Patent Application
20220251448
The invention relates to compounds of formula I,
wherein R11, R21, A11, A, Z, X11, X21, Y11, Y12, Sp11, Sp21, o and p have one of the meanings as given in claim 1. The invention further relates to a method of production of said compounds, to the use of said compounds in LC media and to LC media comprising one or more compounds of formula I. Further, the invention relates to a method of production of such LC media, to the use of such media in LC devices, and to a LC device comprising a LC medium according to the present invention. The present invention further relates to a process for the fabrication such liquid crystal display and to the use of the liquid crystal mixtures according to the invention for the fabrication of such liquid crystal display.
Liquid-crystalline media have been used for decades in electro-optical displays for information display. The liquid crystal displays used at present are usually those of the TN (“twisted nematic”) type. However, these have the disadvantage of a strong viewing-angle dependence of the contrast.
In addition, so-called VA (“vertically aligned”) displays are known which have a broader viewing angle. The LC cell of a VA display contains a layer of an LC medium between two transparent electrodes, where the LC medium usually has a negative value of the dielectric (DC) anisotropy. In the switched-off state, the molecules of the LC layer are aligned perpendicular to the electrode surfaces (homeotropically) or have a tilted homeotropic alignment. On application of an electrical voltage to the two electrodes, a realignment of the LC molecules parallel to the electrode surfaces takes place. Furthermore, so-called IPS (“in plane switching”) displays and later, FFS (“fringe-field switching”) displays have been reported (see, inter alia, S. H. Jung et al., Jpn. J. Appl. Phys., Volume 43, No. 3, 2004, 1028), which contain two electrodes on the same substrate, one of which is structured in a comb-shaped manner and the other is unstructured. A strong, so-called “fringe field” is thereby generated, i.e. a strong electric field close to the edge of the electrodes, and, throughout the cell, an electric field which has both a strong vertical component and a strong horizontal component. FFS displays have a low viewing-angle dependence of the contrast. FFS displays usually contain an LC medium with positive dielectric anisotropy, and an alignment layer, usually of polyimide, which provides planar alignment to the molecules of the LC medium.
Furthermore, FFS displays have been disclosed (see S. H. Lee et al., Appl. Phys. Lett. 73(20), 1998, 2882-2883 and S. H. Lee et al., Liquid Crystals 39(9), 2012, 1141-1148), which have similar electrode design and layer thickness as FFS displays, but comprise a layer of an LC medium with negative dielectric anisotropy instead of an LC medium with positive dielectric anisotropy. The LC medium with negative dielectric anisotropy shows a more favorable director orientation that has less tilt and more twist orientation compared to the LC medium with positive dielectric anisotropy, as a result of which these displays have a higher transmission.
A further development are the so-called PS (polymer sustained) or PSA (polymer sustained alignment) displays, for which the term “polymer stabilised” is also occasionally used. The PSA displays are distinguished by the shortening of the response times without significant adverse effects on other parameters, such as, in particular, the favourable viewing-angle dependence of the contrast.
In these displays, a small amount (for example 0.3% by weight, typically <1% by weight) of one or more polymerizable compound(s) is added to the LC medium and, after introduction into the LC cell, is polymerised or crosslinked in situ, usually by UV photopolymerization, between the electrodes with or without an applied electrical voltage. The addition of polymerizable mesogenic or liquid-crystalline compounds, also known as reactive mesogens or “RMs”, to the LC mixture has proven particularly suitable. PSA technology has hitherto been employed principally for LC media having negative dielectric anisotropy.
Unless indicated otherwise, the term “PSA” is used below as representative of PS displays and PSA displays.
In the meantime, the PSA principle is being used in diverse classical LC displays. Thus, for example, PSA-VA, PSA-OCB, PSA-IPS, PSA-FFS and PSA-TN displays are known. The polymerisation of the polymerizable compound(s) preferably takes place with an applied electrical voltage in the case of PSA-VA and PSA-OCB displays, and with or without an applied electrical voltage in the case of PSA-IPS displays. As can be demonstrated in test cells, the PS(A) method results in a ‘pretilt’ in the cell. In the case of PSA-OCB displays, for example, it is possible for the bend structure to be stabilised so that an offset voltage is unnecessary or can be reduced. In the case of PSA-VA displays, the pretilt has a positive effect on the response times. A standard MVA or PVA pixel and electrode layout can be used for PSA-VA displays. In addition, however, it is also possible, for example, to manage with only one structured electrode side and no protrusions, which significantly simplifies production and at the same time results in very good contrast at the same time as very good light transmission.
PSA-VA displays are described, for example, in JP 10-036847 A, EP 1 170 626 A2, U.S. Pat. Nos. 6,861,107, 7,169,449, US 2004/0191428 A1, US 2006/0066793 A1 and US 2006/0103804 A1. PSA-OCB displays are described, for example, in T.-J- Chen et al., Jpn. J. Appl. Phys. 45, 2006, 2702-2704 and S. H. Kim, L.-C- Chien, Jpn. J. Appl. Phys. 43, 2004, 7643-7647. PSA-IPS displays are described, for example, in U.S. Pat. No. 6,177,972 and Appl. Phys. Lett. 1999, 75(21), 3264. PSA-TN displays are described, for example, in Optics Express 2004, 12(7), 1221. PSA-VA-IPS displays are disclosed, for example, in WO 2010/089092 A1.
Like the conventional LC displays described above, PSA displays can be operated as active-matrix or passive-matrix displays. In the case of active-matrix displays, individual pixels are usually addressed by integrated, non-linear active elements, such as, for example, transistors (for example thin-film transistors or “TFTs”), while in the case of passive-matrix displays, individual pixels are usually addressed by the multiplex method, both methods being known from the prior art.
In the prior art, polymerizable compounds of the following formula, for example, are used for PSA-VA:
in which P denotes a polymerizable group, usually an acrylate or methacrylate group, as described, for example, in U.S. Pat. No. 7,169,449.
Below the polymer layer which induces the above mentioned pretilt, an orientation layer—usually a polyimide—provides the initial alignment of the liquid crystal regardless of the polymer stabilisation step of the production process.
The effort for the production of a polyimide layer, treatment of the layer and improvement with bumps or polymer layers is relatively great. A simplifying technology which on the one hand reduces production costs and on the other hand helps to optimise the image quality (viewing-angle dependence, contrast, response times) would therefore be desirable. Rubbed polyimide has been used for a long time to align liquid crystals. The rubbing process causes a number of problems: mura, contamination, problems with static discharge, debris, etc.
Photoalignment is a technology for achieving liquid crystal (LC) alignment that avoids rubbing by replacing it with a light-induced orientational ordering of the alignment surface. This can be achieved through the mechanisms of photodecomposition, photodimerization, and photoisomerization (N. A. Clark et al. Langmuir 2010, 26(22), 17482-17488, and literature cited therein) by means of polarised light. However, still a suitably derivatised polyimide layer is required that comprises the photoreactive group. A further improvement would be to avoid the use of polyimide at all. For VA displays this was achieved by adding a self-alignment agent to the LC that induces homeotropic alignment in situ by a self-assembling mechanism as disclosed in WO 2012/104008 and WO 2012/038026.
N. A. Clark et al. Langmuir 2010, 26(22), 17482-17488 have shown that it is possible to self-assemble a compound of the following structure
onto a substrate to give a monolayer that is able to be photoaligned to induce homogeneous alignment of a liquid crystal. However, a separate step of self-assembly before manufacture of the LC cell is required and the nature of the azo-group causes reversibility of the alignment when exposed to light.
Another functional group known to enable photoalignment is the phenylethenylcarbonyloxy group (cinnamate). Photocrosslinkable cinnamates are known from the prior art, e.g. of the following structure
as disclosed in EP0763552. From such compounds, polymers can be obtained, for example the following
This material was used in a photoalignment process, as disclosed in WO 99/49360, to give an orientation layer for liquid crystals. A disadvantage of orientation layers obtained by this process is that they give lower voltage holding ratios (VHR) than polyimides.
