by F, cyclohexene-1,4-diyl, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, tetrahydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl;

[0320] Z 81 and Z 82Each of these can be independently represented as -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CO-O-, -O-CO-, -C2H4-, -C2F4-, -CF2CH2-, -CH2CF2-, -CFHCFH-, -CFHCH2-, -CH2CFH-, -CF2CFH-, -CFHCF2-, -CH=CH-, -CF=CH-, -CH=CF-, -CF=CF-, -C≡C- or a single bond;

[0321] n represents 0, 1, 2, or 3, preferably 0, 1, or 2, very preferably 0 or 1, and particularly preferably 0; and

[0322] m represents 0, 1, 2 or 3, preferably 0, 1 or 2, very preferably 1 or 2, especially 1.

[0323] In formula VIII, A 81 and A 82 Preferably, it represents phenylene-1,4-diyl, which may also be mono- or poly-substituted with F, as well as cyclohexane-1,4-diyl, cyclohexene-1,4-diyl, tetrahydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl, very preferably phenylene-1,4-diyl, which may also be mono- or poly-substituted with F, or cyclohexane-1,4-diyl.

[0324] In formula VIII, Z 81 and Z 82 Preferred representations are -CF2O-, -OCF2-, or single bonds, with single bonds being highly preferred.

[0325] In formula VIII, A 81 and A 82 Special preference indicates, , or

[0326] Where L represents halogen, CF3 or CN, preferably F.

[0327] Further preferred compounds are those of formula VIII, wherein R 81 and R 82 Each of them independently represents H, F, or an alkyl, alkoxy, alkenyl, or alkynyl group having 1 to 8, preferably 1 to 5, carbon atoms, each optionally substituted with a halogen, particularly F.

[0328] R 81 and R 82 Preferably, H represents an alkyl or alkoxy group having 1 to 7 carbon atoms, an alkenyl or alkynyl group having 2 to 7 carbon atoms having 2 to 7 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms having 3 to 12 carbon atoms.

[0329] Preferably, R 81 and R 82 At least one of them is not H, and R is particularly preferred. 81 and R 82 Neither of them are H. R 81 Alkyl groups are highly preferred. 82 Furthermore, H, alkyl, or fluorine are preferred. Very particularly preferred is R. 81 alkyl and R 82 It is H or an alkyl group. R 81 R 82 Each and every one of them, very particularly preferred, represents a non-branched alkyl group having 1 to 5 carbon atoms. If R 81 and R 82 The substituted alkyl, alkoxy, alkenyl, or alkynyl groups are indicated by the presence of two R groups. 81 and R 82 The total number of C atoms in the sample is preferably less than 10.

[0330] Preferred compounds of formula VIII are selected from compounds of formula VIIIa:

[0331]

[0332] Where R 1 and R 2 The same or different may refer to a straight-chain alkyl group having 1 to 15 carbon atoms, a straight-chain alkenyl group having 2 to 15 carbon atoms, or a branched alkyl or alkenyl group having 3 to 15 carbon atoms, wherein one or more CH2 groups of these groups may be independently replaced by each other. The substitution is made, and one or more of the H atoms can be replaced by fluorine, preferably R. 1 and R 2 All of these refer to straight-chain alkyl groups having 1 to 6 carbon atoms.

[0333] The most preferred compounds of formula VIIIa are selected from compounds of formulas VIIIa-1 to VIIIa-35:

[0334]

[0335]

[0336]

[0337]

[0338]

[0339]

[0340]

[0341]

[0342] Where v is an integer from 1 to 6.

[0343] Further preferred compounds of formula VIII are selected from the following sub-formulas:

[0344]

[0345]

[0346] Where R 81 R 82 Let L have the above meanings, where L preferably represents F, and r, s, and t are independently 0, 1, 2, 3, or 4. r is preferably 1 or 2, very preferably 2, and s and t are independently preferably 0 or 1, very preferably 0. R 81 and R 82 In particular, it independently represents n-alkyl groups having 1 to 5 carbon atoms.

[0347] In a first very preferred embodiment, the compounds of formulas VIII-1 to VIII-6 are selected from compounds of formulas VIII-1a to VIII-6a, particularly compounds of formula VIII-3a:

[0348]

[0349]

[0350] Where R 81 R 82 r and s have the meanings defined above.

[0351] In a second, very preferred embodiment, the compounds of formulas VIII-1 to VIII-6 are selected from compounds of formulas VIII-1b to VIII-6b, particularly compounds of formula VIII-3b:

[0352]

[0353]

[0354] Where R 81 R 82 L, r, and s have the meanings defined above.

[0355] In a third, very preferred embodiment, the compounds of formulas VIII-1 to VIII-6 are selected from compounds of formulas VIII-1c to VIII-6c, particularly compounds of formula VIII-3c:

[0356]

[0357] Where R 81 R 82 L, r, and s have the meanings defined above.

[0358] In the fourth very preferred embodiment, the compounds of formulas VIII-1 to VIII-6 are selected from the compounds of formulas VIII-1d to VIII-6d, particularly the compounds of formula VIII-3d.

[0359]

[0360] Where R 81 R 82 L, r, and s have the meanings defined above.

[0361] In a particularly preferred embodiment, the medium according to the invention comprises one or more compounds selected from formulas VIII-1a to VIII-6a and one or more compounds selected from formulas VIII-1b to VIII-6b.

[0362] Very particularly preferred is that the medium comprises one or more compounds selected from compounds of formulas VIII-3a, VIII-3b, VIII-3c, and VIII-3d:

[0363]

[0364] Where R 81 R 82 L and r have the meanings defined above, and preferably r is 0.

[0365] The most preferred compounds of formula VIII specifically include one or more of the following:

[0366]

[0367]

[0368]

[0369]

[0370] Alternatively or additionally, compounds of formula VIII may be used:

[0371]

[0372]

[0373]

[0374]

[0375]

[0376] In a preferred embodiment, the medium comprises one or more compounds of formula IX.

[0377]

[0378] in

[0379] R 1 and R 2 The same or different representations of H, halogen, straight-chain alkyl or alkoxy groups having 1 to 15 carbon atoms, straight-chain alkenyl or alkenyloxy groups having 2 to 15 carbon atoms, or branched alkyl, alkoxy, alkenyl, or alkenyloxy groups each having 3 to 15 carbon atoms, wherein one or more CH2 groups of these groups may be independently represented by each other. -C≡C-, -CF₂O-, -OCF₂-, -CH=CH-, are replaced by -O-, -CO-O-, or -O-CO- in such a way that the O atoms are not directly connected to each other, and one or more of the H atoms can be replaced by halogens.

[0380] L 11 and L 12 Each can be independently represented as F, Cl, CF3, or CHF2.

[0381] L 13 and L 14 Each can be independently represented as H, F, Cl, CF3, or CHF2.

[0382] Y 1 It represents H, F, Cl, CF3, CHF2 or CH3, preferably H or CH3, and

[0383] n is 0 or 1.

[0384] The preferred LC medium is a compound of formula IX, where n is 0, Y represents H or CH3, more preferably H, and L 11 and L 12 It represents F.

[0385] The most preferred compounds of formula IX are selected from compounds of formulas IX-1 to IX-35.

[0386]

[0387]

[0388]

[0389]

[0390]

[0391]

[0392]

[0393]

[0394]

[0395]

[0396] In a preferred embodiment of the invention, the medium comprises one or more compounds of formula X.

[0397]

[0398] in

[0399] express ,

[0400] express or ,

[0401] R X This refers to a straight-chain or branched alkyl or alkoxy group having 1 to 15 carbon atoms, wherein one or more CH2 groups among these groups can be independently separated from each other. -C≡C-, -CF₂O-, -OCF₂-, -CH=CH-, -O-, -CO-O-, or -O-CO- are used to replace the O atoms in such a way that the O atoms are not directly connected to each other, and wherein, in addition, one or more H atoms may be replaced by halogens, preferably by F.

[0402] X X This indicates F, Cl, CN, SF5, SCN, NCS, or a haloalkyl or haloalkoxy group having 1 to 6 carbon atoms, or a haloalkenyl or haloalkenoxy group having 2 to 6 carbon atoms.

[0403] Z X It represents -C2H4-, -CH2O-, CF2O, -CH=CH- or a single bond.

[0404] In compound X, R X Preferably, it represents an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, which is preferably linear.

[0405] In compound X, X X Preferably, it is F, Cl, or a monofluoro or polyfluoroalkyl or alkoxy group having 1, 2, or 3 carbon atoms, or a monofluoro or polyfluoroalkenyl group having 2 or 3 carbon atoms. X X More preferably, F, Cl, CF3, CHF2, OCF3, OCHF2, OCFHCF3, OCFHCHF2, OCFHCHF2, OCF2CH3, OCF2CHF2, OCF2CHF2, OCF2CF2CHF2, OCF2CF2CHF2, OCF2CF2CHF2, OCFHCF2CF3, OCFHCF2CHF2, OCF2CF2CF3, OCF2CF2CClF2, OCClFCF2CF3, OCH=CF2 or CH=CF2, very preferably F or OCF3, in addition CF3, OCF=CF2, OCHF2 or OCH=CF2, very particularly preferred F, OCF3 or CF3, most preferably F.

[0406] Preferred compounds of formula X are selected from the following sub-formulas:

[0407]

[0408] Where R X X has one of the meanings given in Formula X and preferably represents a straight-chain alkyl group having 1 to 6 carbon atoms, very preferably ethyl, propyl, or butyl, or a straight-chain alkenyl group having 2 to 6 carbon atoms, very preferably vinyl or 1-propenyl, most preferably vinyl, and X X It has one of the meanings given in formula X and preferably represents F, CF3 or OCF3, with F being very preferred.

[0409] The most preferred compound X is selected from the following sub-formulas:

[0410]

[0411]

[0412]

[0413]

[0414]

[0415]

[0416]

[0417]

[0418] Preferably, the LC medium comprises one or more compounds selected from formulas X1-1, X1-3, X2-1, and X2-3.

[0419] In a preferred embodiment of this disclosure, the medium further comprises one or more compounds of formula XI.

[0420]

[0421] in

[0422] R 111 and R 112 The same or different representations of F or Cl, or having the group R as defined above for formula IIA-1 2A One meaning is that it preferably contains F or Cl, or a straight-chain alkyl group having 1 to 7 carbon atoms, or a straight-chain alkenyl group having 2 to 7 carbon atoms.

[0423] X 111 X 112 and X 113 The same or different representations of H, F, Cl, CF3 or CHF2 are preferred. 111 X 112 and X 113 At least one of them represents F,

[0424]

[0425] In a preferred embodiment of this disclosure, the medium further comprises one or more compounds of formula XII.

[0426]

[0427] in

[0428] R 12 Having the R of claim 1 2A The given meaning preferably indicates an alkyl group having 1 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms.

[0429] and Representing each other independently or ,and Alternative representation

[0430] L 121 L 122 and L 123 H or F can be represented independently of each other.

[0431] Y 12It represents H or CH3, with H being preferred.

[0432] X 12 The term represents a halogen, a haloalkyl or haloalkoxy group having 1 to 3 carbon atoms, or a haloalkenyl or haloalkenoxy group having 2 or 3 carbon atoms, preferably F, Cl, CF3, OCF3 or OCHF2, more preferably F or OCF3.

[0433] Preferred compounds of formula XII are selected from compounds of formulas XII-1 to XII-4.

[0434]

[0435]

[0436] The groups that appear have the meanings given above.

[0437] The compound of formula XII-4 is highly preferred.

[0438] Further preferred implementation schemes are listed below:

[0439] a) A liquid crystal medium comprising at least one compound of formula Z-1 to Z-8, preferably of formulas Z-2, Z-4 and Z-6, and most preferably of compound Z-4.

[0440]

[0441]

[0442] Where R Z Having the above for R 2A The indicated meaning, and preferably, refers to an alkyl group having 1 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms.

[0443] (O) represents O or a single bond, and alkyl represents an alkyl group having 1 to 7 carbon atoms.

[0444] b) A preferred liquid crystal medium according to the present invention comprises one or more substances containing tetrahydronaphthyl or naphthyl units, for example, compounds of formulas N-1 to N-5.

