Liquid crystal compounds

Abstract

The present invention relates to novel polymerizable liquid crystal compounds of formula (I), liquid crystal mixtures comprising said compounds and their use for optical and electro-optical devices. TIFF2024532651000040.tif39169 [In the ceremony A and B represent unsubstituted or substituted carbocyclic or heterocyclic aromatic groups; SP1, SP2 and SP3 are substituted or unsubstituted linear or branched C1-C 18 represents an alkylene group, X1, X2, X3 and X4 are selected from the group consisting of -O-, etc.; BP1 and BP2 represent polymerizable groups, A1, A2, A3 and A4 are selected from the group consisting of hydrogen, etc. A compound represented by the formula:

Description

[Technical field]

[0001] The present invention relates to displacement curable liquid crystals (LCPs) having high optical anisotropy, and the use of such LCPs in the fabrication of substantially uniform or patterned films in which the orientation of the LCP molecules can be controlled.

[0002] In the display industry, optical LCP films are used to provide or enhance optical or electro-optical effects, for example for polarizers. Displays are becoming thinner and thinner, which has led to an increased demand from the industry for thinner optical LCP films that provide the desired optical or electro-optical effects, such as retardation films.

[0003] A retardation film is a type of optical element that changes the polarization state of light passing through it. When light passes through a phase retarder, its polarization direction changes due to the birefringence and thickness of the phase retarder. One of the biggest challenges in fabricating phase retarders is to create high performance films with small variations. By using liquid crystals with high birefringence, the required retardation value can be achieved with a small amount of liquid crystal compound.

[0004] Highly birefringent LCP materials with high birefringence may be accessible for thin optical films, especially thin retardation films.

[0005] Therefore, the objective of the present invention was to search for new LCP materials that have high birefringence and are applicable to optical films.

[0006] A first aspect of the present invention is a compound of formula (I): [ka] A and B each independently represent an unsubstituted or substituted carbocyclic or heterocyclic aromatic group selected from a monocyclic ring of 5 or 6 atoms, two adjacent monocyclic rings of 5 or 6 atoms, a bicyclic ring system of 8, 9 or 10 atoms, or a tricyclic ring system of 13 or 14 atoms; SP1, SP2 and SP3 are each independently a substituted or unsubstituted linear or branched C1-C 18 represents an alkylene group, in which one, two, three, four or more CH-2, CH or C groups may be replaced by a group selected from the group consisting of -CH=CH-, -C≡C-, -O-, -S-, -NR'CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR', provided that the spacer group does not contain two adjacent heteroatoms; X1, X2, X3 and X4 are each independently selected from the group consisting of -O-, -S-, -NR'-, -CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR' and a single bond; R' is hydrogen, C1-C 18 alkyl groups; BP1 and BP2 each independently represent a polymerizable group; A1, A2, A3 and A4 are each independently hydrogen, -OR, -COOR, -OCOR, -CONR, -OCOOR, -OCONR and C1-C 18 alkyl groups, R is an unsubstituted or substituted carbocyclic or heterocyclic aromatic group selected from a monocyclic ring of 5 or 6 atoms, a monocyclic ring of two adjacent 5 or 6 atoms, a bicyclic ring system of 8, 9 or 10 atoms, or a tricyclic ring system of 13 or 14 atoms; a substituted or unsubstituted straight-chain or branched C 1-18alkyl groups, wherein one, two, three or more CH-2, CH or C groups may be replaced by a group selected from the group consisting of -CH=CH-, -C≡C-, -O-, -S-, -NR'CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR', provided that the spacer group does not contain two adjacent heteroatoms, wherein R'' is hydrogen, C1-C 18 alkyl groups] The present invention provides a compound, preferably a liquid crystal, represented by the formula:

[0007] Preferred are: A and B each independently represent 5, 6, 10 or 14 ring atoms; Preferably, A and B each independently represent an unsubstituted or substituted furan, benzene, especially phenylene; a pyridine, triazine, pyrimidine, naphthalene, phenanthrene, biphenylene or tetralin radical; More preferably, A and B each independently represent unsubstituted or substituted naphthalene, phenanthrene, biphenylene or phenylene; Most preferably, A and B each independently represent unsubstituted or substituted naphthalene, biphenylene or phenylene, and Most especially preferred is when A is phenylene and B is naphthalene, which may be unsubstituted or substituted; SP1, SP2 and SP3 are each independently a substituted or unsubstituted linear or branched C1-C 18 Alkylene groups, preferably C1-C 12 Alkylene groups, more preferably C1-C 10an alkylene group, most preferably a C1-C8 alkylene group, especially most preferably a C1-C6 alkylene group, and even more especially most preferably a C3-C6 alkylene group, in which one, two, three or more CH-2, CH or C groups may be replaced by a group selected from the group consisting of: -CH=CH-, -C≡C-, -O-, -S-, -NR'CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR', the spacer group does not contain two adjacent heteroatoms; preferably, wherein one, two, three, four or more CH-2, CH or C groups are not replaced; X1, X2, X3 and X4 are each independently selected from the group consisting of -O-, -S-, -NR'-, -CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR' and a single bond; where R' is hydrogen, C1-C 18 an alkyl group, preferably a C1-C6 alkyl group, more preferably selected from the group consisting of methyl or ethyl; Preferably, X1, X2, X3 and X4 are each independently selected from the group consisting of -O-, -CO-, -COO-, -OOC-, -OCOO-, and a single bond, more preferably, X1, X2, X3 and X4 are each independently selected from the group consisting of -O-, -COO-, -OOC-, and a single bond; BP1 and BP2 each independently of the other represent a polymerizable group; preferably, the groups BP1 and BP2 each independently of the other represent CH2=C(Ph)-, CH2=CW-COO-, CH2=CH-COO-Ph-, CH2=CW-CO-NH-, CH2=CH-O-, CH2=CH-OOC-, Ph-CH=CH-, CH2=CH-Ph-, CH2=CH-Ph-O-, R 3 -Ph-CH=CH-COO-, R 3 -OOC-CH=CH-Ph-O- and 2-W-epoxyethyl, W represents hydrogen, chloride, phenyl or C1-C6 alkyl; R 3 represents C1-C6 alkyl, but R3 When is attached to an aryl group, R 3 may represent hydrogen or C1-C6 alkoxy; In particular, the groups BP1 and BP2, each independently of the other, are preferably selected from the group consisting of CH2=CW-COO-, CH2=CH-O-, and CH2=CH-OOC-, W represents hydrogen, chloride, aryl or C1-C6 alkyl, preferably hydrogen or C1-C6 alkyl, especially methyl or ethyl; A1, A2, A3 and A4 are each independently hydrogen, -OR, -COOR, -OCOR, -CONR, -OCOOR, -OCONR and C1-C 18 Alkyl groups, preferably C1-C 12 Alkyl groups, more preferably C1-C 10 alkyl groups, most preferably C1-C8 alkyl groups, especially most preferably C1-C6 alkyl groups, even more especially most preferably C3-C6 alkyl groups; R is hydrogen, substituted or unsubstituted linear or branched C 1-18 Alkyl groups, preferably C1-C 12 Alkyl groups, more preferably C1-C 10 alkyl groups, most preferably C1-C8 alkyl groups, especially most preferably C1-C6 alkyl groups, even more especially most preferably C3-C6 alkyl groups; preferably, in which one, two, three or more CH-2, CH or C groups may be replaced by a group selected from the group consisting of -CH=CH-, -C≡C-, -O-, -S-, -NR'CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR', the spacer group does not contain two adjacent heteroatoms, Preferably, R is hydrogen, substituted or unsubstituted linear or branched C 1-18 alkyl groups, in which one, two CH-2, CH or C groups are not replaced; Preferred are compounds of formula (I) in which A3 and A4 are the same and A1 and A2 are the same or different.