In WO 00/05189 polymerizable direactive mesogenic cinnamates are disclosed for the use in polymerizable LC mixtures for e.g. optical retarders.
A structurally related compound of the following formula
comprising two cinnamic acid moieties is disclosed in GB 2 306 470 A for the use as component in liquid crystalline polymer films. This type of compound has not been used or proposed for the use as photoalignment agent.
A very similar compound is published in B.M.I. van der Zande et al., Liquid Crystals, Vol. 33, No. 6, June 2006, 723-737, in the field of liquid crystalline polymers for patterned retarders, and has the following structure:
WO 2017/102068 A1 discloses the same structure for the purpose of a polyimide-free homogeneous photoalignment method.
Further, M. H. Lee et al. published in Liquid Crystals (https://doi.org/10.1080/02678292.2018.1441459) a polyimide-free homogeneous photoalignment method induced by polymerizable liquid crystal containing cinnamate moiety of the following formula:
WO 2018/008581 A1 provides a liquid crystal display device that is equipped with: a liquid crystal layer containing a liquid crystal material; a sealing material positioned so as to surround the liquid crystal layer when seen from a planar view; a pair of substrates which sandwich the liquid crystal layer and are joined to one another by the sealing material; and an alignment control layer positioned so as to contact the liquid crystal layer in the region surrounded by the sealing material when seen from a planar view. Therein, the alignment control layer aligns the liquid crystal material in the horizontal direction relative to the substrate surface, and contains a polymer containing a unit derived from at least a specific first monomer of the following formulae:
WO 2018/139507 A1 addresses the problem of controlling the alignment of liquid crystal molecules of a liquid crystal display element not having an alignment film by using a non-colored alignable monomer of the following formulae:
Both types of the above-suggested monomers are limited in their solubility in modern liquid crystalline mixtures and limited in their processability especially in view of modern methods for mass production.
Thus, there is a great demand for new photoreactive mesogens that enable photoalignment of a liquid crystal mixture in situ, i.e. after assembly of the display, by means of linearly polarized light.
In addition to this requirement, the corresponding photoreactive mesogen should provide, preferably at the same time, a liquid crystal display having favourable high dark state and a favourable high voltage holding ratio. Furthermore, the amount of photoreactive mesogens in the nematic LC medium should be a low as possible and the process for the production should be obtainable from a process that is compatible with common mass production processes, e.g. in terms of favourable short processing times.
Other aims of the present invention are immediately evident to the person skilled in the art from the following detailed description.
Surprisingly, the inventors have found out that one or more of the above-mentioned aims can be achieved by providing a compound according to formula I,
A photoreactive group according to the present invention is a functional group of a molecule that causes a change of the geometry of the molecule either by bond rotation, skeletal rearrangement or atom- or group-transfer, or by dimerization, upon irradiation with light of a suitable wavelength that can be absorbed by the molecule.
The term “mesogenic group” as used herein is known to the person skilled in the art and described in the literature, and means a group which, due to the anisotropy of its attracting and repelling interactions, essentially contributes to causing a liquid-crystal (LC) phase in low-molecular-weight or polymeric substances. Compounds containing mesogenic groups (mesogenic compounds) do not necessarily have to have an LC phase themselves. It is also possible for mesogenic compounds to exhibit LC phase behaviour only after mixing with other compounds and/or after polymerisation. Typical mesogenic groups are, for example, rigid rod- or disc-shaped units. An overview of the terms and definitions used in connection with mesogenic or LC compounds is given in Pure Appl. Chem. 2001, 73(5), 888 and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368.
A photoreactive mesogen according to the present invention is a mesogenic compound comprising one or more photoreactive groups.
Examples of photoreactive groups are —C═C— double bonds and azo groups (—N═N—).
Examples of molecular structures and sub-structures comprising such photoreactive groups are stilbene, (1,2-difluoro-2-phenyl-vinyl)-benzene, cinnamate, 4-phenylbut-3-en-2-one, chalcone, coumarin, chromone, pentalenone and azobenzene.
According to the present application, the term “linearly polarised light” means light, which is at least partially linearly polarized. Preferably, the aligning light is linearly polarized with a degree of polarization of more than 5:1. Wavelengths, intensity and energy of the linearly polarised light are chosen depending on the photosensitivity of the photoalignable material. Typically, the wavelengths are in the UV-A, UV-B and/or UV-C range or in the visible range. Preferably, the linearly polarised light comprises light of wavelengths less than 450 nm, more preferably less than 420 nm at the same time the linearly polarised light preferably comprises light of wavelengths longer than 280 nm, preferably more than 320 nm, more preferably over 350 nm.
The term “organic group” denotes a carbon or hydrocarbon group.
The term “carbon group” denotes a mono- or polyvalent organic group containing at least one carbon atom, where this either contains no further atoms (such as, for example, —C≡C—) or optionally contains one or more further atoms, such as, for example, N, O, S, P, Si, Se, As, Te or Ge (for example carbonyl, etc.). The term “hydrocarbon group” denotes a carbon group which additionally contains one or more H atoms and optionally one or more heteroatoms, such as, for example, N, O, S, P, Si, Se, As, Te or Ge.
“Halogen” denotes F, Cl, Br or I.
A carbon or hydrocarbon group can be a saturated or unsaturated group. Unsaturated groups are, for example, aryl, alkenyl or alkynyl groups. A carbon or hydrocarbon radical having 3 or more atoms can be straight-chain, branched and/or cyclic and may also contain spiro links or condensed rings.
The terms “alkyl”, “aryl”, “heteroaryl”, etc., also encompass polyvalent groups, for example alkylene, arylene, heteroarylene, etc.
The term “aryl” denotes an aromatic carbon group or a group derived therefrom. The term “heteroaryl” denotes “aryl” as defined above, containing one or more heteroatoms.
Preferred carbon and hydrocarbon groups are optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy having 1 to 40, preferably 1 to 25, particularly preferably 1 to 18, C atoms, optionally substituted aryl or aryloxy having 6 to 40, preferably 6 to 25, C atoms, or optionally substituted alkylaryl, arylalkyl, alkylaryloxy, arylalkyloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy having 6 to 40, preferably 6 to 25, C atoms.
Further preferred carbon and hydrocarbon groups are C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 allyl, C4-C40 alkyldienyl, C4-C40 polyenyl, C6-C40 aryl, C6-C40 alkylaryl, C6-C40 arylalkyl, C6-C40 alkylaryloxy, C6-C40 arylalkyloxy, C2-C40 heteroaryl, C4-C40 cycloalkyl, C4-C40 cycloalkenyl, etc. Particular preference is given to C1-C22 alkyl, C2-C22 alkenyl, C2-C22 alkynyl, C3-C22 allyl, C4-C22 alkyldienyl, C6-C12 aryl, C6-C20 arylalkyl and C2-C20 heteroaryl.
Further preferred carbon and hydrocarbon groups are straight-chain, branched or cyclic alkyl radicals having 1 to 40, preferably 1 to 25, C atoms, which are unsubstituted or mono- or polysubstituted by F, Cl, Br, I or CN and in which one more non-adjacent CH2 groups may each be replaced, independently of one another, by —C(Rz)═C(Rz)—, —C≡C—, —N(Rz)—, —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a way that O and/or S atoms are not linked directly to one another.
Rz preferably denotes H, halogen, a straight-chain, branched or cyclic alkyl chain having 1 to 25 C atoms, in which, in addition, one or more nonadjacent C atoms may be replaced by —O—, —S—, —CO—, —CO—O—, —O—CO— or —O—CO—O— and in which one or more H atoms may be replaced by fluorine, an optionally substituted aryl or aryloxy group having 6 to 40 C atoms, or an optionally substituted heteroaryl or heteroaryloxy group having 2 to 40 C atoms.
Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, trifluoromethyl, perfluoro-n-butyl, 2,2,2-trifluoroethyl, perfluorooctyl and perfluorohexyl.
Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl and cyclooctenyl.
Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl and octynyl.
Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2-methylbutoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecoxy and n-dodecoxy.
Preferred amino groups are, for example, dimethylamino, methylamino, methylphenylamino and phenylamino.
Aryl and heteroaryl groups can be monocyclic or polycyclic, i.e. they can contain one ring (such as, for example, phenyl) or two or more rings, which may also be fused (such as, for example, naphthyl) or covalently bonded (such as, for example, biphenyl), or contain a combination of fused and linked rings. Heteroaryl groups contain one or more heteroatoms, preferably selected from O, N, S and Se. A ring system of this type may also contain individual non-conjugated units, as is the case, for example, in the fluorene basic structure.
Particular preference is given to mono-, bi- or tricyclic aryl groups having 6 to 25 C atoms and mono-, bi- or tricyclic heteroaryl groups having 2 to 25 C atoms, which optionally contain fused rings and are optionally substituted. Preference is furthermore given to 5-, 6- or 7-membered aryl and heteroaryl groups, in which, in addition, one or more CH groups may be replaced by N, S or O in such a way that O atoms and/or S atoms are not linked directly to one another.
Preferred aryl groups are derived, for example, from the parent structures benzene, biphenyl, terphenyl, [1,1′:3′,1″ ]terphenyl, naphthalene, anthracene, binaphthyl, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene, spirobifluorene, etc.
Preferred heteroaryl groups are, for example, 5-membered rings, such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 6-membered rings, such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, or condensed groups, such as indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalin-imidazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, benzoisoquinoline, acridine, phenothiazine, phenoxazine, benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthridine, phenanthroline, thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithienothiophene, dihydrothieno [3,4-b]-1,4-dioxin, isobenzothiophene, dibenzothiophene, benzothiadiazothiophene, or combinations of these groups. The heteroaryl groups may also be substituted by alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl or further aryl or heteroaryl groups.
The (non-aromatic) alicyclic and heterocyclic groups encompass both saturated rings, i.e. those containing exclusively single bonds, and also partially unsaturated rings, i.e. those which may also contain multiple bonds. Heterocyclic rings contain one or more heteroatoms, preferably selected from Si, O, N, S and Se.
The (non-aromatic) alicyclic and heterocyclic groups can be monocyclic, i.e. contain only one ring (such as, for example, cyclohexane), or polycyclic, i.e. contain a plurality of rings (such as, for example, decahydronaphthalene or bicyclooctane). Particular preference is given to saturated groups. Preference is furthermore given to mono-, bi- or tricyclic groups having 3 to 25 C atoms, which optionally contain fused rings and are optionally substituted. Preference is furthermore given to 5-, 6-, 7- or 8-membered carbocyclic groups, in which, in addition, one or more C atoms may be replaced by Si and/or one or more CH groups may be replaced by N and/or one or more non-adjacent CH2 groups may be replaced by —O— and/or —S—.
Preferred alicyclic and heterocyclic groups are, for example, 5-membered groups, such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran, pyrrolidine, 6-membered groups, such as cyclohexane, silinane, cyclohexene, tetrahydropyran, tetrahydrothiopyran, 1,3-dioxane, 1,3-dithiane, piperidine, 7-membered groups, such as cycloheptane, and fused groups, such as tetrahydronaphthalene, decahydronaphthalene, indane, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, octahydro-4,7-methanoindane-2,5-diyl.
The aryl, heteroaryl, carbon and hydrocarbon radicals optionally have one or more substituents, which are preferably selected from the group comprising silyl, sulfo, sulfonyl, formyl, amine, imine, nitrile, mercapto, nitro, halogen, C1-12 alkyl, C6-12 aryl, C1-12 alkoxy, hydroxyl, or combinations of these groups.
Preferred substituents are, for example, solubility-promoting groups, such as alkyl or alkoxy, and electron-withdrawing groups, such as fluorine, nitro or nitrile.
Preferred substituents, unless stated otherwise, also referred to as “L” above and below, are F, Cl, Br, I, —CN, —NO2, —NCO, —NCS, —OCN, —SCN, —C(═O)N(Rz)2, —C(═O)Y1, —C(═O)Rz, —N(Rz)2, in which Rz has the meaning indicated above, and Y1 denotes halogen, optionally substituted silyl or aryl having 6 to 40, preferably 6 to 20, C atoms, and straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 C atoms, preferably 2 to 12, in which one or more H atoms may optionally be replaced by F or Cl.
“Substituted silyl or aryl” preferably means substituted by halogen, —CN, Ry1, —ORy1, —CO—Ry1, —CO—O—Ry1, —O—CO—Ry1 or —O—CO—O—Ry1, in which Ry1 has the meaning indicated above.
Particularly preferred substituents L are, for example, F, Cl, CN, CH3, C2H5, —CH(CH3)2, OCH3, OC2H5, CF3, OCF3, OCHF2, OC2F5, furthermore phenyl.
Above and below “halogen” denotes F, Cl, Br or I.
Above and below, the terms “alkyl”, “aryl”, “heteroaryl”, etc., also encompass polyvalent groups, for example alkylene, arylene, heteroarylene, etc.
The term “director” is known in prior art and means the preferred orientation direction of the long molecular axes (in case of calamitic compounds) or short molecular axes (in case of discotic compounds) of the liquid-crystalline molecules. In case of uniaxial ordering of such anisotropic molecules, the director is the axis of anisotropy.
The term “alignment” or “orientation” relates to alignment (orientation ordering) of anisotropic units of material such as small molecules or fragments of big molecules in a common direction named “alignment direction”. In an aligned layer of liquid-crystalline material, the liquid-crystalline director coincides with the alignment direction so that the alignment direction corresponds to the direction of the anisotropy axis of the material.
The term “planar orientation/alignment”, for example in a layer of an liquid-crystalline material, means that the long molecular axes (in case of calamitic compounds) or the short molecular axes (in case of discotic compounds) of a proportion of the liquid-crystalline molecules are oriented substantially parallel (about 180°) to the plane of the layer.
The term “homeotropic orientation/alignment”, for example in a layer of a liquid-crystalline material, means that the long molecular axes (in case of calamitic compounds) or the short molecular axes (in case of discotic compounds) of a proportion of the liquid-crystalline molecules are oriented at an angle θ (“tilt angle”) between about 80° to 90° relative to the plane of the layer.
The terms “uniform orientation” or “uniform alignment” of an liquid-crystalline material, for example in a layer of the material, mean that the long molecular axes (in case of calamitic compounds) or the short molecular axes (in case of discotic compounds) of the liquid-crystalline molecules are oriented substantially in the same direction. In other words, the lines of liquid-crystalline director are parallel.
The wavelength of light generally referred to in this application is 550 nm, unless explicitly specified otherwise.
The birefringence Δn herein is defined by the following equation
Δn=ne−no
wherein ne is the extraordinary refractive index and no is the ordinary refractive index and the effective average refractive index nav. is given by the following equation
n
av.=[(2no2+ne2)/3]1/2
The extraordinary refractive index ne and the ordinary refractive index no can be measured using an Abbe refractometer.
In the present application the term “dielectrically positive” is used for compounds or components with Δε>3.0, “dielectrically neutral” with −1.5≤Δε≤3.0 and “dielectrically negative” with Δε<−1.5. Δε is determined at a frequency of 1 kHz and at 20° C. The dielectric anisotropy of the respective compound is determined from the results of a solution of 10% of the respective individual compound in a nematic host mixture. In case the solubility of the respective compound in the host medium is less than 10% its concentration is reduced by a factor of 2 until the resultant medium is stable enough at least to allow the determination of its properties. Preferably, the concentration is kept at least at 5%, however, to keep the significance of the results as high as possible. The capacitance of the test mixtures are determined both in a cell with homeotropic and with homogeneous alignment. The cell gap of both types of cells is approximately 20 μm. The voltage applied is a rectangular wave with a frequency of 1 kHz and a root mean square value typically of 0.5 V to 1.0 V; however, it is always selected to be below the capacitive threshold of the respective test mixture.