[0445]

[0446]

[0447] Where R 1N and R 2N Each has its own independent characteristics targeting R. 2A The meaning of the indication preferably represents a straight-chain alkyl, a straight-chain alkoxy, or a straight-chain alkenyl group, and

[0448] Z1 and Z 2 Each of these can be represented independently as -C2H4-, -CH=CH-, -(CH2)4-, -(CH2)3O-, -O(CH2)3-, -CH=CHCH2CH2-, -CH2CH2CH=CH-, -CH2O-, -OCH2-, -COO-, -OCO-, -C2F4-, -CF=CF-, -CF=CH-, -CH=CF-, -CF2O-, -OCF2-, -CH2-, or a single bond.

[0449] c) Preferred mixtures comprise one or more difluorodibenzo-p-chromium compounds selected from formula BC, chromium compounds of formula CR, and fluorophenanthrene compounds of formulas PH-1 and PH-2.

[0450]

[0451]

[0452] Where R B1 R B2 R CR1 R CR2 R P1 R P2 Each has independently possessing R in Equation III 31 The meaning of "preferably" is an alkyl or alkoxy group having 1-6 C atoms, where c is 0, 1 or 2.

[0453] Particularly preferred compounds of formulas BC, CR, and PH-1 are compounds BC-1 to BC-7, CR-1 to CR-5, and BP-1 to BP-7.

[0454]

[0455]

[0456]

[0457]

[0458]

[0459] in

[0460] alkyl and alkyl * Each independently represents a straight-chain alkyl group having 1 to 6 carbon atoms, and

[0461] alkenyl and alkenyl * Each of them independently represents a straight-chain alkenyl group having 2 to 6 C atoms.

[0462] More preferably, it contains one, two or three compounds of the formula BC-2, BC-3, BP-2 and / or BP-3, very preferably BP-2 and / or BP-3, especially a mixture of BP-3 compounds.

[0463] d) Preferred mixtures contain one or more Ininium compounds,

[0464]

[0465] in

[0466] R 11 R 12 , and R 13 Each of these groups independently represents a straight-chain alkyl, alkoxy, alkoxyalkyl, or alkenyl group having 1-6 carbon atoms.

[0467] R 12 and R 13 Halogens can be represented alternatively, with F being preferred.

[0468] express

[0469]

[0470] i represents 0, 1, or 2.

[0471] Preferred In compounds are those of formulas In-1 to In-16 as described below:

[0472]

[0473]

[0474]

[0475]

[0476] Compounds of formulas In-1, In-2, In-3 and In-4 are particularly preferred.

[0477] e) Preferred mixtures additionally contain one or more compounds of formulas L-1 to L-5,

[0478]

[0479]

[0480] in

[0481] R, R 1 and R 2 Each of them independently possesses the above-mentioned characteristics for R in Equation IIA.2A The meaning of the term is as follows: alkyl indicates an alkyl group having 1-6 carbon atoms. The parameter s indicates 1 or 2.

[0482] Compounds of formulas L-1 to L-9 are preferably used at a concentration of 5-15 wt%, particularly 5-12 wt%, and very particularly preferably 8-10 wt%.

[0483] f) Preferred mixtures additionally contain one or more compounds of formula IIA-Y.

[0484]

[0485] Where R 11 and R 12 Having the above in Equation IIA for R 2A One of the given meanings, and L 1 and L 2 , which may be the same or different from F or Cl.

[0486] Preferred compounds of formula IIA-Y are selected from the following sub-formulas.

[0487]

[0488]

[0489]

[0490]

[0491] Wherein, Alkyl and Alkyl* each independently represent a straight-chain alkyl group having 1-6 carbon atoms, Alkoxy represents a straight-chain alkoxy group having 1-6 carbon atoms, Alkenyl and Alkenyl* each independently represent a straight-chain alkenyl group having 2-6 carbon atoms, and O represents an oxygen atom or a single bond. Alkenyl and Alkenyl* preferably represent CH2=CH-, CH2=CHCH2CH2-, CH3-CH=CH-, CH3-CH2-CH=CH-, CH3-(CH2)2-CH=CH-, CH3-(CH2)3-CH=CH-, or CH3-CH=CH-(CH2)2-.

[0492] The particularly preferred compounds of formula IIA-Y are selected from the following sub-formulas:

[0493]

[0494] Alkoxy and Alkoxy* have the meanings defined above and preferably represent methoxy, ethoxy, n-propyloxy, n-butyloxy or n-pentyloxy, and most preferably both are butyloxy.

[0495] Preferably, the medium according to the invention comprises a stabilizer selected from compounds of formulas ST-1 to ST-23:

[0496]

[0497]

[0498]

[0499]

[0500]

[0501]

[0502]

[0503]

[0504]

[0505]

[0506]

[0507]

[0508] in

[0509] R ST The group represents H, an alkyl or alkoxy group having 1 to 15 carbon atoms, wherein, furthermore, one or more CH2 groups in these groups may be independently separated from each other. -C≡C-, -CF₂O-, -OCF₂-, -CH=CH-, -O-, -CO-O-, -O-CO- are substituted in such a way that the O atoms are not directly connected to each other, and wherein, in addition, one or more H atoms may be substituted with halogens.

[0510] express

[0511]

[0512]

[0513]

[0514] Z STEach of these can be independently represented as -CO-O-, -O-CO-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CH2-, -CH2CH2-, -(CH2)4-, -CH=CH-, -CH2O-, -C2F4-, -CH2CF2-, -CF2CH2-, -CF=CF-, -CH=CF-, -CF=CH-, -CH=CH-, -C≡C-, or a single bond.

[0515] L 1 and L 2 Each can be represented independently as F, Cl, CF3, or CHF2.

[0516] n is an integer from 0 to 12, preferably 5, 6, 7, 8 or 9, and very preferably 7.

[0517] n2, in each occurrence, is either the same or different, preferably an integer from 1 to 12, preferably 2, 3, 4, 5, or 6, very preferably 3, and

[0518] R S In each occurrence, whether identically or differently, it preferably represents an alkyl group having 1 to 6 carbon atoms, preferably n-butyl.

[0519] p represents 1 or 2,

[0520] q represents 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0521] Among compounds of formula ST, compounds of the following formula are particularly preferred.

[0522]

[0523] Where n = 1, 2, 3, 4, 5, 6 or 7, preferably n = 1 or 7.

[0524]

[0525] Where n = 1, 2, 3, 4, 5, 6, or 7, preferably n = 3.

[0526]

[0527] Where n = 1, 2, 3, 4, 5, 6, or 7, preferably n = 3.

[0528]

[0529]

[0530]

[0531]

[0532] In compounds of formula ST-3a and ST-3b, n preferably represents 3. In compounds of formula ST-2a, n preferably represents 7.

[0533] A particularly preferred mixture according to the invention comprises one or more stabilizers selected from compounds of formula ST-2a-1, ST-3a-1, ST-3b-1, ST-8-1, ST-9-1, and ST-12:

[0534]

[0535]

[0536]

[0537] Based on the mixture, the compounds of formulas ST-1 to ST-23 are preferably present in the liquid crystal mixture according to the invention in an amount of 0.005-0.5%.

[0538] If the mixture according to the invention contains two or more compounds of formulas ST-1 to ST-23, then based on the mixture, in the case of two compounds, the concentration is increased accordingly to 0.01-1%.

[0539] However, based on the mixtures according to the invention, the total proportion of compounds of formulas ST-1 to ST-23 should not exceed 2%.

[0540] The liquid crystal medium (also referred to herein as a liquid crystal host mixture) according to the invention is suitable for use in polymer-stabilized displays. For this purpose, the medium according to the invention optionally comprises one or more polymerizable compounds of formula P:

[0541] P-Sp-A 1 -(Z 1 -A 2 ) z -RP

[0542] These are independent of each other and appear the same or different each time.

[0543] P represents a polymerizable group.

[0544] Sp represents a spacer group or a single bond.

[0545] A 1 A 2 This indicates an aromatic, heteroaromatic, alicyclic, or heterocyclic group, preferably having 4 to 25 ring atoms. It may also contain a fused ring, and it is unsubstituted, or monosubstituted or polysubstituted.

[0546] Z1 Represents -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -(CH2) n1 -, -CF2CH2-, -CH2CF2-, -(CF2) n1 -, -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, -CH=CH-CO-O-, -O-CO-CH=CH-, -CH2-CH2-CO-O-, -O-CO-CH2-CH2-, -CR 0 R 00 - or single key,

[0547] R 0 R 00 It represents H or an alkyl group having 1 to 12 carbon atoms.

[0548] R represents H, L, or P-Sp-,

[0549] L represents F, Cl, -CN, P-Sp- or a straight-chain, branched, or cycloalkyl group having 1 to 25 C atoms, wherein one or more non-adjacent CH2 groups are optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- in such a way that the O and / or S atoms are not directly connected to each other, and wherein one or more H atoms are each optionally replaced by P-Sp-, F, or Cl.

[0550] z is 0, 1, 2, or 3, and

[0551] n1 is 1, 2, 3 or 4.

[0552] As used in this article, the term "reliability" refers to the quality of a display's performance over time and under varying stress loads, such as optical load, temperature, humidity, and voltage. It also includes display effects such as image lag (surface and line image lag), mura, yogore, etc., which are known to those skilled in the art of LC displays. A standard parameter used for classifying reliability is the voltage hold-up ratio (VHR) value, a measure of maintaining a constant voltage in a tested display. Among other factors, a high VHR is a prerequisite for high reliability in LC media.

[0553] Unless otherwise stated, the term "PSA" will be used hereinafter when referring generally to displays of polymer-maintained alignment type, and the term "PS" will be used when referring to a specific display mode (such as PS-VA, PS-TN, etc.).

[0554] As used herein, the terms “active layer” and “switchable layer” refer to a layer in an electro-optic display, such as an LC display, comprising one or more molecules (e.g., LC molecules) having structural and optical anisotropy, which change their orientation when subjected to external stimuli such as an electric or magnetic field, resulting in a change in the layer’s transmittance to polarized or unpolarized light.

[0555] As used herein, the terms "tilt" and "tilt angle" should be understood to refer to the tilted orientation of LC molecules of the LC medium relative to the cell surface in an LC display (preferably a PSA display). The tilt angle here represents the average angle (< 90°) between the longitudinal molecular axis (LC director) of the LC molecules and the outer plate parallel to the plane forming the LC cell. Lower tilt angle values ​​(i.e., larger deviations from 90°) correspond to larger tilts. Suitable methods for measuring tilt angles are provided in the embodiments. Unless otherwise stated, the tilt angle values ​​disclosed in the context are related to this measurement method.

[0556] As used herein, the terms “reactive mesocrystalline” and “RM” should be understood to mean a compound comprising a mesocrystalline or liquid crystal framework and one or more functional groups attached thereto suitable for polymerization, and said functional groups are also referred to as “polymerizable groups” or “P”.

[0557] Unless otherwise stated, the term “polymerizable compound” as used herein should be understood as a polymerizable monomeric compound.

[0558] As used herein, the term “low molecular weight compound” should be understood to mean a monomeric compound and / or a compound not prepared by polymerization, as opposed to “polymeric compound” or “polymer”.

[0559] As used herein, the term "non-polymerizable compound" should be understood to mean a compound that does not contain functional groups suitable for polymerization under the conditions typically applied to RM polymerization.

[0560] As used herein, the term "mesocrystalline group" is known to those skilled in the art and described in the literature, and it refers to a group that substantially contributes to the formation of a liquid crystal (LC) phase in a low molecular weight or polymeric substance due to the anisotropy of its attractive and repulsive interactions. A compound containing a mesocrystalline group (mesocrystalline compound) does not necessarily have an LC phase by itself. Mesocrystalline compounds may also exhibit LC phase behavior only when mixed with other compounds and / or after polymerization. Typical mesocrystalline groups are, for example, rigid rod-shaped or disk-shaped units. The terms and definitions used in relation to mesocrystalline or LC compounds are given in Pure Appl. Chem. 2001, 73(5), 888 and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368.

[0561] As used herein, the terms “optically active” and “chiral” are synonymous for materials that can induce helical pitch in nematic host materials, also known as “chiral dopants”.

[0562] As used herein, the term "spacer group" (also referred to as "Sp" in the context) is known to those skilled in the art and 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 group" or "spacer base" means a flexible group, such as an alkylene group, that connects a mesocrystalline group and a polymerizable group (one or more) in a polymerizable mesocrystalline compound.