[0008] More preferably, A and B each independently represent unsubstituted or substituted naphthalene, biphenylene or phenylene; Most especially preferred is when A is phenylene and B is naphthalene, which may be unsubstituted or substituted; SP1, SP2 and SP3 are identical; or SP1 and SP2 are identical but different from SP3; where SP1, SP2 and SP3 are substituted or unsubstituted straight or branched C1-C 10 an alkylene group, most preferably a C1-C8 alkylene group, especially most preferably a C1-C6 alkylene group, and even more especially most preferably a C3-C6 alkylene group; in which one, two, three or more CH-2, CH or C groups may be replaced by a group selected from the group consisting of -CH=CH-, -C≡C-, -O-, -S-, -NR'CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR', the spacer group does not contain two adjacent heteroatoms; preferably, wherein one, two, three, four or more CH-2, CH or C groups are not replaced; X1, X2, X3 and X4 are the same; or X1 and X2 are the same but different from X3 and X4; where X1, X2, X3 and X4 are selected from the group consisting of -O-, -S-, -NR'-, -CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR' and a single bond; where R' is hydrogen, C1-C 18 an alkyl group, preferably a C1-C6 alkyl group, more preferably selected from the group consisting of methyl or ethyl; Preferably, X1, X2, X3 and X4 are each independently selected from the group consisting of -O-, -CO-, -COO-, -OOC-, -OCOO-, and a single bond, more preferably, X1, X2, X3 and X4 are each independently selected from the group consisting of -O-, -COO-, -OOC-, and a single bond; BP1 and BP2 are each independently preferably selected from the group consisting of CH2=CW-COO-, CH2=CH-O-, and CH2=CH-OOC-, where W represents hydrogen, chloride, aryl or C1-C6 alkyl, preferably hydrogen or C1-C6 alkyl, especially methyl or ethyl; A1, A2, A3 and A4 are each independently hydrogen, -OR, -COOR, -OCOR, and C1-C 18 Alkyl groups, preferably C1-C 12 Alkyl groups, more preferably C1-C 10 alkyl groups, most preferably C1-C8 alkyl groups, especially most preferably C1-C6 alkyl groups, even more especially most preferably C3-C6 alkyl groups; R is hydrogen, substituted or unsubstituted linear or branched C 1-18 Alkyl groups, preferably C1-C 12 Alkyl groups, more preferably C1-C 10 alkyl groups, most preferably C1-C8 alkyl groups, especially most preferably C1-C6 alkyl groups, even more especially most preferably C3-C6 alkyl groups; preferably, in which one, two, three or more CH-2, CH or C groups may be replaced by a group selected from the group consisting of -CH=CH-, -C≡C-, -O-, -S-, -NR'CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR', the spacer group does not contain two adjacent heteroatoms, Preferably, R is hydrogen, substituted or unsubstituted linear or branched C 1-18alkyl groups, in which one, two CH-2, CH or C groups are not replaced; Preferred are compounds of formula (I) in which A3 and A4 are the same and A1 and A2 are the same or different.

[0009] In the context of the present invention, the expression "carbocyclic or heterocyclic aromatic group" preferably has the meaning of 5, 6, 10 or 14 ring atoms, for example furan, benzene, pyridine, triazine, pyrimidine, naphthalene, phenanthrene, biphenylene or tetralin units, preferably naphthalene, phenanthrene, biphenylene or phenylene, more preferably naphthalene, biphenylene or phenylene, most preferably phenylene.

[0010] In the context of the present invention, the expression "substituted carbocyclic or heterocyclic aromatic group" has the meaning, for example, of being unsubstituted or mono- or polysubstituted. Preferred substituents of the carbocyclic or heterocyclic aromatic group are at least one halogen, hydroxyl, polar group, acryloyloxy, alkylacryloyloxy, alkoxy, alkylcarbonyloxy, alkyloxycarbonyloxy, alkyloxocarbonyloxy, methacryloyloxy, vinyl, vinyloxy and / or allyloxy group, where the alkyl residue preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Preferred polar groups are nitro, cyano or carboxy groups, and / or unsubstituted, mono- or polysubstituted cyclic, linear or branched C1-C 18 Alkyl. C1-C 18 Preferred substituents of alkyl are methyl, fluorine and / or chlorine, in which one or more, preferably non-adjacent, CH2 groups may be replaced independently of one another by a linking group, preferably selected from -O-, -CO-, -COO- and / or -OCO-.

[0011] In the context of the present invention, the expression "monocyclic ring of 5 or 6 atoms" has the meaning, for example, of furan, benzene, preferably phenylene, pyridine, pyrimidine.

[0012] Bicyclic ring systems of 8, 9 or 10 atoms are, for example, naphthalene, biphenylene or tetralin.

[0013] A tricyclic ring system of 13 or 14 atoms is, for example, phenanthrene.

[0014] The term "phenylene" as used in the context of the present invention preferably denotes a 1,2-, 1,3- or 1,4-phenylene group, which is optionally substituted. It is preferred that the phenylene group is either a 1,3-phenylene group or a 1,4-phenylene group. The 1,4-phenylene group is especially preferred.