Δε is defined as (ε∥−ε⊥), whereas εav. is (ε∥+2 ε⊥)/3. The dielectric permittivity of the compounds is determined from the change of the respective values of a host medium upon addition of the compounds of interest. The values are extrapolated to a concentration of the compounds of interest of 100%. A typical host medium is ZLI-4792 or ZLI-2857 both commercially available from Merck, Darmstadt.
For the present invention,
denote trans-1,4-cyclohexylene,
denote 1,4-phenylene.
For the present invention the groups —CO—O—, —COO— —C(═O)O— or —CO2— denote an ester group of formula
and the groups —O—CO— —OCO—, —OC(═O)—, —O2C— or —OOC— denote an ester group of formula
Furthermore, the definitions as given in C. Tschierske, G. Pelzl and S. Diele, Angew. Chem. 2004, 116, 6340-6368 shall apply to non-defined terms related to liquid crystal materials in the instant application.
In detail, the present invention relates to compounds or photoreactive mesogens of formula I,
wherein
Further preferred are compounds of formula I, wherein
Further preferred are compounds of formula I, wherein
In the instant application, polymerizable groups (P) are groups that are suitable for a polymerisation reaction, such as, for example, free-radical or ionic chain polymerisation, polyaddition or polycondensation, or for a polymer-analogous reaction, for example addition or condensation onto a main polymer chain. Particular preference is given to groups for chain polymerisation, in particular those containing a C═C double bond or —C≡C— triple bond, and groups which are suitable for polymerisation with ring opening, such as, for example, oxetane or epoxide groups.
Preferred groups P11 are selected from the group consisting of CH2═CW1—CO—O—, CH2═CW1—CO—,
CH2═CW2—(O)k3—, CW1═CH—CO—(O)k3—, CW1═CH—CO—NH—, CH2═CW1—CO—NH—, CH3—CH═CH—O—, (CH2═CH)2CH—OCO—, (CH2═CH—CH2)2CH—OCO—, (CH2═CH)2CH—O—, (CH2═CH—CH2)2N—, (CH2═CH—CH2)2N—CO—, HO—CW2W3—, HS—CW2W3—, HW2N—, HO—CW2W3—NH—, CH2═CW1—CO—NH—, CH2═CH—(COO)k1-Phe-(O)k2—, CH2═CH—(CO)k1-Phe-(O)k2—, Phe-CH═CH—, HOOC—, OCN— and W4W5W6Si—, wherein W1 denotes H, F, Cl, CN, CF3, phenyl or alkyl having 1 to 5 C atoms, in particular H, F, Cl or CH3, W2 and W3 each, independently of one another, denote H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl, W4, W5 and W6 each, independently of one another, denote Cl, oxaalkyl or oxacarbonylalkyl having 1 to 5 C atoms, W7 and W8 each, independently of one another, denote H, Cl or alkyl having 1 to 5 C atoms, Phe denotes 1,4-phenylene, which is optionally substituted by one or more radicals L as defined above which are other than P-Sp-, k1, k2 and k3 each, independently of one another, denote 0 or 1, k3 preferably denotes 1, and k4 denotes an integer from 1 to 10.
Particularly preferred groups P11 are selected from the group consisting of CH2═CW1—CO—O—, in particular CH2═CH—CO—O—, CH2═C(CH3)—CO—O— and CH2═CF—CO—O—, furthermore CH2═CH—O—, (CH2═CH)2CH—O—CO—, (CH2═CH)2CH—O—,
Very particularly preferred groups P11 are selected from the group consisting of acrylate, methacrylate, fluoroacrylate, furthermore vinyloxy, chloroacrylate, oxetane and epoxide groups, and of these preferably an vinyloxy, acrylate or methacrylate group.
The compounds of formula I are preferably selected from compounds of the sub-formulae I-1 to I-9,
wherein R11, R21, A11, X11, X21, Y11, Y12, Sp11, and Sp21 have one of the meanings as given above in formula I, A12 to A23 have one of the meanings for A in formula I, and Z11 to Z22 have one of the meanings for Z as given above under formula I.
Further preferred are compounds of formula I-1, wherein
Further preferred are compounds of formula I, wherein
Further preferred compounds of formula I are selected from the following compounds of formulae I-1a to I-4c.
wherein L, R11, R21, A11, X11, X21, Y11, Y12, Sp11, and Sp21 have one of the meanings as given above in formula I, A12 to A23 have one of the meanings for A in formula I, and Z11 to Z22 have one of the meanings for Z as given above under formula I.
Further preferred are compounds of formula I-1a, wherein
Further preferred are compounds of formula I, wherein
Further preferred compounds of formula I are selected from the following compounds:
wherein L, R11, R21, A11, Y11, Y12, X11, X21, Sp11, and Sp21 have one of the meanings as given above in formula I, A12 and A22 have one of the meanings for A in formula I, and Z11 and Z22 have one of the meanings for Z as given above under formula I.
Further preferred are compounds of formula I-1a-1, wherein
Further preferred are compounds of formula I, wherein
Further preferred compounds of formula I-2a-1 to I-3b-2 are selected from the following compounds:
wherein L, R11, R21, Y11, Y12, X11, X21, Sp11, and Sp12 have one of the meanings as given above in formula I, and
the group
is each and independently
or denotes
furthermore
wherein L have one of the meanings as given above in formula I, and preferably denotes F, Cl, OCH3, COCH3 or alkyl having 1 to 6 C Atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or X21-Sp21-R21.
Further preferred compound of formula I and subformulae thereof are selected from compounds wherein the groups —X11-Sp11-R11 and X21-Sp21-R21 are selected from different groups, such as
—X11-Sp11-P11 and —X21-Sp21-P21,
—X11-Sp11-P21 and —X21-Sp21-P11,
—P11 and —X21-Sp21-P21, or
—X11-Sp11-P21 and —P11.
However it is likewise preferred that the groups —X11-Sp11-R11 and X21-Sp21—R21 are identical, such as —X11-Sp11-P21 and —X21-Sp21-P21.
Especially preferred compounds of formula I are selected from compounds of the following sub-formula:
wherein Sp11 and Sp21 have one of the meanings as given above in formula I, and Y denotes methyl or ethyl.
In particular preferred compounds of formula I are selected from compounds of the formulae I-1a-1-3, I-1a-1-4, I-1a-1-6, I-1a-1-9, I-1a-1-10, or I-1a-1-12.
Preferred intermediate compounds (6) from which the compounds of formula I are preferably synthesised, are obtainable or obtained according to or in analogy to the procedure described in the following scheme:
The compounds of formula I are prepared by methods known per se, as described in the literature (for example in the standard works, such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), to be precise under reaction conditions which are known and suitable for the said reactions. Use can also be made here of variants known per se, which are not mentioned here in greater detail.
Preferably the compounds of formula I are synthesised, are obtainable or obtained according to or in analogy to the procedure described in the following scheme:
In another preferred embodiment, the compounds of formula I are synthesised, are obtainable or obtained according to or in analogy to the procedure described in the following scheme:
The compounds of formula I and subformulae thereof can be preferably utilized in a mixture comprising one or more mesogenic or liquid-crystalline compounds.
Therefore, the present invention relates to the use compounds of formula I and subformulae thereof in a liquid crystal mixture.
Further the present invention relates to liquid crystal mixtures comprising a photoalignment component A) comprising one or more photoreactive mesogens of formula I, and a liquid-crystalline component B), hereinafter also referred to as “LC host mixture”, comprising one or more mesogenic or liquid-crystalline compounds.