[0563] Similarly, in the compounds of formulas Ia and Ib, the spacer group connects the central hydrocarbon group to a photoactive, stable sterically hindered amine functional group.

[0564] In the context, It represents the trans-1,4-cyclohexyl ring.

[0565] In groups In the diagram, it is shown that the single bond between two ring atoms can be attached to any free position on the benzene ring.

[0566] In this context, "organic group" refers to a carbon or hydrocarbon group.

[0567] "Carbon group" refers to a monovalent or polyvalent organic group containing at least one carbon atom, wherein the group does not contain other atoms (e.g., -C≡C-) or optionally contains one or more other atoms, such as N, O, S, B, P, Si, Se, As, Te, or Ge (e.g., carbonyl group). The term "hydrocarbon group" 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.

[0568] "Halogen" refers to F, Cl, Br or I, with F or Cl being preferred.

[0569] -CO-, -C(=O)-, and -C(O)- represent carbonyl groups, i.e. .

[0570] The carbon or hydrocarbon group can be saturated or unsaturated. Unsaturated groups are, for example, aryl, alkenyl, or alkynyl groups. Carbon or hydrocarbon groups having more than 3 carbon atoms can be straight-chain, branched, and / or cyclic, and may also contain spirolinked or fused rings.

[0571] The terms "alkyl", "aryl", and "heteroaryl" also include polyvalent groups, such as alkylene, arylene, and heteroarylene.

[0572] The term "aryl" refers to an aromatic carbon group or a group derived therefrom. The term "heteroaryl" refers to an "aryl" group as defined above that contains one or more heteroatoms (preferably selected from N, O, S, Se, Te, Si, and Ge).

[0573] Preferred carbon and hydrocarbon groups are optionally substituted, and are straight-chain, branched, or cyclic alkyl, alkenyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyl, and alkoxy carbonyloxy groups having 1 to 40, preferably 1 to 20, very preferably 1 to 12 C atoms; optionally substituted aryl or aryloxy groups having 5 to 30, preferably 6 to 25 C atoms; or optionally substituted alkylaryl, aralkyl, alkylaryloxy, arylalkyloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy, and aryloxycarbonyloxy groups having 5 to 30, preferably 6 to 25 C atoms, wherein one or more C atoms may also be replaced by heteroatoms (preferably selected from N, O, S, Se, Te, Si, and Ge).

[0574] Further preferred carbon and hydrocarbon groups are C1-C. 20 Alkyl, C2-C 20 alkenyl, C2-C 20 alkynyl group, C3-C 20 Allyl, C4-C 20 Alkyl diene group, C4-C 20 Polyene, C6-C 20cycloalkyl, C4-C 15 Cycloalkenyl, C6-C 30 Aryl, C6-C 30 Alkyl aryl, C6-C 30 Aryl group, C6-C 30 Alkyl aryloxy, C6-C 30 arylalkoxy, C2-C 30 heteroaryl, C2-C 30 heteroaryloxyl.

[0575] C1-C is particularly preferred. 12 Alkyl, C2-C 12 alkenyl, C2-C 12 alkynyl group, C6-C 25 Aryl and C2-C 25 Mixed aromatic compounds.

[0576] Further preferred carbonyl and hydrocarbon groups are straight-chain, branched, or cyclic alkyl groups having 1-20, preferably 1-12 C atoms, which are unsubstituted or mono- or polysubstituted with F, Cl, Br, I, or CN, and one or more non-adjacent CH2 groups may be independently converted to -C(R) x )=C(R x )-、-C≡-、-N(R x -, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-, -O-CO-O- are used to replace O and / or S atoms in a way that prevents them from being directly connected to each other.

[0577] R x Preferably, it represents H, F, Cl, CN, a straight-chain, branched, or cyclic alkyl chain having 1 to 25 C atoms, wherein one or more non-adjacent C atoms may be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, and one or more H atoms may be replaced by F or Cl, or it represents an optionally substituted aryl or aryloxy group having 6 to 30 C atoms, or an optionally substituted heteroaryl or heteroaryloxy group having 2 to 30 C atoms.

[0578] Preferred alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, dodecyl, trifluoromethyl, perfluoron-butyl, 2,2,2-trifluoroethyl, perfluorooctyl, perfluorohexyl, etc.

[0579] Preferred alkenyl groups include, for example, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, etc.

[0580] Preferred alkynyl groups include, for example, ethynyl, propynyl, butynyl, penynyl, hexynyl, octyynyl, etc.

[0581] Preferred alkoxy groups include, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, 2-methylbutoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecoxy, n-dodecoxy, etc.

[0582] Preferred amino groups include, for example, dimethylamino, methylamino, methylphenylamino, phenylamino, etc.

[0583] Aryl and heteroaryl groups can be monocyclic or polycyclic, meaning they can contain one ring (e.g., phenyl) or two or more rings, and can be fused (e.g., naphthyl) or covalently bonded (e.g., biphenyl), or a combination of fused and linking rings. Heteroaryl groups contain one or more heteroatoms, preferably selected from O, N, S, and Se.

[0584] Particularly preferred are mono-, di-, or tricyclic aryl groups having 6-25 carbon atoms and mono-, di-, or tricyclic heteroaryl groups having 5-25 ring atoms, optionally containing a fused ring and optionally substituted. Further preferred are 5-, 6-, or 7-membered aryl and heteroaryl groups, wherein one or more CH groups may be replaced by N, S, or O in such a manner that the O atoms and / or S atoms are not directly linked to each other.

[0585] Preferred aryl groups include, for example, phenyl, biphenyl, terphenyl, [1,1':3',1'']-terphenyl-2'-yl, naphthyl, anthracene, bidinaphthyl, phenanthryl, 9,10-dihydro-phenanthryl, pyrene, dihydropyrene. , 2-naphthylbenzene, 3-benzo[a]benzene, 3-penta]benzene, benzo[a]pyrene, fluorene, indene, indo[a]fluorene, spirobifluorene, etc.

[0586] Preferred heteroaryl groups are, for example, 5-membered rings, such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazolium, furan, thiophene, selenophene, oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 6-membered rings, such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetraazine, 1,2,3,4-tetraazine, 1,2,3,5-tetraazine, or fused groups, such as indole, isoindole, indole Azine, Indazole, Benzimidazole, Benzitriazole, Purine, Naphthemidazole, Phenylenazole, Pyridinazole, Pyrazinazole, Quinoxaline, Benzooxazole, Naphthemidazole, Anthraxazole, Phenylenazole, Isoxazole, Benzothiazol, Benzofuran, Isobenzofuran, Dibenzofuran, Quinoline, Isoquinoline, Pteridine, Benzo-5,6-quinoline, Benzo-6,7-quinoline, Benzo- 7,8-quinoline, benzoisoquinoline, acridine, phenothiazine, phenothiazine, benzopyridinium, quinoxaline, phenothiazine, naphthidine, azacarbazole, benzocarbine, phenanthridine, phenanthroxaline, thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithieno[2,3b]thiophene, isobenzo[2,3b]thiophene, dibenzo[2,3b]thiophene, benzo[2,3b]thiophene, benzo[2,3b]thiophene, di[2,3b]thiophene, isobenzo[2,3b]thiophene, dibenzo[2,3b]thiophene, ...

[0587] The aryl and heteroaryl groups mentioned in the context may also be substituted by alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl or other aryl or heteroaryl groups.

[0588] (Non-aromatic) alicyclic and heterocyclic groups can include both saturated rings (i.e., rings containing only single bonds) and partially unsaturated rings (i.e., those containing multiple bonds). Heterocyclic groups contain one or more heteroatoms, preferably selected from Si, O, N, S, and Se.

[0589] The (non-aromatic) alicyclic and heterocyclic groups can be monocyclic, i.e., containing only one ring (e.g., cyclohexane), or polycyclic, i.e., containing multiple rings (e.g., decahydronaphthalene or bicyclooctane). Saturated groups are particularly preferred. Furthermore, mono-, bi-, or tricyclic groups having 5-25 ring atoms are preferred, optionally containing fused rings and optionally substituted. Further preferred are 5-, 6-, 7-, or 8-membered carbocyclic groups, wherein one or more C atoms may be replaced by Si and / or one or more CH groups may be replaced by N and / or one or more non-adjacent CH2 groups may be replaced by -O- and / or -S-.

[0590] Preferred alicyclic and heterocyclic groups are, for example, 5-membered groups, such as cyclopentane, tetrahydrofuran, tetrahydrothiophene, and pyrrolidine; 6-membered groups, such as cyclohexane, silinane, cyclohexene, tetrahydropyran, tetrahydrothioran, 1,3-dioxane, 1,3-dithiane, and 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, and octahydro-4,7-bridged methylene indane-2,5-diyl.

[0591] Preferred substituents are, for example, solubility-promoting groups, such as alkyl or alkoxy groups; electron-withdrawing groups, such as fluorine, nitro or nitrile groups; or substituents used to increase the glass transition temperature (Tg) of the polymer, especially bulky groups, such as tert-butyl or optionally substituted aryl groups.

[0592] Preferred substituents, hereinafter also referred to as "L" S ", for example, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)N(R x )2、-C(=O)Y 1 -C(=O)R x -N(R) x )2, a straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy or alkoxy carbonyloxy having 1 to 25 C atoms, wherein one or more H atoms may optionally be replaced by F or Cl, an optionally substituted silyl having 1 to 20 Si atoms, or an optionally substituted aryl having 6 to 25, preferably 6 to 15 C atoms.

[0593] Where R x Represents H, F, Cl, CN, or a straight-chain, branched, or cyclic alkyl group having 1 to 25 C atoms, wherein one or more non-adjacent CH2- groups are optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- in such a way that the O- and / or S- atoms are not directly connected to each other, and wherein one or more H atoms are each optionally replaced by F, Cl, P-, or P-Sp-, and

[0594] Y 1 It represents halogens.

[0595] "Substituted silyl or aryl" preferably indicates that it is substituted with halogen, -CN, R 0 -OR 0 -CO-R 0 -CO-OR 0-O-CO-R 0 OR-O-CO-OR 0 Replace, where R 0 It represents H or an alkyl group having 1 to 20 carbon atoms.

[0596] Particularly preferred substituents L include, for example, F, Cl, CN, NO2, CH3, C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5, and also phenyl.

[0597] A 1 and A 2 Highly preferred expression Where L has one of the above meanings and r represents 0, 1, 2, 3 or 4, in particular

[0598] express or

[0599] The polymerizable group P is a group suitable for polymerization reactions (e.g., free radical or ionic chain polymerization, addition polymerization, or condensation polymerization), or a group suitable for polymer-analogous reactions (e.g., addition or condensation on the polymer backbone). Groups suitable for chain polymerization are particularly preferred, especially those containing C=C double bonds or -C≡C- triple bonds, and groups suitable for ring-opening polymerization, such as oxobutyl or epoxy groups.

[0600] The preferred group P is selected from the group consisting of: CH2=CW 1 -CO-O-、CH2=CW 1 -CO-、 , , , CH2=CW 2 -(O) k3 -、CW 1 =CH-CO-(O) k3 -、CW 1 =CH-CO-NH-、CH2=CW 1 -CO-NH-, CH3-CH=CH-O-, (CH2=CH)2CH-OCO-, (CH2=CH-CH2)2CH-OCO-, (CH2=CH)2CH-O-, (CH2=CH-CH2)2N-, (CH2=CH-CH2)2N-CO-, HO-CW 2 W 3 -、HS-CW2 W 3 -、HW 2 N-, HO-CW 2 W 3 -NH-, CH2=CW 1 -CO-NH-, CH2=CH-(COO) k1 -Phe-(O) k2 - CH2=CH-(CO) k1 -Phe-(O) k2 -, Phe-CH=CH-, HOOC-, OCN- and W 4 W 5 W 6 Si-, where W 1 It represents H, F, Cl, CN, CF3, phenyl, or alkyl groups having 1 to 5 carbon atoms, especially H, F, Cl, or CH3, W 2 and W 3 Each independently represents H or an alkyl group having 1 to 5 carbon atoms, particularly H, methyl, ethyl, or n-propyl, W 4 W 5 and W 6 Each independently represents Cl, an oxaalkyl or oxacarbonylalkyl group having 1 to 5 carbon atoms, and W. 7 and W 8 Each of the above-defined groups independently represents H, Cl, or an alkyl group having 1 to 5 C atoms; Phe represents 1,4-phenylene, which is optionally substituted with one or more L groups other than P-SP- as defined above; k1, k2, and k3 each independently represent 0 or 1, k3 preferably represents 1; and k4 represents an integer from 1 to 10.