[0015] The term "halogen" refers to a chloro, fluoro, bromo or iodo substituent, preferably a chloro or fluoro substituent.

[0016] In alkyl, alkoxy, alkylcarbonyloxy, acryloyloxyalkoxy, acryloyloxyalkyl, acryloyloxyalkene, alkyloxycarbonyloxy, alkylacryloyloxy, methacryloyloxyalkoxy, methacryloyloxyalkyl, methacryloyloxyalkene, alkylmethacryloyloxy, alkylmethacryloyloxy, alkylvinyl, alkylvinyloxy and alkylaryloxy as well as in alkylene, when used in the context of the present invention, the alkyl residues, respectively the alkylene residues, denote cyclic, linear or branched, substituted or unsubstituted alkyl, respectively alkylene, in which one or more, preferably non-adjacent, -CH2- groups may be replaced by a linking group; where the term "linking group", when used in the context of the present invention, preferably denotes [ka] Selected from, where: R 1 represents a hydrogen atom or a C1-C6 alkyl; However, the oxygen atoms of the linking group are not directly linked to each other.

[0017] Further, the alkyl residue can be, for example, C1-C 18 Alkyl, especially C1-C 12 Alkyl, preferably C1-C 10 alkyl, more preferably C1-C8 alkyl, and most preferably C1-C6 alkyl. Thus, arylene is, for example, C1-C 18 Alkylene, especially C1-C 12 Alkylene, preferably C1-C 10 Alkylene, more preferably C1-C8 alkylene, and most preferably C1-C6 alkylene.

[0018] In the context of the present invention, the definitions of alkyl given below are equally applicable to alkylene.

[0019] C1-C6 alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl or hexyl.

[0020] C1-C8 alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl.

[0021] C1-C 10 Alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl.

[0022] C1-C 12Alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl.

[0023] C1-C 18 Alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl.

[0024] The substituents of the alkyl and alkylene are preferably hydroxy, ether groups, ester groups, halogens such as fluorine and / or chlorine.

[0025] Preferably, the present invention relates to a compound of formula (II): [ka] [In the ceremony BP1, BP2, SP1, SP2, SP3, X1, X2, X3, X4, A1 and A2 have the same meanings and preferences as given above.] The present invention provides a compound, preferably a liquid crystal, represented by the formula:

[0026] A preferred embodiment of the present invention comprises A1 and A2 are the same and are preferably -OR, -COOR, -OCOR, and C1-C 18 Alkyl groups, preferably C1-C 12 Alkyl groups, more preferably C1-C 10 alkyl groups, most preferably C1-C8 alkyl groups, especially most preferably C1-C6 alkyl groups, even more especially most preferably C3-C6 alkyl groups; or A1 is hydrogen, -OR, -COOR, -OCOR, and C1-C 18 Alkyl groups, preferably C1-C 12Alkyl groups, more preferably C1-C 10 alkyl groups, most preferably C1-C8 alkyl groups, especially most preferably C1-C6 alkyl groups, even more especially most preferably C3-C6 alkyl groups, and The compounds of formula (II), preferably liquid crystals, wherein A2 is hydrogen.

[0027] Starting materials are either commercially available or readily prepared and are well known to those skilled in the art.

[0028] LCP material as used within the context of this application shall mean a liquid crystal material comprising liquid crystal monomers and / or liquid crystal oligomers and / or liquid crystal polymers and / or crosslinked liquid crystals. When the liquid crystal material comprises liquid crystal monomers, such monomers can typically be polymerized after creating anisotropy in the LCP material, for example by contact with an alignment layer. Polymerization can be initiated by heat treatment or by exposure to actinic radiation, preferably including UV light. The LCP material may comprise only one type of liquid crystal compound, but may also comprise further polymerizable and / or non-polymerizable compounds, not all of which need to be liquid crystal compounds. In addition, the LCP material may contain, but is not limited to, antioxidants, initiators, such as photoinitiators, accelerators, dyes, inhibitors, activators, fillers, chain transfer inhibitors, pigments, antistatic agents, flame retardants, thickeners, thixotropic agents, surfactants, viscosity modifiers, extender oils, plasticizers, tackifiers, catalysts, sensitizers, stabilizers, such as phenol derivatives, such as 4-ethoxyphenol or 2,6-di-tert-butyl-4-methyl-phenol (BHT), leveling agents; dispersants; polymer binders and / or monomeric compounds that can be converted to polymer binders by polymerization, or, in the case of emulsion paints and printing inks, dispersing aids, such as those disclosed in U.S. Pat. No. 5,798,147; hydrophobizing agents, adhesives, flow improvers, defoamers, degassing agents, diluents, adjuvants, colorants, dyes and pigments, cure inhibitors, such as hydroquinone, p-tert.-butylcatechol; 2,6-di It may contain additives including tert.-butyl-p-methylphenol; phenothiazine; N-phenyl-2-naphthylamine; or photoalignable monomers or oligomers or polymers as described in EP 1 090 325 B, chiral additives, isotropic or anisotropic fluorescent and / or non-fluorescent dyes, in particular dichroic dyes.

[0029] It will be understood that the compounds of the present invention may be used in the preparation of LCP mixtures. Such mixtures may be prepared by mixing the compounds of formula (I) with one or more additional components. Organic solvents may be used in the preparation of these mixtures.

[0030] Thus, a second aspect of the present invention provides an LCP mixture comprising a compound of formula (I) and one or more additional components.

[0031] The LCP mixture may also include a suitable organic solvent.

[0032] Examples of solvents that may be used in the preparation of such liquid crystal mixtures include, but are not limited to, acetone, cyclopentanone (CP), cyclohexanone (CH), methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), N-ethylpyrrolidone, N-vinylpyrrolidone, N,N-dimethylacetamide (AN), tetrahydrofuran (THF), 1,3-dioxolane (DXG), ethylene glycol, dipropylene glycol, butyl carbitol, ethyl carbitol acetate, dipropylene glycol monomethyl ether, ethyl acetate (EA), 1-methoxy-2-propanol acetate (MPA), gamma-butyrolactone (BL), propylene glycol monoacetate, propylene glycol diacetate, dipropylene glycol monomethyl ether, dimethyl sulfoxide (DMSO).