The media according to the invention preferably comprise from 0.01 to 10%, particularly preferably from 0.05 to 5% and most preferably from 0.1 to 3% of component A) comprising compounds of formula I according to the invention.
The media preferably comprise one, two or three, more preferably one or two and most preferably one compound of the formula I according to the invention.
In a preferred embodiment component A) consists of compounds of formula I.
In a preferred embodiment, the LC-host mixture (component B) according to the present invention comprises one or more, preferably two or more, low-molecular-weight (i.e. monomeric or unpolymerized) compounds. The latter are stable or unreactive with respect to a polymerisation reaction or photoalignment under the conditions used for the polymerisation of the polymerizable compounds or photoalignment of the photoreactive mesogen of formula I.
In principle, a suitable host mixture is any dielectrically negative or positive LC mixture which is suitable for use in conventional VA, IPS or FFS displays.
Suitable LC mixtures are known to the person skilled in the art and are described in the literature. LC media for VA displays having negative dielectric anisotropy are described in for example EP 1 378 557 A1.
Suitable LC mixtures having positive dielectric anisotropy which are suitable for LCDs and especially for IPS displays are known, for example, from JP 07-181 439 (A), EP 0 667 555, EP 0 673 986, DE 195 09 410, DE 195 28 106, DE 195 28 107, WO 96/23 851, WO 96/28 521 and WO2012/079676.
Preferred embodiments of the liquid-crystalline medium having negative or positive dielectric anisotropy according to the invention are indicated below and explained in more detail by means of the working examples.
The LC host mixture is preferably a nematic LC mixture, and preferably does not have a chiral LC phase.
In a preferred embodiment of the present invention the LC medium contains an LC host mixture with negative dielectric anisotropy. Preferred embodiments of such an LC medium, and the corresponding LC host mixture, are those of sections a)-z) below:
denotes
denotes
denotes
denotes
denotes
and
denotes
in which
denotes
In another preferred embodiment of the present invention the LC medium contains an LC host mixture with positive dielectric anisotropy. Preferred embodiments of such an LC medium, and the corresponding LC host mixture, are those of sections aa)-mmm) below:
—O—, —CO—O— or —O—CO— in such a way that O atoms are not linked directly to one another,
each, independently of one another, denote
each, independently of one another, denote
denotes
denotes
is preferably
Further preferred embodiments are indicated below:
In a preferred embodiment, the liquid crystal mixture according to the present invention further comprises a polymerizable component C) comprising one or more polymerizable compounds.
The polymerizable compounds can be selected from isotropic or mesogenic polymerizable compounds known to the skilled person in the art.
Preferably, the polymerizable component C) comprises one or more polymerizable compounds of formula P,
Pa-(Spa)s1-A2-(Za-A1)n2-(Spb)s2-Pb P
wherein the individual radicals have the following meanings:
Preferred spacer groups Spa,b are selected from the formula Sp″-X″, so that the radicals P-Sp- and Pa/b-Spa/b- conforms to the formulae P-Sp″-X″— and Pa/b-Sp″-X″—, respectively, wherein
X″ is preferably —O—, —S—, —CO—, —C(O)O—, —OC(O)—, —O—C(O)O—, —CO—NR0—, —NR0—CO—, —NR0—CO—NR0— or a single bond.
Typical spacer groups Sp″ are, for
example, —(CH2)p1—, —(CH2CH2O)q1—CH2CH2—, —CH2CH2—S—CH2CH2—, —CH2CH2—NH—CH2CH2— or —(SiR00R000—O)p1—, wherein p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R00 and R000 have the meanings indicated above.
Particularly preferred groups -Sp″-X″— are —(CH2)p1—, —(CH2)p1—O—, —(CH2)p1—O—CO—, —(CH2)p1—O—CO—O—, wherein p1 and q1 have the meanings indicated above.
Particularly preferred groups Sp″ are, for example, in each case straight-chain ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene.
Particularly preferred monomers of formula P are the following:
In a particularly preferred embodiment of the present invention the LC mixture, or component C), comprises one or more compounds of formula P10-1.
wherein the parameters are defined as described above and P1 and P2 preferably denote acrylate or methacrylate.
Particularly preferred compounds of formula P10-1 are selected from the group of the following subformulae
wherein each n4 denote independently of each other an integer between 2 and 10, preferably 3, 4, 5 or 6.
In another preferred embodiment, the polymerizable component C) comprises one or more polymerizable compounds of formula CC,
Pa-Spa-(Ap)n2-Spb-Pb CC
wherein the individual radicals have the following meanings:
Preferred spacer groups Spa,b are selected from the formula Sp″-X″, so that the radicals P-Sp- and Pa/b-Spa/b- conforms to the formulae P-Sp″-X″— and Pa/b-Sp″-X″—, respectively, wherein
X″ is preferably —O—, —S—, —CO—, —C(O)O—, —OC(O)—, —O—C(O)O—, —CO—NR0—, —NR0—CO—, —NR0—CO—NR0— or a single bond.
Typical spacer groups Sp″ are, for example, a single bon, —(CH2)p1—, —(CH2CH2O)q1—CH2CH2—, —CH2CH2—S—CH2CH2—, —CH2CH2—NH—CH2CH2— or —(SiR00R000—O)p1—, wherein p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R00 and R000 have the meanings indicated above.
Particularly preferred groups -Sp″-X″— are a single bond, —(CH2)p1—, —(CH2)p1—O—, —(CH2)p1—O—CO—, —(CH2)p1—O—CO—O—, wherein p1 and q1 have the meanings indicated above.
Particularly preferred groups Sp″ are, for example, in each case straight-chain methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene.
Particularly preferred monomers of formula CC are the following:
In another preferred embodiment, the polymerizable component C) in accordance with the present invention may comprise, preferably consists of, one or more compounds of formula Palk,
P″-Sp′-P″ Palk
wherein the individual radicals have the meanings:
Preferred spacer groups Sp′ are selected from the formula —X″-Sp″-X″—
X″ is preferably —O—, —S—, —CO—, —C(O)O—, —OC(O)—, —O—C(O)O—, —CO—NR0—, —NR0—CO—, —NR0—CO—NR0— or a single bond.
Typical spacer groups Sp″ are, for
example, —(CH2)p1—, —(CH2CH2O)q1—CH2CH2—, —CH2CH2—S—CH2CH2—, —CH2CH2—NH—CH2CH2— or —(SiR00R000—O)p1—, wherein p1 and q1 are integers from 1 to 20, and R00 and R000 have the meanings indicated above.
Particularly preferred groups X″-Sp″-X″— are —(CH2)p1—, —(CH2CH2O)q1—CH2CH2— —(CH2)p1—O—, —(CH2)p1—O—CO—, —(CH2)p1—O—CO—O—, —O—(CH2)p1—O—, —O—CO—(CH2)p1—O—CO—, —O—CO—O—(CH2)p1—O—CO—O—, —O—(CH2)p1—, —O—CO—(CH2)p1—, —O—CO—O—(CH2)p1—, wherein p1 and q1 have the meanings indicated above.
Particularly preferred groups Sp″ are, for example, in each case straight-chain ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene,
furthermore —(CH2CH2O)q1—(CH2CH2)p1—, —(CH2CH2)p1—(OCH2CH2)q1—, or —(CH2CH2)p1—(CH2CH2O)q1—(CH2CH2)r1 wherein p1, q1 and r1 each and independently denotes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.
Particularly preferred monomers of formula P are the following:
The polymerizable compounds of formulae I, P, CC and Palk are also suitable for polymerisation without an initiator, which is associated with considerable advantages, such as, for example, lower material costs and, in particular, reduced contamination of the LC medium by possible residual amounts of the initiator or degradation products thereof. The polymerisation can thus also be carried out without addition of an initiator. The LC medium thus, in a preferred embodiment, comprises no polymerisation initiator.