[0601] The preferred group P is selected from the group consisting of: CH2=CW 1 -CO-O-、CH2=CW 1 -CO-、 , , , CH2=CW 2 -O-、CH2=CW 2 -、CW 1 =CH-CO-(O) k3 -、CW 1 =CH-CO-NH-、CH2=CW 1-CO-NH-, (CH2=CH)2CH-OCO-, (CH2=CH-CH2)2CH-OCO-, (CH2=CH)2CH-O-, (CH2=CH-CH2)2N-, (CH2=CH-CH2)2N-CO-, CH2=CW 1 -CO-NH-, CH2=CH-(COO) k1 -Phe-(O) k2 - CH2=CH-(CO) k1 -Phe-(O) k2 -、Phe-CH=CH- and W 4 W 5 W 6 Si-, where W 1 It represents H, F, Cl, CN, CF3, phenyl, or alkyl groups having 1 to 5 carbon atoms, especially H, F, Cl, or CH3, W 2 and W 3 Each independently represents H or an alkyl group having 1 to 5 carbon atoms, particularly H, methyl, ethyl, or n-propyl, W 4 W 5 and W 6 Each independently represents Cl, an oxaalkyl or oxacarbonylalkyl group having 1 to 5 carbon atoms, and W. 7 and W 8 Each of them independently represents H, Cl or an alkyl group having 1 to 5 C atoms, Phe represents 1,4-phenylene, k1, k2 and k3 each independently represent 0 or 1, k3 preferably represents 1, and k4 represents an integer from 1 to 10.

[0602] The most preferred group P is selected from the group consisting of: CH2=CW 1 -CO-O-, especially CH2=CH-CO-O-, CH2=C(CH3)-CO-O- and CH2=CF-CO-O-, as well as CH2=CH-O-, (CH2=CH)2CH-O-CO-, (CH2=CH)2CH-O-, and .

[0603] Other particularly preferred polymerizable groups P are selected from ethylene oxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxobutyl, and epoxy groups, with the most preferred groups being acrylate and methacrylate.

[0604] If the spacer group Sp is different from a single bond, it is preferably of the formula Sp"-X", such that each group P-Sp- is equivalent to the formula R-Sp"-X"-, wherein

[0605] "Sp" represents a straight-chain or branched alkylene group having 1 to 20, preferably 1 to 12, carbon atoms, optionally mono- or poly-substituted with F, Cl, Br, I, or CN, and wherein one or more non-adjacent CH2 groups are each independently substituted with -O-, -S-, -NH-, or -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- are replaced by O and / or S atoms that are not directly connected to each other.

[0606] 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 )-, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -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 bonds

[0607] R 0 and R 00 Each independently represents H or an alkyl group having 1-20 carbon atoms, and

[0608] Y 2 and Y 3 Each can be represented independently as H, F, Cl, or CN.

[0609] X" is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, or -CO-NR. 0 -、-NR 0 -CO-、-NR 0 -CO-NR 00 - or a single key.

[0610] Typical spacer groups Sp and -Sp"-X"- are, for example, -(CH2). p1 -、-(CH2) p1 -O-、-(CH2) p1 -O-CO-、-(CH2) p1 -CO-O-、-(CH2) p1 -O-CO-O-、-(CH2CH2O) q1 -CH2CH2-, -CH2CH2-S-CH2CH2-, -CH2CH2-NH-CH2CH2- 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 It has the meaning mentioned above.

[0611] The particularly preferred groups Sp and -Sp"-X"- are -(CH2). p1 -、-(CH2) p1 -O-、-(CH2) p1 -O-CO-、-(CH2) p1 -CO-O-、-(CH2) p1 -O-CO-O-, where p1 and q1 have the meanings stated above.

[0612] The particularly preferred group Sp" in each case is a straight-chain ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methylimino-ethylene, 1-methylalkylene, vinylene, propenylene, and butenylene.

[0613] In a preferred embodiment of the invention, compounds of formula P and its subforms contain spacer groups Sp substituted with one or more polymerizable groups P, such that the group Sp-P corresponds to Sp(P). s s is ≥2 (branched polymerizable groups).

[0614] The preferred P compound according to this preferred embodiment is one in which s is 2, i.e., a compound containing the group Sp(P)2. The most preferred P compound according to this preferred embodiment contains a group selected from the following formulas:

[0615]

[0616]

[0617] Where P is defined as in equation P.

[0618] Alkyl refers to a straight-chain or branched alkylene group with a single bond or having 1 to 12 carbon atoms, which is unsubstituted or monosubstituted or polysubstituted with F, Cl or CN, and wherein one or more non-adjacent CH2 groups are each independently bonded to each other in such a manner that the O atom and / or S atom are not directly connected to each other via -C(R) 0 )=C(R 0 )-、-C≡C-、-N(R 0 )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- substitution, where R 0 It has the meaning indicated above.

[0619] aa and bb each independently represent 0, 1, 2, 3, 4, 5, or 6.

[0620] X has one of the meanings indicated by X", and is preferably O, CO, SO2, O-CO-, CO-O or a single bond.

[0621] The preferred spacer group Sp(P)2 is selected from formulas S1, S2 and S3.

[0622] The highly preferred spacer group Sp(P)2 is selected from the following formulas:

[0623]

[0624] In compounds of formula P and its sub-formulas as described above and below, P is preferably selected from the group consisting of: vinyloxy groups, acrylates, methacrylates, fluoroacrylates, chloroacrylates, oxetanes and epoxides, and most preferably selected from acrylates and methacrylates.

[0625] More preferably, compounds of formula P and its sub-formulas as described above and below, wherein all polymerizable groups P present in the compound have the same meaning and very preferably represent acrylates or methacrylates, most preferably methacrylates.

[0626] In compounds of formula P and its sub-formulas as described above and below, R preferably represents P-Sp-.

[0627] More preferably, compounds of formula P and its derivatives as described above and below, wherein Sp represents a single bond or -(CH2). p1 -、-O-(CH2) p1 -、-O-CO-(CH2) p1 Or -CO-O-(CH2) p1 Where p1 is 2, 3, 4, 5 or 6, and if Sp is -O-(CH2)p1 -、-O-CO-(CH2) p1 Or -CO-O-(CH2) p1 Then, the O-atom or CO-group is attached to the benzene ring, respectively.

[0628] More preferably, compounds of formula P and its sub-formulas as described above and below, wherein at least one Sp group is a single bond.

[0629] More preferably, compounds of formula P and its sub-formulas as described above and below, wherein at least one Sp group is different from a single bond and is preferably selected from -(CH2). p1 -、-O-(CH2) p1 -、-O-CO-(CH2) p1 Or -CO-O-(CH2) p1 Where p1 is 2, 3, 4, 5 or 6, and if Sp is -O-(CH2) p1 -、-O-CO-(CH2) p1 Or -CO-O-(CH2) p1 Then, the O-atom or CO-group is attached to the benzene ring, respectively.

[0630] The highly preferred group -A in formula P 1 -(ZA 2 ) z -Selected from the following formula

[0631]

[0632]

[0633] At least one benzene ring is substituted with at least one L group and the benzene ring is optionally further substituted with one or more L or P-Sp groups.

[0634] Preferred formula P and its sub-formula compounds are selected from the following preferred embodiments, including any combination thereof:

[0635] - All the P groups in this compound have the same meaning.

[0636] - -A 1 -(ZA 2 ) z -Selected from formulas A1, A2, and A5,

[0637] - This compound happens to contain two polymerizable groups (represented by the group P).

[0638] - This compound contains exactly three polymerizable groups (represented by the group P).

[0639] - P is selected from the group consisting of acrylates, methacrylates, and oxetanes, with acrylates or methacrylates being particularly preferred.

[0640] - P is methacrylate,

[0641] - All Sp groups are single bonds.

[0642] - At least one of the Sp groups is a single bond and at least one of the Sp groups is different from a single bond.

[0643] - When Sp is different from a single bond, it is -(CH2). p2 -、-(CH2) p2 -O-、-(CH2) p2 -CO-O-、-(CH2) p2 -O-CO-, where p2 is 2, 3, 4, 5 or 6, and the O atom or CO- group is attached to the benzene ring.

[0644] - Sp represents a single bond or -(CH2). p2 -、-(CH2) p2 -O-、-(CH2) p2 -CO-O-、-(CH2) p2 -O-CO-, where p2 is 2, 3, 4, 5 or 6, and the O atom or CO- group is attached to the benzene ring.

[0645] - R stands for P-Sp-,

[0646] - R does not indicate or contains a polymerizable group.

[0647] - R does not represent or contains a polymerizable group and represents a straight-chain, branched, or cyclic alkyl group having 1 to 25 carbon atoms, wherein one or more non-adjacent CH2 groups are optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- in such a way that the O and / or S atoms are not directly connected to each other, and wherein one or more H atoms are each optionally replaced by F, Cl, or L. a Replacement

[0648] -L or L' indicates F, Cl, or CN.

[0649] -L is F.

[0650] Suitable and preferred compounds of formula P are selected from the following formula:

[0651]

[0652]

[0653]

[0654]

[0655]

[0656]

[0657]

[0658]

[0659]

[0660]

[0661]

[0662] Each of the groups has the following meaning:

[0663] P 1 P 2 P 3 Each group independently represents either an acrylate group or a methacrylate group.

[0664] Sp 1 Sp 2 Sp 3 Each of these groups independently represents a single bond or a spacer group having one of the meanings indicated by the context for Sp, and is particularly preferred to represent -(CH2). p1 -, -(CH2) p1 -O-, -(CH2) p1 -CO-O-, -(CH2) p1 -O-CO- or -(CH2) p1 -O-CO-O-, where p1 is an integer from 1 to 12, and in addition, the group P 1 -Sp 1 -, P 2 -Sp 2 -and P 3 -Sp 3 One or more of the representations R in - aa The condition is the presence of the group P. 1 -Sp 1 -, P 2 -Sp 2 and P 3 -Sp 3 - at least one of them is different from R aa ,

[0665] R aaIt represents H, F, Cl, CN, or a straight-chain or branched alkyl group having 1 to 25 C atoms, wherein one or more other non-adjacent CH2 groups may also be independently separated by -C(R) 0 )=C(R 00 -, -C≡C-, -N(R) 0 -, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-, -O-CO-O- can be substituted in such a way that the O and / or S atoms are not directly bonded to each other, and one or more of the other H atoms can be replaced by F, Cl, CN or P. 1 -Sp 1 - Alternatively preferred are straight-chain or branched groups having 1 to 12 carbon atoms, optionally mono- or polyfluorinated alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy (wherein the alkenyl and alkynyl groups have at least two carbon atoms and the branched groups have at least three carbon atoms).

[0666] R 0 R 00 Each of these terms independently, and in each instance, either identically or differently, represents H or an alkyl group having 1 to 12 carbon atoms.

[0667] R y and R z Each can be independently represented as H, F, CH3, or CF3.

[0668] X 1 X 2 and X 3 Each can be independently represented as -CO-O-, -O-CO-, or a single bond.

[0669] Z 1 Represents -O-, -CO-, -C(R) y R z - or -CF2CF2-,

[0670] Z 2 and Z 3 Each can be independently represented as -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CF2O-, -OCF2-, or -(CH2). n - where n is 2, 3, or 4.

[0671] L, in each occurrence, may represent F, Cl, CN, or a straight-chain or branched, optionally mono- or polyfluorinated alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy group having 1 to 12 carbon atoms, preferably representing F.

[0672] L' and L" independently represent H, F, or Cl,

[0673] k represents 0 or 1,

[0674] r represents 0, 1, 2, 3, or 4.

[0675] s represents 0, 1, 2, or 3.

[0676] t represents 0, 1, or 2.

[0677] x represents 0 or 1.

[0678] Compounds of formulas P2, P13, P17, P22, P23, P24, P30, P31 and P32 are particularly preferred.