[0033] Most preferred are cyclopentanone (CP), cyclohexanone (CH), methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), ethyl acetate (EA), 1-methoxy-2-propanol acetate (MPA), 1,3-dioxolane (DXG), and dimethyl sulfoxide (DMSO).

[0034] The dichroic dye refers to a dye whose absorbance varies between the long axis direction and the short axis direction of the molecule. The dichroic dye preferably absorbs visible light. Examples of the dichroic dye include azo dyes, acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, and anthraquinone dyes. These dichroic dyes can be used individually or in combination. The amount of the dichroic dye used relative to 100 parts by weight of the liquid crystal mixture is 0.01 parts by weight to 40 parts by weight, preferably 0.05 parts by weight to 15 parts by weight.

[0035] The compounds of the present invention may also be used in forming an LCP layer by casting an LCP compound according to the first aspect of the invention or an LCP mixture according to the second aspect of the invention onto a substrate.

[0036] Accordingly, a third aspect of the invention is a method of forming an LCP network, preferably an LCP film, comprising the steps of: forming an LCP layer comprising a compound of formula (I) or preferably an LCP mixture comprising a compound of formula (I); and polymerizing the LCP layer.

[0037] The present invention also includes, in a fourth aspect of the invention, a crosslinked and / or polymerized LCP network, preferably an LCP film, comprising a compound of formula (I) or an LCP mixture in crosslinked and / or polymerized form.

[0038] The LCP network, preferably the LCP film, has a birefringence preferably in the range of 0.28 to 0.45 (±0.01 to 0.02), more preferably in the range of 0.30 to 0.40 (±0.01), most preferably in the range of 0.31 to 0.40 (±0.01), especially most preferably in the range of 0.33 to 0.40 (±0.01). The birefringence (Δn) was obtained from the retardation (here at 550 nm) and thickness values ​​determined by measurements using an ellipsometer according to the formula (Δn=retardation / thickness). The thickness of the sample is measured by a stylus step gauge.

[0039] A fifth aspect of the present invention provides the use of a compound of formula (I) in the preparation of an optical or electro-optical device.

[0040] The use of a liquid crystal mixture according to the third aspect of the invention in the preparation of an optical or electro-optical device is also included in this aspect of the invention.

[0041] A sixth aspect of the invention provides an optical or electro-optical device comprising a compound of formula (I) in a crosslinked state.

[0042] An optical or electro-optical device comprising an LCP liquid crystal mixture according to the third aspect of the invention in a crosslinked state is also included in this aspect of the invention.

[0043] The LCP mixture can be applied onto a support. The support can be rigid or flexible and can have any form or shape. For example, the support can be an object with a complex surface. In principle, the support can be made of any material. Preferably, the support comprises plastic, glass or metal, or is a silicon wafer. If the support is flexible, the support is preferably a plastic or metal foil. Preferably, the surface of the support is flat. In some applications, the support can include local surface structures, such as microstructures, such as microlenses or microprisms, or structures that show abrupt changes in shape, such as rectangular structures. Preferably, the support is transparent.

[0044] The support may move during deposition of the LCP mixture. For example, a layer of the LCP mixture may be produced in a continuous roll-to-roll process by depositing the material composition on a moving flexible foil, preferably made of plastic or metal. The resulting film may then be wound onto a roll together with the support foil, or the film may be peeled off from the support, and the film may then be wound as a free-standing film without the support.

[0045] The support may have additional layers, such as organic layers, dielectric layers or metal layers. The layers may have various functions, for example, the organic layer may be coated as a primer layer to enhance the compatibility of the coated material with the support. The metal layer may be used as an electrode when used in electro-optical devices, such as displays, or may have the function of a reflector. The support may also be an optical element or device with a specific function, such as a substrate for an LCD, which may include thin film transistors, electrodes or color filters. In another example, the support is a device that includes an OLED layer structure. The support may also be a retarder film, a polarizer, such as a polarizing film or sheet polarizer, a reflective polarizer, such as the commercially available Vikuity™ DBEF film.

[0046] The LCP mixture can be applied to the support by any suitable method, such as extrusion, casting, molding, 2D or 3D printing or coating. Suitable coating methods are, for example, spin coating, blade coating, knife coating, kiss roll coating, die coating, dipping, brushing, casting with a bar, roller coating, flow coating, wire coating, spray coating, dip coating, curtain coating, air knife coating, reverse roll coating, gravure coating, metering rod (Meyer bar) coating, slot die (extrusion) coating, roller coating, flexographic coating. Suitable printing methods include silk screen printing, relief printing, such as flexographic printing, jet printing, intaglio printing, such as direct gravure printing or offset gravure printing, lithographic printing, such as offset printing, or stencil printing, such as screen printing.

[0047] The layer of the LCP mixture need not cover the entire surface of the support: rather, the layer may be applied in the form of a pattern, for example by printing, or may be treated after deposition to have the form of a pattern, for example by photolithographic methods.

[0048] Alignment of LCPs can be achieved by any known means for aligning liquid crystals. For example, the support may have an alignment surface, which means that the surface has the ability to align liquid crystals. The support can be pre-aligned without further processing. For example, when a plastic substrate is used as the support, the support can be aligned on the surface due to the manufacturing method, such as extrusion or stretching of the substrate. It is also possible to brush the support or imprint a directional microstructure to create alignment ability. Alternatively, a thin layer of material can be coated on the support that is specifically designed for alignment performance. The layer can be further brushed or treated to have a directional microstructure on the surface, for example by imprinting. If the thin layer comprises a photo-aligning material, alignment can be created by exposure to alignment light.

[0049] To define an orientation pattern of the liquid crystal in the LCP layer, the alignment surface of the substrate may exhibit a pattern of alignment directions. Preferably, an alignment layer comprising a photoalignable material is used for this purpose, and the alignment pattern is induced by selective exposure to alignment light of different polarized planes.

[0050] In the present invention, a new compound with high birefringence has been found, which is represented by the formula I of the present invention. In addition, the compound represented by the formula I can be aligned with low energy by an alignment layer, preferably by using a photoalignment material, which provides a way to a more economical process with less energy consumption.

[0051] In addition, it has surprisingly been found that compounds of formula I exhibit very good alignment quality without crystallization.