The polymerizable component C) or the LC medium as a whole may also comprise one or more stabilisers in order to prevent undesired spontaneous polymerisation of the RMs, for example during storage or transport. Suitable types and amounts of stabilisers are known to the person skilled in the art and are described in the literature. Particularly suitable are, for example, the commercially available stabilisers from the Irganox® series (BASF SE), such as, for example, Irganox® 1076. If stabilisers are employed, their proportion, based on the total amount of the RMs or the polymerizable component, is preferably 10-10,000 ppm, particularly preferably 50-1000 ppm.
The media according to the invention preferably comprise from 0.01 to 10%, particularly preferably from 0.05 to 7.5% and most preferably from 0.1 to 5% of the compounds of component C) comprising compounds of formula P according to the invention. The media preferably comprise one, two or three, more preferably one or two and most preferably one compound of the formula P according to the invention.
By means of suitable additives, the liquid-crystalline phases of the present invention can be modified in such a way that they can be used in all types of liquid-crystal display element that have been disclosed hitherto. Additives of this type are known to the person skilled in the art and are described in detail in the literature (H. Kelker/R. Hatz, Handbook of Liquid Crystals, Verlag Chemie, Weinheim, 1980). For example, pleochroic dyes can be added for the production of coloured guest-host systems or substances can be added in order to modify the dielectric anisotropy, the viscosity and/or the alignment of the nematic phases.
The media according to the invention are prepared in a manner conventional per se. In general, the components are dissolved in one another, preferably at elevated temperature.
Accordingly the present invention relates further to method for the production of an LC medium according to the present invention, comprising the step of mixing one or more compounds of formula I with a liquid-crystalline component B) comprising one or more mesogenic or liquid-crystalline compounds as described above.
The present invention further relates to a process for the fabrication of liquid crystal displays comprising at least the steps of:
The present invention further relates to the use of the liquid crystal mixtures according to the invention for the fabrication of a liquid crystal display.
The present invention further relates to liquid crystal displays fabricated by the process described above.
In the following, the production process according to the present invention is described in greater detail.
The first substrate includes a pixel electrode and a common electrode for generating an electric field substantially parallel to a surface of the first substrate in the pixel region. Various kinds of displays having at least two electrodes on one substrate are known to the skilled person wherein the most significant difference is that either both the pixel electrode and the common electrode are structured, as it is typical for IPS displays, or only the pixel electrode is structured and the common electrode is unstructured, which is the case for FFS displays.
It has to be understood that the present invention refers to any kind of electrode configurations suitable for generating an electric field substantially parallel to a surface of the first substrate in the pixel region, mentioned above, i.e. IPS as well as FFS displays.
The process according to the present invention is independent of the kind of substrate or material of the surface which is in contact with the liquid crystal mixture according to the invention, during and after this process. Examples of materials used for the substrates or surfaces are organic polymers including polyimide, indium tin oxide (ITO), indium zinc oxide (IZO), silicon nitride (SiNx) and silicon dioxide (SiO2). The process is especially suitable for the use in displays containing substrates that do not have a polyimide layer on one or more of the surfaces that are in contact with the liquid crystal.
In case one or more substrates contain a polyimide layer, the polyimide can be rubbed or not rubbed, preferably not rubbed.
Hence, the invention relates to a display produced by the process according to the invention in which the substrates contain a rubbed or unrubbed polyimide layer, preferably an unrubbed polyimide layer.
The invention further relates to a display produced by the process according to the invention in which none or only one of the top and bottom substrates contains a polyimide layer.
In one embodiment of the present invention the liquid crystal composition is injected between the first and second substrates or is filled into the cell by capillary force after combining the first and second substrates. In an alternative embodiment, the liquid crystal composition may be interposed between the first and second substrates by combining the second substrate to the first substrate after loading the liquid crystal composition on the first substrate. Preferably, the liquid crystal is dispensed dropwise onto a first substrate in a process known as “one drop filling” (ODF) process, as disclosed in for example JPS63-179323 and JPH10-239694, or using the Ink Jet Printing (IJP) method.
In a preferred embodiment, the process according to the invention contains a process step where the liquid crystal inside the display panel is allowed to rest for a period of time in order to evenly redistribute the liquid crystal medium inside the panel (herein referred to as “annealing”).
However it is likewise preferred that the annealing step is combined with a previous step, such as edge sealant pre-curing. In which case a ‘separate’ annealing step may not be necessary at all.
For the production of the displays according to the present invention, the photoreactive mesogen of formula I is preferably allowed to redistribute in the panel. After filling and assembly, the display panel is annealed for a time between 1 min and 3 h, preferably between 2 min and 1 h and most preferably between 5 min and 30 min. The annealing is preferably performed at room temperature.
In an alternative embodiment, the annealing is performed at elevated temperature, preferably at above 20° C. and below 140° C., more preferably above 40° C. and below 100° C. and most preferably above 50° C. and below 80° C.
Preferably the annealing is performed at elevated temperature, preferably 30° C. above the clearing point of the utilized host mixture, more preferably 20° C. above the clearing point of the utilized host mixture, and most preferably 5 to 15° C. above the clearing point of the utilized host mixture.
In a preferred embodiment, one or more of the process steps of filling the display, annealing, photoalignment and curing of the polymerizable compound is performed at a temperature above the clearing point of the liquid crystal host mixture.
During the photoalignment of the liquid crystal inside the liquid crystal panel, anisotropy is induced by exposing the display or the liquid crystal layer to linearly polarised light.
In a preferred embodiment of the present invention the photoreactive component A) comprising one or more compounds of formula I, is photoaligned in a first step using linearly polarised light and in a second step further cured using linearly polarized or unpolarised UV light. In the second step the optional component C) is also further cured.
In another preferred embodiment, the linearly polarised light applied according to the inventive process is ultraviolet light which enables simultaneous photoalignment and photocuring of the photoreactive component A) comprising one or more compounds of formula I, and, if present, photocuring of the polymerizable component C).
Photoalignment of the photoreactive compounds of formula I and curing of the polymerizable groups of compounds of formula I and the curing of the optional polymerizable compounds of formula P can be performed simultaneously or stepwise. In case the process is split into different steps, the individual steps can be performed at the same temperature or at different temperatures.
After the photoalignment and curing step(s) a so-called “post-curing” step can optionally be performed by irradiation with UV-light and/or visible light (both either linearly or unpolarised) at reduced temperature in order to remove unreacted polymerizable compounds. The post-curing is preferably performed at above 0° C. and below the clearing point of the utilized LC mixture, preferably 20° C. and below 60° C.° C., and most preferably above 20° C. and below 40° C.
The polymerizable compounds are optionally polymerised or crosslinked (if a polymerizable compound contains two or more polymerizable groups) with the application of an electrical field. The polymerisation can be carried out in one or more steps.
Suitable and preferred polymerisation methods for component C) are, for example, thermal or photopolymerization, preferably photopolymerization, in particular UV photopolymerization. One or more initiators can optionally also be added here. Suitable conditions for the polymerisation and suitable types and amounts of initiators are known to the person skilled in the art and are described in the literature. Suitable for free-radical polymerisation are, for example, the commercially available photoinitiators Irgacure651®, Irgacure184®, Irgacure907®, Irgacure369® or Darocure1173® (BASF SE). If an initiator is employed, its proportion is preferably 0.001 to 5% by weight, particularly preferably 0.001 to 1% by weight.
The present invention also relates to electro-optical liquid-crystal display elements containing a liquid-crystalline medium according to the invention, which is preferably homogeneously aligned. In a preferred embodiment the liquid crystal display is of the IPS or FFS mode.
Further combinations of the embodiments and variants of the invention in accordance with the description arise from the claims.