[0679] Further preferred tri-reactive compounds P15 to P30, especially P17, P18, P19, P22, P23, P24, P25, P26, P30, P31 and P32.

[0680] In compounds of formulas P1 to P32

[0681] Preferred or

[0682] Wherein L, in each occurrence, has the same or different meanings given above or below, and preferably F, Cl, CN, NO2, CH3, C2H5, C(CH3)3, CH(CH3)2, CH2CH(CH3)C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5 or P-Sp-, very preferably F, Cl, CN, CH3, C2H5, OCH3, COCH3, OCF3 or P-Sp-, more preferably F, Cl, CH3, OCH3, COCH3 or OCF3, especially F or CH3.

[0683] The most particularly preferred compounds of formula P are selected from Table E below.

[0684] In order to produce a PSA display, a polymerizable compound contained in an LC medium is polymerized or crosslinked in situ in the LC medium (between the substrates of the LC display) by optionally applying voltage to the electrodes simultaneously (if a compound contains two or more polymerizable groups).

[0685] The structure of the PSA display according to the invention corresponds to the typical geometry of a PSA display, as described in the prior art cited at the beginning. A geometry without protrusions is preferred, particularly those electrodes on the color filter side that are unstructured and have slots only on the TFT side. A particularly suitable and preferred electrode structure for a PS-VA display is described, for example, in US 2006 / 0066793A1.

[0686] The preferred PSA-type LC display of the present invention includes:

[0687] - A first substrate, comprising a pixel electrode defining a pixel region (the pixel electrode is connected to a switching element disposed in each pixel region and optionally includes a microslit pattern), and optionally a first alignment layer disposed on the pixel electrode.

[0688] - A second substrate, comprising a common electrode layer (which may be disposed over the entire portion of the second substrate facing the first substrate), and an optional second alignment layer.

[0689] - An LC layer is disposed between the first substrate and the second substrate and includes an LC medium comprising a polymerizable component and a liquid crystal body. The polymerizable component comprises one or more compounds of formula R, and the liquid crystal body comprises as described above and below, wherein the polymerizable component may also be polymerized.

[0690] The first and / or second alignment layers control the alignment orientation of the LC molecules in the LC layer. For example, in a PS-VA display, the alignment layers are selected to impart vertical (or perpendicular) alignment (i.e., perpendicular to the surface) or tilted alignment to the LC molecules. Such alignment layers may, for example, contain polyimide, which may also be rubbed or prepared by photoalignment methods.

[0691] An LC layer with an LC dielectric can be deposited between the substrates of a display using methods conventionally used by display manufacturers, such as the so-called drop-fill (ODF) method. The polymerizable components of the LC dielectric are then polymerized, for example, by UV photopolymerization. This polymerization can be carried out in one step or in two or more steps.

[0692] A PSA display may include other components such as color filters, black matrices, passivation layers, optical delay layers, transistor elements for addressing individual pixels, etc., all of which are well known to those skilled in the art and can be used without creative skill.

[0693] Those skilled in the art can design electrode structures depending on the individual display type. For example, for a PS-VA display, multi-domain orientation of LC molecules can be initiated by providing electrodes with slits and / or bumps or protrusions to generate two, four or more different tilted alignment directions.

[0694] Following polymerization, the polymerizable compound forms a cross-linked polymer, which causes a certain pre-tilt of LC molecules within the LC medium. Without being bound by specific theories, it is believed that at least a portion of the cross-linked polymer formed by the polymerizable compound will separate from the LC medium or precipitate out, forming a polymer layer on the substrate or electrode, or on an alignment layer provided thereon. Microscopic measurements (such as SEM and AFM) have confirmed that at least a portion of the formed polymer accumulates at the LC / substrate interface.

[0695] Polymerization can be carried out in one step. Alternatively, polymerization can be carried out first in the first step (optionally with voltage applied simultaneously) to create a pre-tilt angle, and then polymerized or crosslinked in a second polymerization step without voltage applied (“final curing”) of compounds that did not react in the first step.

[0696] Suitable and preferred polymerization methods are, for example, thermal or photopolymerization, preferably photopolymerization, especially UV-induced photopolymerization, which can be achieved by exposing the polymerizable compound to UV radiation.

[0697] Optionally, one or more polymerization initiators may be added to the LC medium. Suitable conditions for polymerization and suitable types and amounts of initiators are known to those skilled in the art and described in the literature. Suitable initiators for free radical polymerization include, for example, commercially available photoinitiators such as Irgacure 651®, Irgacure 184®, Irgacure 907®, Irgacure 369®, or Darocure 1173® (Ciba AG). If a polymerization initiator is used, its proportion is preferably 0.001 to 5% by weight, particularly preferably 0.001 to 1% by weight.

[0698] The polymerizable compounds according to the invention are also suitable for initiator-free polymerization, which comes with considerable advantages, such as low material costs and, in particular, less LC media contamination due to possible residual initiators or their degradation products. Polymerization can therefore be carried out without the addition of an initiator. In a preferred embodiment, the LC medium therefore does not contain a polymerization initiator.

[0699] The LC medium may also contain one or more stabilizers to prevent undesirable spontaneous polymerization of RM, for example, during storage or transport. Suitable types and amounts of stabilizers are known to those skilled in the art and described in the literature. Particularly suitable stabilizers are, for example, those commercially available from the Irganox® series (Ciba AG), such as Irganox® 1076. If a stabilizer is used, its proportion is preferably 10-500,000 ppm, particularly preferably 50-50,000 ppm, based on the total amount of RM or polymerizable component (component P).

[0700] The polymerizable compounds of formula P do indeed exhibit particularly good UV absorption, and are therefore particularly suitable for manufacturing methods of PSA displays that include one or more of the following characteristics:

[0701] - In a display, a polymerizable medium is exposed to UV light in a two-step process, comprising a first UV exposure step (“UV-1 step”) to create a tilt angle, and a second UV exposure step (“UV-2 step”) to complete the polymerization.

[0702] - The polymerizable medium in the display is exposed to UV light generated by an energy-saving UV lamp (also known as a "green UV lamp"). These lamps are characterized by relatively low intensity in their absorption spectrum of 300-380 nm (1 / 100-1 / 10 of that of a conventional UV1 lamp), and they are preferably used in the UV2 step, but are also optionally used in the UV1 step when avoiding high intensity is necessary for the method.

[0703] - In the display, the polymerizable medium is exposed to UV light generated by a UV lamp, which has a radiation spectrum shifted to a longer wavelength (preferably 340 nm or longer) to avoid the short UV light exposure in the PS-VA method.

[0704] Both low-intensity and UV light shifted to longer wavelengths are used to protect the organic layer from potential damage caused by UV light.

[0705] Preferred embodiments of the present invention relate to a method of manufacturing a PSA display as described in the context, comprising one or more of the following features:

[0706] - The polymerizable LC medium is exposed to UV light in a 2-step process, which includes a first UV exposure step (“UV-1 step”) to create a tilt angle, and a second UV exposure step (“UV-2 step”) to complete the polymerization.

[0707] -Polymerizable LC media exposed to UV lamps with a power of 0.5 mW / cm² 2 Up to 10 mW / cm 2UV light with an intensity in the wavelength range of 300-380 nm is preferably used in the UV2 step, and optionally also in the UV1 step.

[0708] - The polymerizable LC medium can be exposed to UV light with a wavelength of 340 nm or longer, and preferably 400 nm or shorter.

[0709] This preferred method is performed, for example, by using a desired UV lamp, or by using a bandpass filter and / or a cutoff filter, which is substantially transmissive to UV light with its respective desired wavelength and substantially blocks UV light with its respective undesired wavelength. For example, when radiation of UV light with a wavelength λ of 300-400 nm is desired, UV exposure can be performed using a broadband pass filter that is substantially transmissive to wavelengths of 300 nm < λ < 400 nm. When radiation of UV light with a wavelength λ greater than 340 nm is desired, UV exposure can be performed using a cutoff filter that is substantially transmissive to wavelengths of λ > 340 nm.

[0710] "Substantially transmits" means that the filter transmits most, preferably at least 50%, of the intensity of the incident light at the desired wavelength. "Substantially blocks" means that the filter does not transmit most, preferably at least 50%, of the intensity of the incident light at the undesired wavelength. "Desired (undesired) wavelength" refers, for example, to wavelengths within (outside) a given λ range in the case of a bandpass filter, and to wavelengths above (below) a given λ value in the case of a cutoff filter.

[0711] This preferred method makes it possible to manufacture displays using longer UV wavelengths, thereby reducing or even avoiding the harmful and damaging effects of short UV light components.

[0712] UV radiation energy is typically 6 to 100 J, depending on the production method and conditions.

[0713] Preferably, the LC medium according to the invention is substantially composed of a polymerizable component (P) comprising one or more polymerizable compounds of formula P as described above and below, and an LC body mixture, as well as an optically active component comprising one or more chiral dopants. However, the LC medium may additionally contain one or more other components or additives, preferably selected from, but not limited to, the following list: comonomers, polymerization initiators, inhibitors, stabilizers, surfactants, wetting agents, lubricants, dispersants, hydrophobic agents, binders, flow improvers, defoamers, degassing agents, diluents, reactive diluents, auxiliaries, colorants, dyes, pigments, and nanoparticles.

[0714] Particularly preferred are LC media containing one, two, or three polymerizable compounds of formula P.

[0715] The preferred proportion of compound P in the LC medium is >0 to < 5%, very preferred is >0 to < 1%, and most preferred is 0.01 to 0.5%.

[0716] In a preferred embodiment, the medium according to the invention preferably contains one or more stabilizers in a total concentration of 10 ppm to 2000 ppm, more preferably 100 ppm to 1000 ppm, even more preferably 150 ppm to 500 ppm, very preferably 200 ppm to 400 ppm, and particularly in the range of 250 ppm to 300 ppm.

[0717] Optionally, the LC medium contains one or more, preferably one or two, type SA self-aligning additives for vertical alignment.

[0718] Self-aligning additives can be polymerized in an LC medium under conditions similar to those applied to the RM in the PSA process. Typically, they are polymerized simultaneously with the RM in the PSA process.

[0719] For example, SA additives for inducing vertical alignment, particularly for SA-VA mode displays, are disclosed in US 2013 / 0182202 A1, US 2014 / 0838581 A1, US 2015 / 0166890 A1 and US2015 / 0252265 A1.

[0720] Preferably, the medium contains one or more self-aligning additives of formula SA.

[0721]

[0722] in

[0723] R SA The group represents H, a straight-chain alkyl or alkoxy group having 1 to 15 carbon atoms, a straight-chain alkenyl or alkenyloxy group having 2 to 15 carbon atoms, or a branched alkyl, alkoxy, alkenyl, or alkenyloxy group each having 3 to 15 carbon atoms, wherein one or more of these CH2 groups can be independently separated from each other. -CH=CH-, -C≡C-, -CF2O-, -OCF2-, -O-, -CO-O-, or -O-CO- are substituted in such a way that the O atoms are not directly connected to each other, and one or more of the H atoms can be substituted by halogens.

[0724] The symbol represents 1,4-phenylene, which is unsubstituted or mono- or polysubstituted with L, or 1,4-cyclohexane-diyl or 1,4-cyclohexene-diyl, wherein one or both of the non-adjacent CH2 groups are optionally replaced by O.

[0725] L represents F, Cl, -CN, P-Sp- or a straight-chain, branched or cyclic alkyl group having 1 to 25 C atoms, wherein one or more non-adjacent CH2- groups are optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- in such a way that the O- and / or S- atoms are not directly connected to each other, and wherein one or more H atoms are each optionally replaced by P-Sp-, F or Cl.

[0726] r is 0 or 1.

[0727] s is 0, 1, 2, 3, or 4.

[0728] t is 0, 1, 2, or 3, where n + t < 5.

[0729] n is 1 or 2.

[0730] R a express

[0731]

[0732] or

[0733]

[0734] in

[0735] p is 1 or 2

[0736] q can be 2, 3, or 4, where each group can be the same or different.

[0737] Indicates substituted or unsubstituted ring systems or fused ring systems.

[0738] Y represents -O-, -S-, -C(O)-, -C(O)O-, -OC(O)-, -NR independently. 11 -or a single key,

[0739] o is 0 or 1.