[0052] The present invention will now be described with reference to the following non-limiting examples, which are provided for illustrative purposes only. Variations on these examples which fall within the scope of the invention will be apparent to those skilled in the art. EXAMPLES

[0053] Definitions used in the examples: 1 H NMR: 1 H nuclear magnetic resonance spectroscopy DMSO-d6: Deuterated dimethyl sulfoxide 300MHz: 300 megahertz m: multiplet, d: doublet, dd: doublet doublet, t: triplet, s: singlet DMF: Dimethylformamide HCl: Hydrochloric acid CH2Cl2: Dichloromethane THF: tetrahydrofuran NMP: N-methyl-2-pyrrolidone CuI: Copper iodide MgSO4: Magnesium sulfate

[0054] In the following examples, the thermotropic phases are abbreviated as follows: T (Cr-N) : Transition temperature from crystalline phase to nematic phase T (N-I) : Transition temperature from nematic phase to isotropic phase

[0055] Example 1: Preparation of propyl 5-[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexoxy]benzoate, compound 1 [ka]

[0056] Preparation of 3-[(6-ethynyl-2-naphthyl)oxy]propan-1-ol, compound 2 [ka] A mixture of 20 g (85.81 mmol) of 6-bromo-2-naphthol, 15.41 g (111.55 mmol) of potassium carbonate, 1.7 g (10.29 mmol) of potassium iodide and 12.16 g (128.7 mmol) of 3-chloropropanol in 50 ml of NMP is heated at 80 °C for 18 h. The solution is then cooled and poured into 400 ml of water / HCl solution. The resulting precipitate is filtered off and washed twice with 200 ml of water. The residue was further purified by silica gel flash column chromatography using a 1:1 mixture of hexane / ethyl acetate to give 22.47 g. After recrystallization from heptane / ethyl acetate (10:1), 18.6 g of compound 2 was obtained as an off-white solid.

[0057] Preparation of 3-[[6-(2-trimethylsilylethynyl)-2-naphthyl]oxy]propan-1-ol, compound 3 [ka] Bis(triphenylphosphine)palladium(II) chloride (2.1 g, 2.99 mmol), CuI (799 mg, 4.195 mmol) and compound 2 are placed in 83.4 ml of triethylamine. The mixture is stirred at 25° C. for 15 min and (trimethylsilyl)acetylene (11.77 g, 119.8 mmol) is added. The suspension is stirred at 80° C. for 2 h, after which a solution of HCl is added dropwise. The mixture is stirred for 30 min, then filtered through hyflo silica and washed three times with 100 ml of ethyl acetate. The solution is extracted with ethyl acetate. The combined organic layers are washed with 5 ml of water and dried over MgSO4. After concentration of the solvent under vacuum, the residue is purified by silica gel flash chromatography using a 1:1 mixture of hexane / ethyl acetate to give 13.41 g of compound 3.

[0058] Preparation of 3-[(6-ethynyl-2-naphthyl)oxy]propan-1-ol, compound 4 [ka] 12.4 g (89.79 mmol) of potassium carbonate are added in portions to a solution of compound 3 in 135 ml of methanol. After stirring at room temperature for 1 hour, the reaction mixture is filtered off on Hyflo / silica and then washed three times with 25 ml of methanol. The solution is then poured into aqueous HCl and then extracted with ethyl acetate. The combined organic layers are dried over MgSO4. After concentration under vacuum, 10.84 g of compound 4 is obtained as a yellowish solid.

[0059] Preparation of propyl 5-iodo-2-[6-(4-iodo-2-propoxycarbonyl-phenoxy)hexoxy]benzoate, compound 5 [ka] A mixture of 9.24 g (30.18 mmol) propyl 2-hydroxy-5-iodo-benzoate, 5.42 g (39.24 mmol) potassium carbonate, 601 mg (3.62 mmol) potassium iodide and 3.68 g (15.09 mmol) 1,6-dibromobutane in 35 ml DMF is heated at 80 ° C for 5 h. The solution is then cooled and poured into 400 ml water / HCl solution. The resulting precipitate is filtered off and washed twice with 50 ml water. Purification by recrystallization in acetonitrile gives 9.44 g of compound 5 as an off-white solid.

[0060] Preparation of propyl 5-[2-[6-(3-hydroxypropoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(3-hydroxypropoxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexoxy]benzoate, compound 6 [ka] Bis(triphenylphosphine)palladium(II) chloride (202 mg, 0.288 mmol), CuI (109 mg, 0.576 mmol), and propyl 5-iodo-2-[6-(4-iodo-2-propoxycarbonyl-phenoxy)hexoxy]benzoate (4 g, 5.765 mmol), 8.02 ml of triethylamine (57.65 mmol) are placed in 40 ml of DMF. The mixture is stirred for 15 min at 25° C. and 3-[(6-ethynyl-2-naphthyl)oxy]propan-1-ol (2.87 g, 12.68 mmol) is added. The suspension is stirred for 8 h at room temperature, after which a solution of HCl is added and the mixture is stirred for 30 min. The reaction mixture is then filtered through Hyflo / silica and washed 3 times with 100 ml of ethyl acetate. The solution is extracted with ethyl acetate. The combined organic layers are washed with water and dried over MgSO4. After the solvent is concentrated under vacuum, the residue is purified by silica gel flash chromatography using a 1:1 mixture of hexane / ethyl acetate to give 4.33 g of compound 6.

[0061] Preparation of propyl 5-[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexoxy]benzoate, compound 1 To 4.33 g (4.859 mmol) of compound 6 in 45 mL of THF and 2.65 g (26.24 mmol) of triethylamine, add 4-dimethylaminopyridine (118.7 mg, 0.97 mmol). Cool the solution to 0° C. and add acryloyl dichloride (2.2 g, 24.29 mmol) dropwise. Then warm the solution to room temperature and allow it to stir for 18 hours. Purify the residue by silica gel flash chromatography using a 1:1 mixture of hexane / ethyl acetate to give 1.2 g of compound 1 as an off-white solid. 1H NMR (400 MHz, DMSO-d6) δ: 8.08 (s, 2H), 7.82 (m, 6H), 7.80 (dd, 2H), 7.55 (dd, 2H), 7.37 (d, 2H), 7.19 (m, 4H), 6.35 (dd, 2H), 6.19 (m, 2H), 5.95 (dd, 2H), 4.32 (t, 4H), 4.20 (q, 8H), 4.10 (t, 4H), 2.16 (qt, 4H), 1.70 (m, 8H), 1.52 (m, 4H), 0.96 (t, 6H)

[0062] Liquid crystal phase transition: Compound 1 was observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, as the temperature increased, the crystalline phase was observed at 105.8°C (T (Cr-N) ) to a nematic phase, and the isotropic phase at 125.7°C (T (N-I) ) appeared.