The invention is explained in greater detail below with reference to working examples, but without intending to be restricted thereby. The person skilled in the art will be able to glean from the examples working details that are not given in detail in the general description, generalise them in accordance with general expert knowledge and apply them to a specific problem.
Besides the usual and well-known abbreviations, the following abbreviations are used:
C: crystalline phase; N: nematic phase; Sm: smectic phase; I: isotropic phase. The numbers between these symbols show the transition temperatures of the substance concerned.
Temperature data are in ° C. unless indicated otherwise.
Physical, physicochemical or electro-optical parameters are determined by generally known methods, as described, inter alia, in the brochure “Merck Liquid Crystals—Licristal®—Physical Properties of Liquid Crystals—Description of the Measurement Methods”, 1998, Merck KGaA, Darmstadt.
Above and below, Δn denotes the optical anisotropy (589 nm, 20° C.) and Δε denotes the dielectric anisotropy (1 kHz, 20° C.). The dielectric anisotropy Δε is determined at 20° C. and 1 kHz. The optical anisotropy Δε is determined at 20° C. and a wavelength of 589.3 nm.
The Δε and Δε values and the rotational viscosity (γ1) of the compounds according to the invention are obtained by linear extrapolation from liquid-crystalline mixtures consisting of 5 to 10% of the respective compound according to the invention and 90-95% of the commercially available liquid-crystal mixture ZLI-2857 (for Δε) or ZLI-4792 (for Δn, γ1) (mixtures, Merck KGaA, Darmstadt).
The compounds used in the present invention are prepared by methods known per se, as described in the literature (for example in the standard works, such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), to be precise under reaction conditions which are known and suitable for the said reactions. Use can also be made here of variants known per se, which are not mentioned here in greater detail.
In the present invention and especially in the following examples, the structures of the mesogenic compounds are indicated by means of abbreviations, also called acronyms. In these acronyms, the chemical formulae are abbreviated as follows using Tables A to C below. All groups CnH2n+1, CmH2m+1 and ClH2l+1 or CnH2n−1, CmH2m−1 and ClH2l−1 denote straight-chain alkyl or alkenyl, preferably 1E-alkenyl, each having n, m and l C atoms respectively. Table A lists the codes used for the ring elements of the core structures of the compounds, while Table B shows the linking groups. Table C gives the meanings of the codes for the left-hand or right-hand end groups. The acronyms are composed of the codes for the ring elements with optional linking groups, followed by a first hyphen and the codes for the left-hand end group, and a second hyphen and the codes for the right-hand end group. Table D shows illustrative structures of compounds together with their respective abbreviations.
wherein n and m each denote integers, and the three dots “ . . . ” are placeholders for other abbreviations from this table.
The following table shows illustrative structures together with their respective abbreviations. These are shown in order to illustrate the meaning of the rules for the abbreviations. They furthermore represent compounds which are preferably used.
wherein n, m and l preferably, independently of one another, denote 1 to 7.
The following table, Table E, shows illustrative compounds which can be used as additional stabilisers in the mesogenic media according to the present invention.
The LC media preferably comprise 0 to 10% by weight, in particular 1 ppm to 5% by weight, particularly preferably 1 ppm to 1% by weight, of stabilisers.
Table F below shows illustrative compounds which can preferably be used as chiral dopants in the mesogenic media according to the present invention.
In a preferred embodiment of the present invention, the mesogenic media comprise one or more compounds selected from the group of the compounds from Table F.
The mesogenic media according to the present application preferably comprise two or more, preferably four or more, compounds selected from the group consisting of the compounds from the above tables.
The liquid-crystal media according to the present invention preferably comprise
Hereinafter, the present invention is described in more detail and specifically with reference to the Examples, which however are not intended to limit the present invention.
Under reflux 13.8 ml (90 mmol) of the diethyl malonate are added to mixture of 34.5 ml of a solution of sodium methylate in ethanol (20%, 50 mmol) and 40 ml ethanol. After 2 h 10 g (50 mmol) of 2-bromoethoxymethylbenzene are added and heating was continued overnight. Water and MTB ether are poured into the cooled reaction mixture. The aqueous layer is extracted with MTB ether. The combined organic layers are washed with brine and dried over sodium sulfate. The solvent is evaporated. The residue is purified by silica chromatography (toluene; toluene/MTB ether 9:1). The isolated material is distilled under vacuum (0.1 mbar, 116-121° C.) to give 1.
A solution of 5 g (20 mmol) of the malonate 1 in 60 ml toluene is added to a suspension of 930 mg (24 mmol) Lithium aluminum hydride in 8 ml Toluene. After 3 h reflux the cooled reaction mixture is quenched with ethyl acetate. The mixture is acidified with 2 mol/l hydrochloric acid (pH 3-4). The aqueous layer is extracted with MTB ether. The combined organic layers are washed with water and dried over sodium sulfate. The solvent is evaporated. The residue is purified by silica chromatography (ethyl acetate) to give 2.
At room temperature 3.4 ml (25 mmol) triethyl amine are added to a mixture of 2.1 g (10 mmol) of the diol 2 and 120 mg DMAP dissolved in 30 ml dichloro methane. Afterwards a solution of 4.5 g (30 mmol) TBDMS-Cl in 15 ml dichloro methane are added to the reaction mixture at 3-4° C. After stirring 16 h at room temperature the mixture is quenched with water. The combined organic layers are washed with brine and dried over sodium sulfate. The solvent is evaporated. The residue is purified by silica chromatography (n-heptane/ethyl acetate 19:1) to give 3.
A solution of 500 mg (1 mmol) of 3 in 13 ml ethyl acetate is hydrogenated using Pd/C-5% at room temperature. The solvent is evaporated. The residue is purified by silica chromatography (n-heptane/ethyl acetate (gradient)) to give 4.
To a mixture consisting of 49.0 g (95%; 137 mmol) of 1-bromo-4-[(E)-2-(4-bromophenyl)vinyl]benzene), 60 ml aqueous potassium hydroxide (47%), 200 ml water and 1200 ml dioxane, 6.3 g (6.9 mmol) Tris(dibenzylideneaceton)dipalladium(0) and 8.8 g (20.7 mmol) 2-Di-t-butylphosphine-2′,4′,6′-tri-i-propyl1,1′-biphenyl are added und the mixture is stirred for 2 h under reflux. The mixture is cooled to room temperature, diluted with water, acidified with aqueous Hydrogen chloride and extracted with ethyl acetate. The combined organic phases are dried with sodium sulfate, filtered and the solvent is evaporated. The residue is purified by silica chromatography (Bu-Cl/THF, gradient 9:1-1:9) and the crude product is subsequently treated with toluene and 2-propanol under reflux, respectively to give 5.
To a mixture of 10.8 g (41 mmol) Triphenyl phosphine in 15 ml THF, 8.4 ml (30 mmol) Diisopropylazodicarboxylate are added slowly not exceeding a temperature of 22° C. Afterwards, 14.8 g (40 mmol) 3,3bis[[tert-butyl(dimethyl)silyl]oxy-methyl]-pentan-1-ol in 20 ml THF and 3.8 g (20 mmol) 5 are added subsequently and the resulting mixture is stirred over night. Isolute® HM-N is added and the solvent is evaporated. The crude product is then purified over silica gel (eluent: n-Heptane/Butylchloride) to give 2.8 g of 6.
To a solution of 2.8 g (2 mmol) of 6 in 20 ml dichloromethane, 4.9 ml (30 mmol) Triethylaminotrishydrofluoride are added at room temperature and stirred overnight. The solvent is than evaporated and the crude product is purified is diluted in hot THF and precipitated with acetonitrile to give 7 after filtration and drying.