[0740] X 1 Each can be represented independently as H, alkyl, fluoroalkyl, OH, NH2, NHR 11 、N(R 11 )2、-PO(OR 11 )2、-SO2R 11 -OR 11 C(O)OH, P or -CHO,

[0741] At least one of the groups X 1 Indicates selection from -OH, -NH2, NHR11 -PO(OR) 11 )2、-SO2R 11 The groups C(O)OH and -CHO,

[0742] Z 1 Independently means –(CO)-CH2(CO)OCH3, –(CO)-CH2(CO)-(C=CH2)-OCH3, –(CO)-CH2(CO)-(CH=CH)-OCH3, –(CO)-(CO)OCH3, –CH2-(CO)-(CO)OCH3, –(CO)-CH3, –(CO)-CH2(CO)-(CH2CH2)-OCH3,

[0743] P represents a polymerizable group.

[0744] R 11 Indicates an alkyl group having 1 to 12 carbon atoms.

[0745] R 12 It represents H, an alkyl group having 1 to 12 carbon atoms, P, or X. 1 ,

[0746] Sp a Sp c Sp d Each of them independently represents a spacer group or a single bond, and

[0747] Sp b It indicates a trivalent or tetravalent group.

[0748] Preferred SA compounds are selected from the following sub-formulas SA-1 to SA-4.

[0749]

[0750] Where s is 0, 1, 2, 3 or 4, preferably 0 or 1, t is 0, 1 or 2, preferably 0 or 1, and the groups appearing have the meaning defined above for formula SA.

[0751] In compounds of formulas SA-1 to SA-4, L preferably represents F or an alkyl group, preferably CH3, C2H5 or C3H7.

[0752] In a preferred embodiment, r2 represents 1 and / or r1 represents 0.

[0753] The polymerizable group P of formula SA and its subforms is preferably methacrylate, acrylate or another substituted acrylate, with methacrylate being the most preferred.

[0754] In the context, in equation SA and its sub-equations, Z 1It is preferred to represent a single bond independently or -CH2CH2-, and very specifically to represent a single bond.

[0755] R a Preferred representation

[0756] or

[0757] Where p is 1, 2, 3, 4, 5, or 6.

[0758] x = 1 or 0, preferably 1, and

[0759] R 22 The derivatives are H, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, or -CH2CH2-tert-butyl.

[0760] in particular

[0761] -O(CH2)2-OH, -O(CH2)3-OH,

[0762]

[0763] or .

[0764] In equation SA and its sub-equations, R SA Preferably, it represents a straight-chain alkyl or branched alkyl group having 1-8 carbon atoms, preferably a straight-chain alkyl group, and more preferably CH3, C2H5, n-C3H7, n-C4H9, n-C5H 11 , n-C6H 13 Or CH2CH(C2H5)C4H9. Furthermore, R SA It can represent an olefinic group, especially OCH2CH=CH2, OCH2CH=CHCH3, OCH2CH=CHC2H5, or an alkoxy group, especially OC2H5, OC3H7, OC4H9, OC5H. 11 and OC6H 13 Particularly preferred, R SA It indicates a straight-chain alkyl group, very specifically C5H. 11 .

[0765] The liquid crystal mixture according to the invention is nematic, preferably at -20°C or lower, more preferably at -30°C or lower, and very preferably at -40°C or lower.

[0766] With regard to the liquid crystal medium according to the invention, it is advantageous to have a nematic phase with a temperature of ≤-20°C to ≥95°C, particularly preferably ≤-30°C to ≥100°C, and very particularly preferably ≤-40°C to ≥105°C.

[0767] The phrase "possessing a nematic phase" here means, on the one hand, that no smectic phase or crystallization is observed at the corresponding temperature at low temperatures, and on the other hand, that the nematic phase does not become clear upon heating (a phase transition to the isotropic phase). Low-temperature studies are conducted in a flow viscometer at the corresponding temperature and verified by storage for at least 100 hours in a test chamber with a layer thickness corresponding to the electro-optic application. If the storage stability in the corresponding test chamber at -20°C is 1000 hours or more, the medium is said to be stable at that temperature. The response times are 500 hours and 250 hours at -30°C and -40°C, respectively. At high temperatures, the clearing point is measured in a capillary using conventional methods.

[0768] In a preferred embodiment, the medium according to the invention has a clearing temperature of 95°C or higher, more preferably 98°C or higher, even more preferably 100°C or higher, particularly 102°C or 103°C or 104°C or 105°C or 106°C or 107°C or 108°C or 109°C or 110°C or higher.

[0769] In a preferred embodiment of the invention, the birefringence of the medium is 0.095 to 0.132, very preferably 0.098 to 0.131, and particularly 0.100 to 0.130.

[0770] In a preferred embodiment, the dielectric anisotropy Δε of the liquid crystal mixture according to the invention is -2.0 to -6.0, more preferably -2.6 to -5.0, very preferably -3.0 to -4.5, and particularly -3.2 to -4.3.

[0771] The rotational viscosity γ1 at 20°C is preferably in the range of 100 to 300 mPas, more preferably in the range of 130 to 250 mPas.

[0772] Further preferred embodiments (alone or in combination) are as follows. The medium preferably comprises:

[0773] - One or more compounds of formula IIA-1-2, selected from compounds of formula CY-n-Om, particularly CY-3-O2, CY-3-O4, CY-5-O2 and / or CY-5-O4, preferably with a total concentration of 5% or 6% to 30%, more preferably 7% to 28%, particularly preferably 8% to 26% or 25% or 24% or 23%;

[0774] - One or more compounds of formula IIA-2-2 and optionally IIA-2-1, more preferably one or more compounds CCY-n-Om and optionally CC-nm, in CCY-3-O1, CCY-3-O2, CCY-4-O2, CCY-3-O3 and / or CCY-5-O2 and optionally CCY-2-1, preferably with a total concentration of 15% to 45%, more preferably 18% to 42%, particularly preferably 20% or 21% or 22% or 23% or 24% or 25% to 40% or to 39% or to 38%;

[0775] - One or more compounds of formula IIA-1-2 and IIA-2-2, wherein the total concentration is 30% to 65%, more preferably 32% to 60%, very preferably 34% to 57%, particularly 35% to 55%;

[0776] - 8% to 30%, preferably 9% to 25%, very preferably 10% to 23% of one or more compounds of formula IIB-2, preferably selected from compounds CPY-2-O2 and CPY-3-O2;

[0777] and / or

[0778] - One or more compounds of formula IIC, with a total concentration of 3% to 12%, more preferably 4% to 11%, and very preferably 4% to 10%;

[0779] and / or

[0780] - One or more compounds of formula IIE, preferably IIE-3, very preferably PGIY-n-Om, especially PGIY-3-O2, with a total concentration of 1% to 6%, more preferably 1.5% to 5%, and very preferably 2% to 4%;

[0781] and / or

[0782] - One or more compounds of formula XI, preferably XI-1, XI-2 and / or XI-4, particularly selected from formulas PGP-nm, PGP-nV, PGP-n-Vm, PGP-n-mV and PGP-n-mVI, preferably selected from formulas PGP-2-3, PGP-2-4, PGP-2-5, PGP-1-V, PGP-2-V and PGP-2-2V1 and / or PGIGI-nm, with a total concentration of 1% to 8%, more preferably 2% to 7% and very preferably 3% to 6%;

[0783] and / or

[0784] - One or more Formula IV compounds, preferably with a total concentration of 10% to 40%, more preferably 13% to 35%, and particularly preferably 15% to 30%;

[0785] and / or

[0786] - One or more IVa compounds, preferably with a total concentration of 5% to 20%, more preferably 7% to 15%, and particularly preferably 9% to 13%;

[0787] and / or

[0788] - One or more IVb compounds, preferably with a total concentration of 8% to 25%, more preferably 12% to 22%, and particularly preferably 15% to 19%;

[0789] and / or

[0790] - One or more compounds of formula IV and one or more compounds of formula IVa and / or IVb, preferably in a total concentration of 9% to 40%, more preferably 11% to 35%, particularly preferably 15% to 33%;

[0791] and / or

[0792] - One or more compounds of formula V, more preferably compounds selected from formula V-2-1 and V-2-2, very preferably selected from V-2-1 and other optional V-2-2, especially CCP-nm and / or CCP-Vn-m and optional CPP-nm, very particularly selected from CCP-3-1, CCP-V-1, CCP-V2-1 and CPP-3-2, preferably with a total concentration of 1% to 20%, more preferably 2% to 17%, very preferably 4% to 15%;

[0793] and / or

[0794] One or more compounds of formula V-3-2, preferably with a total concentration of 1% to 10%, more preferably 2% to 8%, and very preferably 3% to 7%;

[0795] and / or

[0796] One or more compounds of formula V-1-8, preferably in a total concentration of 0.5% to 10%, more preferably 1% to 6%, and very preferably 2% to 4%;

[0797] and / or

[0798] One or more SA compounds, with a total concentration of 0.025% or higher,

[0799] or

[0800] One or more SA compounds, with a total concentration of 0.025% to 0.08%,

[0801] or

[0802] One or more SA compounds, with a total concentration of 0.1% to 2.5%,

[0803] and / or

[0804] - One or more compounds selected from formulas V-1-1 and V-1-6, particularly CCC-nm and / or CCC-nV, very particularly CCC-3-V and / or CCC-VV, preferably in a total concentration of 1% to 20%, more preferably 2% to 17%, and very preferably 3% to 14%;

[0805] and / or

[0806] One or more compounds of the formula COYOIC-nm

[0807] and / or

[0808] One or more compounds of the formula COY-n-Om and / or CCOY-n-Om

[0809] and / or

[0810] 0.1% to 3% of compounds PPGU-3-F and / or PPGU-(c5)-F,

[0811] and / or

[0812] 0.1% to 3% of the compound 3-fluoro-4'-alkyl-4-[4-(naphth-2-yl)phenyl]-1,1'-biphenyl:

[0813]

[0814] Wherein the alkyl group is methyl, ethyl, n-propyl, n-butyl, n-pentyl, or n-hexyl, preferably n-propyl.

[0815] And / or 0.1-3% of 2-(4-methylphenyl)-6-propylnaphthalene:

[0816] .

[0817] The liquid crystal medium according to the present invention has a high voltage retention rate value in the liquid crystal cell.

[0818] Typically, liquid crystal media with low addressing voltages or threshold voltages exhibit lower voltage retention rates than those with higher addressing voltages or threshold voltages, and vice versa.

[0819] As used herein, the term "dielectrically positive compound" refers to a compound having Δε > 1.5, the term "dielectrically neutral compound" refers to those having -1.5 ≤ Δε ≤ 1.5, and the term "dielectrically negative compound" refers to those having Δε < -1.5. Here, the dielectric anisotropy of the compound is determined by dissolving 10% of the compound in a liquid crystal matrix in at least one test cell and measuring the capacitance of the resulting mixture. In each case, the test cell has a layer thickness of 20 µm and has vertical and surface alignment at 1 kHz. The measurement voltage is typically 0.5 V–1.0 V, but is always below the capacitance threshold of each liquid crystal mixture studied.

[0820] All temperature values ​​described in this invention are expressed in °C.

[0821] The mixture according to the invention is applicable to all VA-TFT applications, such as, for example, VAN, MVA, (S)-PVA, ASV, PSA (polymer sustaining VA), and PS-VA (polymer stable VA). It is also applicable to IPS (in-plane switching) and FFS (edge ​​field switching) applications with negative Δε, particularly UB-FFS.

[0822] It will be self-evident to those skilled in the art that the VA, IPS or FFS mixtures according to the present invention may also contain compounds in which, for example, H, N, O, Cl and F are substituted with corresponding isotopes.

[0823] The compounds according to the invention can be synthesized by or similar methods described in the literature (e.g., in standard works, such as Houben-Weyl, Methoden der Organischen Chemie [Methods of OrganicChemistry], Georg-Thieme-Verlag, Stuttgart), under reaction conditions known and suitable for the reactions. Variations known per se may also be used herein, but are not mentioned further. In particular, they can be prepared as described or similar to the reaction schemes below. Other methods for preparing the compounds of the invention can be obtained from the examples.