[0063] Example 2: Preparation of propyl 5-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]phenoxy]hexoxy]benzoate, compound 7 [ka]

[0064] Preparation of 6-[(6-bromo-2-naphthyl)oxy]hexan-1-ol, compound 8a [ka] Compound 8a is prepared according to the process for compound 2 described in Example 1, except that 3-chloropropanol is replaced with 3-bromohexanol.

[0065] Preparation of 6-[[6-(2-trimethylsilylethynyl)-2-naphthyl]oxy]hexan-1-ol, compound 8b [ka] Compound 8b is prepared according to the process for compound 3 described in Example 1, except that compound 2 is replaced with compound 8a.

[0066] Preparation of 6-[(6-ethynyl-2-naphthyl)oxy]hexan-1-ol, compound 9 [ka] Compound 9 is prepared according to the process for compound 4 described in Example 1, except that compound 3 is replaced with compound 8b.

[0067] Preparation of 1-(6-chlorohexoxy)-4-iodo-benzene, compound 10 [ka] To a solution of 4-iodophenol (25 g, 113.6 mmol) in 250 ml of THF is added 6-chlorohexanol (19.4 g, 142 mmol) and triphenylphosphine (37.25 g, 142 mmol). The mixture is cooled to 0° C. and diisopropyl azodicarboxylate (28.72 g, 142 mmol) in 250 ml of THF is added dropwise. After the addition, the reaction is allowed to cool to room temperature and stirred for 18 hours. The solution is then concentrated under vacuum and the residue is purified by silica gel flash chromatography using a 1:4 mixture of hexane / ethyl acetate to give 35.4 g of compound 10 as an off-white solid.

[0068] Preparation of propyl 5-iodo-2-[6-(4-iodophenoxy)hexoxy]benzoate, compound 11 [ka] To a mixture of 12.05 g (39.37 mmol) of propyl 2-hydroxy-5-iodo-benzoate, 7.07 g (51.18 mmol) of potassium carbonate, 784 mg (4.73 mmol) of potassium iodide in 40 ml of DMF, 20 g (50.06 mmol) of 1-(6-chlorohexoxy)-4-iodo-benzene in 50 ml of DMF is added dropwise. After heating at 80° C. for 18 hours, the solution is then cooled and poured into 400 mL of water / HCl solution. The resulting precipitate is filtered off and purified by silica gel flash chromatography using a 9:1 mixture of hexane / ethyl acetate to give 23.3 g of compound 11 as a yellowish solid.

[0069] Preparation of propyl 5-[2-[6-(6-hydroxyhexoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(6-hydroxyhexoxy)-2-naphthyl]ethynyl]phenoxy]hexoxy]benzoate, compound 12 [ka] Compound 12 is prepared according to the process described in Example 1 for compound 6, except that compound 5 is replaced with compound 11.

[0070] Preparation of propyl 5-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]phenoxy]hexoxy]benzoate, compound 7 Compound 7 is prepared according to the process for compound 1 described in Example 1, except that compound 6 is replaced with compound 12. 1H NMR (400 MHz, THF-d8) δ: 7.91 (dd, 3H), 7.70 (m, 4H), 7.60 (dd, 1H), 7.55-7.40 (m, 4H), 7.20 (m, 1H), 7.16-7.08 (m, 4H), 6.91 (d, 1H), 6.33 (dd, 2H), 6.11 (dd, 2H), 5.77 (dd, 2H), 4.22 (t, 2H), 4.11 (m, 10H), 4.02 (t, 2H), 1.9-1.4 (m, 26H), 1.03 (t, 3H) Liquid crystal phase transition: T (Cr-N) : 83.3℃, ​​T (N-I) : 146.3℃

[0071] Example 3: Preparation of methyl 2-[6-[2-methoxycarbonyl-4-[2-[6-(11-prop-2-enoyloxyundecoxy)-2-naphthyl]ethynyl]phenoxy]hexoxy]-5-[2-[6-(11-prop-2-enoyloxyundecoxy)-2-naphthyl]ethynyl]benzoate, compound 14 [ka]

[0072] Preparation of 11-[(6-bromo-2-naphthyl)oxy]undecan-1-ol, compound 15 [ka] Compound 15 is prepared according to the process for compound 2 described in Example 1, except that 3-chloropropanol is replaced with 11-bromoundecanol.

[0073] Preparation of 11-[[6-(2-trimethylsilylethynyl)-2-naphthyl]oxy]undecan-1-ol, compound 16 [ka] Compound 16 is prepared according to the process for compound 3 described in Example 1, except that compound 2 is replaced with compound 15.

[0074] Preparation of 11-[(6-ethynyl-2-naphthyl)oxy]undecan-1-ol, compound 17 [ka] Compound 17 is prepared according to the process described in Example 1 for compound 4, except that compound 3 is replaced with compound 16.

[0075] Preparation of methyl 5-iodo-2-[6-(4-iodo-2-methoxycarbonyl-phenoxy)hexoxy]benzoate, compound 18 [ka] Compound 18 is prepared according to the process for compound 5 described in Example 1, except that propyl 2-hydroxy-5-iodo-benzoate is replaced with methyl 2-hydroxy-5-iodo-benzoate.

[0076] Preparation of methyl 5-[2-[6-(11-hydroxyundecoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(11-hydroxyundecoxy)-2-naphthyl]ethynyl]-2-methoxycarbonyl-phenoxy]hexoxy]benzoate, compound 19 [ka] Compound 19 is prepared according to the process for compound 6 described in Example 1, except that compound 5 is replaced with compound 18.

[0077] Preparation of methyl 2-[6-[2-methoxycarbonyl-4-[2-[6-(11-prop-2-enoyloxyundecoxy)-2-naphthyl]ethynyl]phenoxy]hexoxy]-5-[2-[6-(11-prop-2-enoyloxyundecoxy)-2-naphthyl]ethynyl]benzoate, compound 14 Compound 14 is prepared according to the process for compound 1 described in Example 1, except that compound 6 is replaced with compound 19. 1 H NMR (400 MHz, THF-d8) δ: 7.94 (d, 2H), 7.90 (d, 2H), 7.70 (dd, 4H), 7.60 (dd, 2H), 7.47 (dd, 2H), 7.13 (m, 6H), 6.32 (dd, 2H), 6.10 (dd, 2H), 5.78 (dd, 2H), 4.10 (m, 12H), 3.82 (s, 6H), 1.9-1.75 (m, 8H), 1.75-1.35 (m, 18H) Liquid crystal phase transition: T (Cr-N) : 110.6℃, T (N-I) : 120.8℃

[0078] Example 4: Preparation of propyl 5-[2-[6-(5-prop-2-enoyloxypentoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(5-prop-2-enoyloxypentoxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexoxy]benzoate, compound 20 [ka]

[0079] Preparation of 5-[(6-bromo-2-naphthyl)oxy]pentan-1-ol, compound 21 [ka] Compound 21 is prepared according to the process for compound 2 described in Example 1, except that 3-chloropropanol is replaced with 5-bromopentanol.