To a suspension of 1.7 g (79% 2.8 mmol) 7 in 8 ml dichloromethane, 55 mg DMAP and 0.9 ml Methacrylic acid (10.5 mmol) and 3.2 ml (17 mmol) N-(3-Dimethylaminopropyl)-N′-ethylcarbodiimid are added not exceeding a temperature of 5° C. After stirring for 1 h at 5° C. the cooling is removed and the mixture is further stirred over night. The crude mixture is filtered over silica gel (DCM) and the solvent is evaporated. The crude product is purified by column chromatography (ACN/MTBE) to give 8 after recrystallization from acetonitrile.
Under an inert gas atmosphere a solution of 83.4 g (32 mmol) 2-(4-bromophenoxy)tetrahydropyran in 800 ml THF is prepared and 213 ml 1.6 mol/l Butyllithium are slowly added at a temperature of −70° C. The mixture is stirred for further 90 mins at this temperature and afterwards, a solution of 72.3 g (35 mmol) triethyl(1,2,2-trifluorovinyl)silane in 200 ml THF are added at a temperature of −70° C. After further stirring the mixture for an additional hour, the cooling is removed and the mixture is stirred overnight. The reaction mixture is quenched with water and extracted with MTBE. The combined organic phases are washed with brine and the combined organic phases are dried over sodium sulfate, filtered and the solvent is removed. The crude product is purified over silica gel (Bu—Cl/n-pentane 7:3) to give 9.
To a solution of 91 g (90%, 23 mmol) 9 in 500 ml THF, 250 ml 1 mol/l Tetrabutylammoniumfluorid in THF (25 mmol) are added at a temperature of 10° C. After stirring the mixture for an additional hour at that temperature, the cooling is removed and the mixture is stirred overnight. The mixture is diluted with MTBE and water is added. The aqueous phase is extracted with MTBE and the combined organic phases are dried over sodium sulfate, filtered and the solvent is evaporated. The crude product is purified over silica gel (butyl chloride) to give 10.
Under an inert gas atmosphere, a solution 165 ml mol/l Butyllithium (15% in n-Hexan; 26 mmol) is slowly added to a solution of 54.8 g (21 mmol) of 10 in 600 ml THF at a temperature of −70° C. After further stirring of this mixture for 1 h at that temperature a solution of 67 g Iodine in 400 ml THF is slowly added. The mixture is subsequently stirred for 30 mins at −70° C. and −50° C., respectively and the cooling is removed. After the mixture is brought to room temperature, water is added and the aqueous phase is extracted with MTBE. The mixture is washed with sodium thiosulfate and the pH of the aqueous phase is adjusted to 9 with 2N sodium hydroxide. The phases are separated and the aqueous phase is extracted with MTBE. The combined organic phases are washed with brine, dried over sodium sulfate, filtered and the solvent is evaporated. The crude product is purified over silica gel (n-Heptane/10% Ethyl acetate) to give 11.
To a solution of 59 g (91% ig; 150 mmol) 11 and 31 g (220 mmol) potassium carbonate in 600 ml THF and 200 ml water, 810 mg CataCXium A and 750 mg Tris(dibenzylidenacetone)Palladium(0) are added under reflux while vigorously stirring. Subsequently, 21.4 g (160 mmol) (4-hydroxyphenyl)boronic acid are added and the mixture is stirred for 2 h under reflux. The mixture is diluted with water, acidified with acetic acid and extracted with MTBE. The combined organic phases are washed with water, brine, dried over sodium sulfate, filtered and the solvent is evaporated. The crude product is purified over silica gel and recrystallized from ethylacetate/n-heptane to give 12.
In analogy to the synthesis steps 1.6 to 1.8, 13 can be obtained from intermediate compound 12.
To a mixture of 11.7 g (44 mmol) Triphenyl phosphine in 15 ml THF, 9.2 ml (42 mmol) Diisopropylazodicarboxylate are added slowly not exceeding a temperature of 22° C. Afterwards, 16.4 g (40 mmol) 3,3bis[[tert-butyl(dimethyl)silyl]oxy-methyl]-pentan-1-ol in 20 ml THF and 5.0 g (96.7%, 20 mmol) 5 are added subsequently and the resulting mixture is stirred over night. Isolute® HM-N is added and the solvent is evaporated. The crude product is then purified over silica gel (eluent: n-Heptane/Butylchloride, 1:1) and subsequently purified over RP-silica gel (MTBE/acetonitrile, 4:6) to give a mixture of 14.
To a solution of 4.1 g (10 mmol) of 14 in 35 ml dichloromethane, 6.8 ml (56 mmol) Triethylaminotrishydrofluoride are added at room temperature and stirred for 2 d. Solute is added and the solvent is evaporated. Finally, the crude product is purified over silica gel (dichloromethane/25-50% THF; dichloromethane/50-100% MTB-Ether) to give 15.
To a suspension of 1 g (88% 2.3 mmol) 15 in 6 ml dichloromethane, 45 mg DMAP and 1.2 ml Methacrylic acid (14 mmol) and 2.5 ml (17 mmol) N-(3-Dimethylaminopropyl)-N′-ethylcarbodiimid are added not exceeding a temperature of 5° C. After stirring for 1 h at 5° C. the cooling is removed and the mixture is further stirred over night. The crude mixture is filtered over silica gel (DCM) and the solvent is evaporated. The crude product is purified by column chromatography (RP-18; acetonitrile/10% water) to give 16 after recrystallization from acetonitrile.
1H NMR (500 MHz, Chloroform-d) δ 7.83-7.76 (m, 2H), 7.73-7.66 (m, 2H), 7.28-7.21 (m, 2H), 6.99-6.92 (m, 2H), 6.39 (p, J=1.1 Hz, 1H), 6.12 (dq, J=2.1, 1.0 Hz, 2H), 5.80 (p, J=1.5 Hz, 1H), 5.60 (p, J=1.5 Hz, 2H), 4.23-4.13 (m, 6H), 2.11 (dd, J=1.6, 1.0 Hz, 3H), 2.02-1.94 (m, 8H), 1.60 (q, J=7.5 Hz, 2H), 0.99 (t, J=7.5 Hz, 3H).
In analogy to the synthesis steps 3.1 to 3.2, 17 can be obtained from intermediate compound 12.
The nematic LC host mixture N-1 is prepared as indicated in the following table:
Unless explicitly stated otherwise, the display cells are made with Corning AF glass of 0.7 mm thickness using 6.4 μm spacer beads and XN-1500T sealant.
For measurement of electro-optics 3 μm thick PI-free IPS cells are made of substrates commercially available from SD-tech and constructed into cells using ITO electrodes having 5 μm electrode spacing and a 3 μm electrode width.
The cells are assembled by hand and then cured using a Omnicure 2000 Mercury lamp with 35 mW/cm2 the irradiation power is thereby measured by an Opsytec UV pad-e spectroradiometer.
The following nematic LC mixtures according to the invention are prepared from the nematic host mixtures listed above and photoalignment additives of formula I, according to the compositions given in the following table.
Unless explicitly stated otherwise, the selected LC mixtures are capillary filled using capillary action at room temp., annealed for 1 h at 100° C. and then irradiated at the same temperature with linearly polarised UV light (35 mW/cm2, Omnicure S2000 Mercury Lamp) for the given time. The cells are then cooled to room temperature. Next, the alignment quality is studied between crossed polarisers on a light box.
At least acceptable uniform planar alignment is achieved with all mixture according to the present invention and under all polarizer configurations an homogeneous transmissive state is observed.
| Number | Date | Country | Kind |
|---|---|---|---|
| 19178130.1 | Jun 2019 | EP | regional |
This application is a U.S. national stage application filed and claiming priority under 35 U.S.C. §§ 120 and 365(a) of International Application No. PCT/EP2020/065144, filed Jun. 2, 2020, which claims priority under 35 U.S.C. § 119 of European Patent Application No. 19178130.1, filed Jun. 4, 2019, each of which applications is incorporated herein by reference in its entirety and for all purposes.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2020/065144 | 6/2/2020 | WO |