[0824] Other mesocrystalline compounds not explicitly mentioned above may also be optionally and advantageously used in the media according to the invention. Such compounds are known to those skilled in the art. Detailed Implementation

[0825] For the purposes of this invention and in the following embodiments, the structures of the liquid crystal compounds are represented by abbreviations and converted to chemical formulas according to Tables A through C below. All groups C m H 2m+1 C n H2n+1 and C l H 2l+1 Or C m H 2m-1 C n H 2n-1 and C l H 2l-1 The groups are straight-chain alkyl or alkylene groups, each having n, m, and l C atoms in various cases. Preferably, n, m, and l are independently 1, 2, 3, 4, 5, 6, or 7. Table A shows the codes for the ring elements of the compound core, Table B lists the bridging units, and Table C lists the symbolic meanings of the left-hand and right-hand end groups of the molecule. Abbreviations consist of the code for the ring element with an optional connecting group, followed by a first hyphen and the code for the left-hand end group, and a second hyphen and the code for the right-hand end group. Table D shows exemplary structures of the compounds and their respective abbreviations.

[0826] Table A: Ring Elements

[0827]

[0828]

[0829]

[0830]

[0831] Table B: Bridging Units

[0832]

[0833] Table C: End bases

[0834]

[0835]

[0836] Where n and m are integers, and the three dots "..." are placeholders for other abbreviations from the table.

[0837] The medium according to the invention preferably comprises one or more compounds mentioned in Table D below.

[0838] Use the following abbreviations:

[0839] (n, m, k, and l are each independent integers, preferably 1 to 9, more preferably 1 to 7; k and l may also be 0 and preferably 0 to 4, more preferably 0 or 2 and most preferably 2; n is preferably 1, 2, 3, 4, or 5; in the combination "-nO-", it is preferably 1, 2, 3, or 4, more preferably 2 or 4; m is preferably 1, 2, 3, 4, or 5; in the combination "-Om", it is preferably 1, 2, 3, or 4, more preferably 2 or 4. The combination "-lVm" is preferably "2V1").

[0840] Table D

[0841]

[0842]

[0843]

[0844]

[0845]

[0846]

[0847]

[0848]

[0849]

[0850]

[0851]

[0852]

[0853]

[0854]

[0855]

[0856]

[0857]

[0858]

[0859]

[0860]

[0861]

[0862]

[0863]

[0864]

[0865]

[0866]

[0867]

[0868]

[0869]

[0870]

[0871]

[0872]

[0873]

[0874]

[0875]

[0876]

[0877]

[0878]

[0879]

[0880]

[0881] Table E

[0882] Table E shows illustrative reactive mesocrystalline compounds that can be used in LC media according to the present invention.

[0883]

[0884]

[0885]

[0886]

[0887]

[0888]

[0889]

[0890]

[0891]

[0892]

[0893]

[0894]

[0895]

[0896]

[0897]

[0898]

[0899]

[0900]

[0901]

[0902]

[0903]

[0904]

[0905] In a preferred embodiment, the mixture according to the invention comprises one or more polymerizable compounds, preferably selected from formulas RM-1 to RM-182. 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-52, RM-54, RM-57, RM-58, RM-64, RM-74, RM-76, RM-88, RM-91, RM-102, RM-103, are particularly preferred. RM-109, RM-116, RM-117,RM-120, RM-121, RM-122, RM-139, RM-140, RM-142, RM-143, RM-145, RM-146, RM-147, RM-149, RM-156 to RM-163, RM-169, RM-170 and RM-171 to RM-183.

[0906] Table F

[0907] Table F shows self-aligning additives for vertical alignment in LC media for SA-VA and SA-FFS displays, which can be used together with polymerizable compounds according to the present invention:

[0908]

[0909]

[0910]

[0911]

[0912]

[0913]

[0914]

[0915]

[0916]

[0917]

[0918]

[0919]

[0920]

[0921]

[0922]

[0923]

[0924]

[0925]

[0926]

[0927]

[0928]

[0929] In a preferred embodiment, the LC media, SA-VA and SA-FFS displays according to the invention comprise one or more SA additives selected from SA-1 to SA-48, preferably selected from SA-14 to SA-48, and very preferably selected from SA-20 to SA-34 and SA-44, in combination with one or more RMs.

[0930] Example

[0931] The present invention will be described in detail through the following non-limiting working examples.

[0932] Use the following abbreviations and symbols:

[0933]

[0934] Unless otherwise expressly stated, all concentrations in this application are expressed as weight percentages and refer to the corresponding mixtures as a whole, which include all solid or liquid crystal components and are solvent-free.

[0935] Unless otherwise stated, all temperature values ​​indicated in this application, such as melting point T(C,N), transformation from smectic (S) to nematic (N) T(S,N), and clearing point T(N,I), are referred to in degrees Celsius (°C). Mp represents the melting point, and cl.p. = clearing point. Furthermore, C = crystalline state, N = nematic phase, S = smectic phase, and I = isotropic phase. The data between these symbols represent transformation temperatures.

[0936] Unless otherwise stated, in each case, all physical properties are and have been determined in accordance with "Merck LiquidCrystals, Physical Properties of Liquid Crystals", Status Nov. 1997, MerckKGaA, Germany, and applied to a temperature of 20 °C, and Δn at 589 nm and Δε at 1 kHz.

[0937] The term "threshold voltage" used in this invention refers to the capacitive threshold (V0), which is also known as the Freedericks threshold, unless otherwise stated. In embodiments, as is generally the case, the optical threshold can also be for a relative contrast ratio of 10% (V0). 10 (This is a quote.)

[0938] Unless otherwise stated, the method for polymerizing polymerizable compounds in a PSA display as described above and below is carried out at a temperature at which the LC medium presents a liquid crystal phase, preferably a nematic phase, and most preferably at room temperature.

[0939] Unless otherwise specified, the preparation of test kits and the measurement of their electro-optic and other properties shall be carried out in accordance with the methods described below or similar to those described below.

[0940] The display used to measure capacitive threshold voltage consists of two parallel glass outer plates 25 µm apart. Each outer plate has an electrode layer on the inside and an unrubbed polyimide alignment layer on the top, which results in vertical alignment of liquid crystal molecules.

[0941] The display or test box used to measure tilt angle consists of two parallel glass outer plates spaced 4µm apart. Each outer plate has an electrode layer on its inner side and a polyimide alignment layer on top, wherein the two polyimide layers rub against each other in antiparallel fashion, resulting in vertical edge alignment of liquid crystal molecules.

[0942] Polymerizable compounds are polymerized in a display or test chamber by irradiating the display with UV light of a defined intensity for a predetermined time while simultaneously applying a voltage (typically 10V-30V AC, 1 kHz) to the display. In the examples, unless otherwise specified, polymerization is carried out using a fluorescent lamp and an intensity of 0 to 20 mW / cm². The intensity is measured using a standard instrument (a Ushio Accumulate UV meter with a center wavelength of 313 nm).

[0943] Transmission measurements were performed in a test cell with a herringbone electrode layout (from Merck Ltd., Japan; 1-pixel herringbone electrode (ITO, 10x10 mm, herringbone angle 47.7°, 3µm line / 3µm space), 3.2µm cell gap, AF-glass, tilt angle 1°).

[0944] Storage stability (LTS) in the bulk of the medium according to the invention at a given temperature T. 本体 The stability was determined by visual inspection. 2 g of the medium of interest was filled into a properly sized, sealed glass container (bottle) placed in a refrigerator at a predetermined temperature. The bottle was checked at defined time intervals for smectic phase formation or crystallization. Two bottles were stored for each material and at each temperature. The test was terminated if crystallization or a smectic phase was observed in at least one of the two corresponding bottles, and the time of the last check before the observation of a higher-order phase was recorded as the corresponding storage stability.

[0945] Mixture Examples

[0946] Use the following stabilizers:

[0947]

[0948]

[0949]

[0950]

[0951] Use the following reactive mesocrystalline material (RM):

[0952]

[0953]

[0954] Use the following self-aligning additives (SA):

[0955]

[0956]

[0957] The nematic LC main mixtures C1, H1, H2 and mixture examples M1 to M14 and P1 to P23 have the compositions and properties given in the table below.

[0958] Main mixture H1

[0959]

[0960] Comparative Example C1

[0961] Comparative Example 1 has the following components:

[0962]

[0963] Mixture Example M1

[0964]

[0965] Mixture Example M2

[0966]

[0967] Mixture Example M3

[0968]

[0969] Mixture Example M4

[0970]

[0971] Mixture Example M5

[0972]

[0973] Mixture Example M6

[0974]

[0975] Mixture Example M7

[0976]

[0977] Mixture Example M8

[0978]

[0979] Mixture Example M9

[0980]

[0981] Main mixture H2

[0982]

[0983] Mixture Example M10

[0984]

[0985] Displays have been fabricated using mixture examples M1 to M10 and comparative mixture C1, and the alignment of the liquid crystal medium has been studied.

[0986] The following results were obtained:

[0987]

[0988] X: Poor; Δ: Acceptable; O: Good

[0989] Reference mixture C1 has an unacceptable orientation and is therefore unsuitable for applications in PS-VA displays. It has been found that the mixture according to the invention brings improvements and surprisingly exhibits acceptable or good orientation.

[0990] Mixture Example M11

[0991]

[0992] Mixture Example M12

[0993]

[0994] Mixture Example M13

[0995]

[0996] Mixture Example M14

[0997]

[0998] polymerizable mixtures

[0999] Polymerizable mixtures P1-P9 were prepared from the nematic mixtures given in Table 1 by adding reactive mesomorphs (RM) of compounds selected from formulas RM-1, RM-17, RM-35, RM-64 and RM-171 in the amounts (%RM) given in Table 1.

[1000] Table 1: Polymerizable Mixtures

[1001]

[1002] Mixture Example P10

[1003] The polymerizable mixture P10 consists of 99.434% of mixture example M1, 0.300% of RM-1, 0.200% of RM-145, 0.050% of RM-163, and 0.001% of Irganox. ® It consists of 1076 and 0.015% of compound ST-3a-1.

[1004] Mixture Example P11

[1005] Mixture P11 consists of 99.685% of mixture M1, 0.3% of RM-1 and 0.015% of stabilizer ST-3a-1.

[1006] Mixture Example P12

[1007] Mixture P12 consists of 99.684% of mixture M2, 0.3% of RM-1, and 0.001% of IRGANOX-1076. ® It consists of 0.015% of the stabilizer ST-3a-1.

[1008] Mixture Example P13

[1009] Mixture P13 consists of 99.685% of mixture M3, 0.3% of RM-35 and 0.015% of stabilizer ST-3a-1.

[1010] Mixture Example P14

[1011] Mixture P14 consists of 99.685% of mixture M4, 0.3% of RM-64 and 0.015% of stabilizer ST-3a-1.

[1012] Mixture Example P15

[1013] Mixture P15 consists of 99.684% of mixture M4, 0.3% of RM-64, and 0.001% of IRGANOX-1076. ® It consists of 0.015% of the stabilizer ST-3a-1.

[1014] Mixture Example P16

[1015] Mixture P16 consists of 99.685% of mixture M1, 0.3% of RM-35 and 0.015% of stabilizer ST-3a-1.

[1016] Mixture Example P17

[1017] Mixture P17 consists of 99.683% of mixture M4, 0.3% RM-35, and 0.002% IRGANOX-1076. ® It consists of 0.015% of the stabilizer ST-3a-1.

[1018] Mixture Example P18

[1019] Mixture P18 consists of 99.685% of mixture M4, 0.3% of RM-145 and 0.015% of stabilizer ST-3b-1.

[1020] Mixture Example P19

[1021] Mixture P19 consists of 99.684% of mixture M4, 0.3% of RM-145, and 0.001% of IRGANOX-1076. ®It consists of 0.015% of the stabilizer ST-3a-1.

[1022] Mixture Example P20

[1023] Mixture P20 consists of 99.685% of mixture M4, 0.3% of RM-171 and 0.015% of stabilizer ST-3a-1.

[1024] Mixture Example P21

[1025] Mixture P21 consists of 99.684% of mixture M4, 0.3% of RM-171, and 0.001% of IRGANOX-1076. ® It consists of 0.015% of the stabilizer ST-3a-1.

[1026] Mixture Example P22

[1027] Mixture P22 consists of 99.435% of mixture M4, 0.5% of RM-171, 0.05% of RM-64 and 0.015% of stabilizer ST-3a-1.