[0080] Preparation of 5-[[6-(2-trimethylsilylethynyl)-2-naphthyl]oxy]pentan-1-ol, compound 22 [ka] Compound 22 is prepared according to the process described in Example 1 for compound 3, except that compound 2 is replaced with compound 21.

[0081] Preparation of 5-[(6-ethynyl-2-naphthyl)oxy]pentan-1-ol, compound 23 [ka] Compound 23 is prepared according to the process described in Example 1 for compound 4, except that compound 3 is replaced with compound 22.

[0082] Preparation of propyl 5-[2-[6-(5-hydroxypentoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(5-hydroxypentoxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexoxy]benzoate, compound 24 [ka] Compound 24 is prepared according to the process for compound 6 described in Example 1, except that compound 4 is replaced with compound 23.

[0083] Preparation of propyl 5-[2-[6-(5-prop-2-enoyloxypentoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(5-prop-2-enoyloxypentoxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexoxy]benzoate, compound 20 Compound 20 is prepared according to the process for compound 1 described in Example 1, except that compound 6 is replaced with compound 24. 1 H NMR (400 MHz, DMSO-d6) δ: 8.07 (s, 2H), 7.80 (m, 6H), 7.71 (dd, 2H), 7.53 (dd, 2H), 7.34 (d, 2H), 7.20 (m, 4H), 6.32 (dd, 2H), 6.18 (m, 2H), 5.93 (dd, 2H), 4.14 (m, 16H), 1.73 (m, 16H), 1.52 (m, 8H), 0.96 (t, 6H) Liquid crystal phase transition: T (Cr-N) : 123℃, T (N-I) : 126.9℃

[0084] Example 5: Preparation of propyl 5-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[5-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexoxy]benzoate, compound 25 [ka]

[0085] Preparation of propyl 5-[2-[6-(6-hydroxyhexoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(6-hydroxyhexoxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexoxy]benzoate, compound 26 [ka] Compound 26 is prepared according to the process for compound 6 described in Example 1, except that compound 4 is replaced with compound 9.

[0086] Preparation of propyl 5-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[5-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexoxy]benzoate, compound 25 Compound 25 is prepared according to the process for compound 1 described in Example 1, except that compound 6 is replaced with compound 26. 1 H NMR (400 MHz, DMSO-d6) δ: 8.07 (s, 2H), 7.80 (m, 6H), 7.71 (dd, 2H), 7.53 (dd, 2H), 7.34 (d, 2H), 7.20 (m, 4H), 6.32 (dd, 2H), 6.18 (m, 2H), 5.93 (dd, 2H), 4.13 (m, 16H), 1.73 (m, 16H), 1.50 (m, 12H), 0.96 (t, 6H) Liquid crystal phase transition: T (Cr-N) : 103.5℃, T (N-I) : 117℃

[0087] Example 6: Preparation of propyl 5-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]-2-[4-[4-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]phenoxy]butoxy]benzoate, compound 30 [ka]

[0088] Preparation of propyl 5-iodo-2-[4-(4-iodophenoxy)butoxy]benzoate, compound 31 [ka] Compound 31 is prepared according to the process for compound 11 described in Example 2, except that 1-(6-chlorohexoxy)-4-iodo-benzene is replaced with 1-(6-chlorobutoxy)-4-iodo-benzene.

[0089] Preparation of propyl 5-[2-[6-(6-hydroxyhexoxy)-2-naphthyl]ethynyl]-2-[4-[4-[2-[6-(6-hydroxyhexoxy)-2-naphthyl]ethynyl]phenoxy]butoxy]benzoate, compound 32 [ka] Compound 32 is prepared according to the process for compound 12 described in Example 2, except that compound 11 is replaced with compound 31.

[0090] Preparation of propyl 5-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]-2-[4-[4-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]phenoxy]butoxy]benzoate, compound 30 Compound 30 is prepared according to the process for compound 1 described in Example 1, except that compound 6 is replaced with compound 31. 1 H NMR (400 MHz, DMSO-d6) δ: 8.05 (s, 2H), 7.82 (m, 4H), 7.72 (dd, 2H), 7.52 (m, 4H), 7.34 (s, 2H), 7.21 (m, 3H), 7.00 (d, 2H), 6.32 (dd, 2H), 6.17 (m, 2H), 5.92 (dd, 2H), 4.14 (m, 14H), 1.92 (m, 4H), 1.79-1.60 (m, 10H), 1.44 (m, 5H), 0.96 (t, 6H) Liquid crystal phase transition: T (Cr-N) : 85.1℃, T (N-I): 158.3℃

[0091] Example 7: Preparation of ethyl 2-[6-[2-ethoxycarbonyl-4-[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]phenoxy]hexoxy]-5-[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]benzoate, compound 33 [ka]

[0092] Preparation of ethyl 2-[6-(2-ethoxycarbonyl-4-iodo-phenoxy)hexoxy]-5-iodo-benzoate, compound 34 [ka] Compound 34 is prepared according to the process for compound 5 described in Example 1, except that propyl 2-hydroxy-5-iodo-benzoate is replaced with ethyl 2-hydroxy-5-iodo-benzoate.

[0093] Preparation of ethyl 2-[6-[2-ethoxycarbonyl-4-[2-[6-(3-hydroxypropoxy)-2-naphthyl]ethynyl]phenoxy]hexoxy]-5-[2-[6-(3-hydroxypropoxy)-2-naphthyl]ethynyl]benzoate, compound 35 [ka] Compound 35 is prepared according to the process for compound 6 described in Example 1, except that compound 5 is replaced with compound 34.