[1028] Mixture Example P23

[1029] Mixture P22 consists of 99.434% of mixture M4, 0.5% of RM-171, 0.05% of RM-64, and 0.001% of IRGANOX-1076. ® It consists of 0.015% of the stabilizer ST-3a-1.

Claims

1. A liquid crystal medium having a clearing temperature of 95°C or higher, comprising... a) 5% to 30% by weight of one or more compounds of formula IIA-1 b) 15%-45% by weight of one or more compounds of formula IIA-2 c) 8% to 30% by weight of one or more compounds of formula IIB. d) 4%-12% by weight of one or more compounds selected from formulas IIC, IIE, and XI. and e) Less than 1% by weight or 0% by weight of one or more compounds of formula IID in R 2A R 2B R 2C R 2D and R 2E The same or different representations of H, a straight-chain alkyl or alkoxy group having 1-15 carbon atoms, a straight-chain alkenyl or alkenyloxy group having 2-15 carbon atoms, or a branched alkyl, alkoxy, alkenyl, or alkenyloxy group each having 3-15 carbon atoms, wherein one or more CH2 groups among these groups can be independently represented by each other. -CH=CH-, -C≡C-, -CF2O-, -OCF2-, -O-, -CO-O-, or -O-CO- are substitutions where the O atoms are not directly connected to each other, and one or more of the H atoms can be replaced by halogens. R 111 and R 112 It may represent F or Cl in the same or different ways, or it may have the group R. 2A One of the meanings, L 1 and L 2 Each can be independently represented as F, Cl, CF3, or CHF2. X 21 X 22 X 23 X 24 X 25 X 26 X 111 X 112 and X 113 They may represent H, F, Cl, CF3, or CHF2, either the same or different. Y represents H, F, Cl, CF3, CHF2, or CH3. Z 2D This indicates a single bond, -CH2CH2-, -CH=CH-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -COO-, -OCO-, -C2F4-, -CF=CF-, or -CH=CHCH2O-. (O) represents O or a single bond. q represents 0, 1, or 2, and v represents an integer from 1 to 6. The following media are excluded: 2.5% of compound CC-3-V1, 10.0% of compound CC-4-V1, 3.0% of compound CC-3-O1, 4.0% of compound CC-3-4, 4.0% of compound CC-3-5, 6.0% of compound CCP-3-1, 6.0% of compound CCP-3-3, 4.0% of compound CCY-3-O1, 4.0% of the compound CCY-3-O2, 4.0% of the compound CCY-3-O3, 4.0% of the compound CCY-4-O2, 4.0% of compound CCY-5-O2 10.0% of compound CPY-2-O2, 10.0% of compound CPY-3-O2, 6.5% of compound CY-3-O2, 10.0% of compound CY-3-O4, 5.0% of compound PYP-2-3, and 3.0% of compound PYP-2-4.

2. The liquid crystal medium according to claim 1, wherein the total concentration of the compounds of formula IIA-1 and IIA-2 is from 30% to 65% by weight.

3. The liquid crystal medium according to claim 1 or 2, wherein the total concentration of compounds of formula IIB and IIC and / or IIE and / or XI is from 13% to 30% by weight.

4. The liquid crystal medium according to one or more of claims 1 to 3, wherein the medium comprises one or more compounds of formula IIA'. in R 2A The group represents H, a straight-chain alkyl or alkoxy group having 1-15 carbon atoms, a straight-chain alkenyl or alkenyloxy group having 2-15 carbon atoms, or a branched alkyl, alkoxy, alkenyl, or alkenyloxy group each having 3-15 carbon atoms, wherein one or more of these CH2 groups can be independently separated from each other. -CH=CH-, -C≡C-, -CF2O-, -OCF2-, -O-, -CO-O-, or -O-CO- are substitutions where the O atoms are not directly connected to each other, and one or more of the H atoms can be replaced by halogens. This indicates 1,4-cyclohexylene or tetrahydropyran-2,5-diyl. L 1 and L 2 Each can be independently represented as F, Cl, CF3, or CHF2. Y represents H, F, Cl, CF3, CHF2, or CH3. Z 2 This indicates -CH2CH2-, -CH=CH-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -COO-, -OCO-, -C2F4-, -CF=CF-, or -CH=CHCH2O-. p represents 0, 1, or 2, and v represents an integer from 1 to 6.

5. The liquid crystal medium according to one or more of claims 1 to 4, wherein the medium comprises one or more compounds of formula IV. in R 41 This indicates an unsubstituted alkyl group having 1 to 7 carbon atoms or an unsubstituted alkenyl group having 2 to 7 carbon atoms, and R 42 This indicates an unsubstituted alkyl group having 1 to 7 carbon atoms, an unsubstituted alkoxy group having 1 to 6 carbon atoms, or an unsubstituted alkenyl group having 2 to 7 carbon atoms. and optionally one or more compounds selected from formulas IVa and IVb in R 41 This indicates an alkyl group having 1-7 carbon atoms or an alkenyl group having 2-7 carbon atoms. R 42 This indicates an alkyl group having 1-7 carbon atoms, an alkoxy group having 1-6 carbon atoms, or an alkenyl group having 2-7 carbon atoms. express or , Z 4 It represents a single bond, -CH2CH2-, -CH=CH-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -COO-, -OCO-, -C2F4-, -C4H8-, or -CF=CF-.

6. The liquid crystal medium according to one or more of claims 1 to 5, wherein the medium comprises one or more compounds of formula V. in R 51 R 52 Each of these can be independently represented as an alkyl group having 1-7 carbon atoms, an alkoxy group having 1-7 carbon atoms, or an alkoxyalkyl group, alkenyl group, or alkenyloxy group each having 2-7 carbon atoms. and Same or different , or , Z 51 Z 52 Each of these can be independently represented as -CH2-CH2-, -CH2-O-, -CH=CH-, -C≡C-, -COO-, or a single bond, and n is 1 or 2.

7. The liquid crystal medium according to one or more of claims 1 to 6, wherein the medium comprises one or more compounds of formula XII. in R 12 Having the R of claim 1 2A The given meaning, and Representing each other independently or ,and Alternative representation or L 121 L 122 and L 123 H or F can be represented independently of each other. Y 12 Indicates H or CH3, X 12 The symbol represents a halogen, a haloalkyl or haloalkoxy group having 1-3 carbon atoms, or a haloalkenyl or haloalkenoxy group having 2 or 3 carbon atoms, preferably F, Cl, CF3, OCF3 or OCHF2, more preferably F or OCF3.

8. The liquid crystal medium according to one or more of claims 1 to 7, wherein the medium comprises one or more compounds of formula P. P-Sp-A 1 -(Z 1 -A 2 ) z -RP Among them, the same or different in each occurrence P represents a polymerizable group. Sp represents a spacer group or a single bond. A 1 A 2 These are groups that independently represent aromatic, heteroaromatic, alicyclic, or heterocyclic groups. They may also contain fused rings, and these rings may be unsubstituted, or monosubstituted or polysubstituted. Z 1 Represents -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -(CH2) n1 -, -CF2CH2-, -CH2CF2-, -(CF2) n1 -, -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, -CH=CH-CO-O-, -O-CO-CH=CH-, -CH2-CH2-CO-O-, -O-CO-CH2-CH2-, -CR 0 R 00 - or single key, R 0 R 00 It represents H or an alkyl group having 1-12 carbon atoms. R represents H, L, or P-Sp-, L represents F, Cl, -CN, P-Sp- or a straight-chain, branched or cyclic alkyl group having 1-25 C atoms, wherein one or more non-adjacent CH2 groups are optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- in such a way that the O and / or S atoms are not directly connected to each other, and wherein one or more H atoms are each optionally replaced by P-Sp-, F or Cl. z is 0, 1, 2, or 3, and n1 is 1, 2, 3 or 4.

9. The liquid crystal medium according to one or more of claims 1 to 8, wherein the medium comprises one or more self-aligning additives of formula SA. in R SA The group represents H, a straight-chain alkyl or alkoxy group having 1-15 carbon atoms, a straight-chain alkenyl or alkenyloxy group having 2-15 carbon atoms, or a branched alkyl, alkoxy, alkenyl, or alkenyloxy group each having 3-15 carbon atoms, wherein one or more of these CH2 groups can be independently separated from each other. -CH=CH-, -C≡C-, -CF2O-, -OCF2-, -O-, -CO-O-, or -O-CO- are substituted in such a way that the O atoms are not directly connected to each other, and one or more of the H atoms can be substituted by halogens. The symbol represents 1,4-phenylene, which is unsubstituted or mono- or polysubstituted with L, or 1,4-cyclohexane-diyl or 1,4-cyclohexene-diyl, wherein one or both of the non-adjacent CH2 groups are optionally replaced by O. L represents F, Cl, -CN, P-Sp- or a straight-chain, branched or cyclic alkyl group having 1-25 C atoms, wherein one or more non-adjacent CH2- groups are optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- in such a way that the O- and / or S- atoms are not directly connected to each other, and wherein one or more H atoms are each optionally replaced by P-Sp-, F or Cl. r is 0 or 1. s is 0, 1, 2, 3, or 4. t is 0, 1, 2, or 3, where n + t < 5. n is 1 or 2. R a express or in p is 1 or 2 q can be 2, 3, or 4, where each group can be the same or different. Indicates substituted or unsubstituted ring systems or fused ring systems. Y represents -O-, -S-, -C(O)-, -C(O)O-, -OC(O)-, -NR independently. 11 -or a single key, o is 0 or 1. X 1 Each can be represented independently as H, alkyl, fluoroalkyl, OH, NH2, NHR 11 、N(R 11 2. -PO(OR) 11 )2、-SO2R 11 -OR 11 C(O)OH, P or -CHO, At least one of the groups X 1 Indicates selection from -OH, -NH2, NHR 11 -PO(OR) 11 )2、-SO2R 11 The groups C(O)OH and -CHO, Z 1 independently represent –(CO)-CH2(CO)OCH3, –(CO)-CH2(CO)-(C=CH2)-OCH3, –(CO)-CH2(CO)-(CH=CH)-OCH3, –(CO)-(CO)OCH3, –CH2-(CO)-(CO)OCH3, –(CO)-CH3, or –(CO)-CH2(CO)-(CH2CH2)-OCH3, P represents a polymerizable group. R 11 Indicates an alkyl group having 1-12 carbon atoms. R 12 It represents H, an alkyl group having 1-12 carbon atoms, P, or X. 1 , Sp a Sp c Sp d Each of them independently represents a spacer group or a single bond, and Sp b It indicates a trivalent or tetravalent group.

10. A liquid crystal display comprising a liquid crystal medium as defined in any one of claims 1 to 9.

11. The liquid crystal display according to claim 10, wherein the display is a VA, IPS, FFS, PS-VA, PS-IPS, PS-FFS, PS-UB-FFS or SA-VA display.

12. Use of the liquid crystal medium according to one or more of claims 1 to 9 in a VA, IPS, FFS, PS-VA, PS-IPS, PS-FFS, PS-UB-FFS or SA-VA display.

13. A method for preparing a liquid crystal medium according to any one of claims 1 to 9, comprising the steps of mixing one or more compounds of formula IIA-1 and IIA-2 as defined in claim 1, as well as IIB and / or IIC and / or IIE and / or optional IID compounds, and optionally mixing with other liquid crystal compounds or additives.

14. A method for manufacturing a liquid crystal display device, comprising at least the following steps: - Provide a first substrate and a second substrate, at least one of which is transparent to light, and provide one electrode on each substrate, or two electrodes on one substrate. - A sealant is formed along the end of one of the first substrate and the second substrate. - An LC medium according to one or more of claims 1 to 11 is provided between the first substrate and the second substrate and the sealant. - The first substrate and the second substrate are combined to form an LC cell. - Bake the sealant at a temperature of approximately 100°C to approximately 140°C for approximately 15 minutes to approximately 120 minutes. - Non-uniform cooling Optionally, if present, a self-aligning liquid crystal layer is formed between the first and second substrates and the sealant by maintaining the temperature of the liquid crystal cell above the clearing point temperature of the self-aligning liquid crystal material comprising the SA compound as defined in claim 9. - and optionally, if present, polymerizing the polymerizable compound of formula P according to claim 8 by irradiation with UV light, preferably while applying a voltage to the electrodes of the liquid crystal display device.

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