[0094] Preparation of ethyl 2-[6-[2-ethoxycarbonyl-4-[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]phenoxy]hexoxy]-5-[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]benzoate, compound 33 Compound 33 is prepared according to the process for compound 1 described in Example 1, except that compound 6 is replaced with compound 35. 1 H NMR (400 MHz, DMSO-d6) δ: 8.07 (s, 2H), 7.82 (m, 6H), 7.70 (dd, 2H), 7.54 (dd, 2H), 7.37 (d, 2H), 7.20 (m, 4H), 6.36 (dd, 2H), 6.19 (m, 2H), 5.95 (dd, 2H), 4.25 (m, 12H), 4.09 (t, 4H), 2.16 (qt, 4H), 1.76 (m, 4H), 1.53 (m, 4H), 1.30 (t, 6H) Liquid crystal phase transition: T (Cr-N) : 123.5℃, T (N-I) : 143℃

[0095] Example 8: Fabrication of an alignment layer using photoalignment material A glass substrate is spin-coated with a photoalignment composition (photoalignment material at 3% solids in cyclopentanone as described in patent publication WO2012 / 085048: a photoactive polymeric material is used as an alignment layer for liquid crystals). The film is dried at 180 °C for 10 min, resulting in a film thickness of about 100 nm. The film is then exposed to alignment light, which is parallel linearly polarized UV (LPUV) light (280-320 nm), at 250 mJ / cm. 2 The plane of polarization is at 0° relative to the reference edge on the substrate.

[0096] Example 9: Preparation of Compound 1 Film A 14.0 wt% solution is prepared by mixing 13.552 wt% Compound 1, 0.140 wt% 2,6-di-tert-butyl-4-methylphenol, 0.280 wt% Irgacure® 369 (Irgacure® 369 has the chemical structure 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1), 0.028 wt% BYK® 378 (solventless silicone leveling agent) in cyclopentanone and thoroughly stirring at room temperature until the solids are completely dissolved. The above polymer solution is spin-coated on a glass plate with the alignment layer of Example 8 to form a liquid crystal film. The film is dried on a temperature-controlled hot plate at 108°C for 1 minute and 30 seconds. The sample is cooled to room temperature, and then photopolymerized by irradiating it with UV light using a mercury lamp in an N2 atmosphere at room temperature of 20 to 25°C for approximately 2 minutes to fix the alignment state of the liquid crystal.

[0097] The resulting film of Example 9 exhibited a very well oriented nematic mesophase at room temperature.

[0098] Example 10: Preparation of Compound 25 Film A 15.0 wt% solution is prepared by mixing 14.775 wt% Compound 25, 0.075 wt% 2,6-di-tert-butyl-4-methylphenol, and 0.150 wt% Irgacure® 369 in cyclohexanone and thoroughly stirring at room temperature until the solids are completely dissolved. The above polymer solution is spin-coated on a glass plate with the alignment layer of Example 8 to form a liquid crystal film. The film is dried at 110°C for 5 minutes on a temperature-controlled hot plate. The sample is cooled to room temperature of 20-25°C, and then photopolymerized by irradiating UV light at room temperature for approximately 2 minutes under a N2 atmosphere using a mercury lamp to fix the alignment state of the liquid crystal.

[0099] The resulting film of Example 10 exhibited a very well oriented nematic mesophase at room temperature.

[0100] Example 11: Preparation of Compound 4 Film A 7.5 wt% solution is prepared by mixing 7.3875 wt% Compound 4, 0.0375 wt% 2,6-di-tert-butyl-4-methylphenol, and 0.075 wt% Irgacure® 369 in cyclohexanone, and thoroughly stirring at room temperature until the solids are completely dissolved. The above polymer solution is spin-coated on a glass plate with the alignment layer of Example 8 to form a liquid crystal film. The film is dried at 120°C for 5 minutes on a temperature-controlled hot plate. The sample is cooled to room temperature, and then photopolymerized by irradiating UV light at room temperature for approximately 2 minutes under N2 atmosphere using a mercury lamp to fix the alignment state of the liquid crystal.

[0101] The resulting film of Example 11 exhibited an oriented nematic mesophase with moderate alignment quality at room temperature.

[0102] Example 12: Preparation of Compound 7 Film 14. Prepare a 15 wt% solution by mixing 370 wt% Compound 7, 0.300 wt% 2,6-di-tert-butyl-4-methylphenol, and 0.300 wt% Irgacure® 369 in cyclopentanone / 3-dioxolane 60 / 40 and stir thoroughly at room temperature until the solids are completely dissolved. The above polymer solution was spin-coated on a glass plate with the alignment layer of Example 8 to form a liquid crystal film. The film was dried at 130°C for 5 minutes on a temperature-controlled hot plate. The sample was cooled to room temperature and then photopolymerized by irradiating UV light using a mercury lamp under N2 atmosphere at room temperature of 20-25°C for approximately 2 minutes to fix the alignment state of the liquid crystal.

[0103] The resulting film of Example 12 exhibited a very well oriented nematic mesophase at room temperature.

[0104] Example 13: Preparation of Compound 20 Film 14.5 A 15 wt% solution is prepared by mixing 20 wt% Compound 20, 0.150 wt% 2,6-di-tert-butyl-4-methylphenol, 0.300 wt% Irgacure® 369 and 0.030 wt% BYK® 378 in cyclopentanone and thoroughly stirring at room temperature until the solids are completely dissolved. The above polymer solution is spin-coated on a glass plate with the alignment layer of Example 8 to form a liquid crystal film. The film is dried at 108°C for 1 minute and 30 seconds on a temperature-controlled hot plate. The sample is cooled to room temperature and then photopolymerized by irradiating UV light using a mercury lamp under a N2 atmosphere at room temperature of 20 to 25°C for approximately 2 minutes to fix the alignment state of the liquid crystal.

[0105] The resulting film of Example 13 exhibited a very well oriented nematic mesophase at room temperature.

[0106] Example 14: Preparation of Compound 30 Film 14. Prepare a 15 wt% solution by mixing 20 wt% Compound 30, 0.150 wt% 2,6-di-tert-butyl-4-methylphenol, 0.300 wt% Irgacure® 369 and 0.030 wt% Tego Flow 0.300 in cyclopentanone and stir thoroughly at room temperature until the solids are completely dissolved. The above polymer solution was spin-coated on a glass plate with the alignment layer of Example 8 to form a liquid crystal film. The film was dried at 148°C for 5 minutes on a temperature-controlled hot plate. The sample was cooled to room temperature and then photopolymerized by irradiating UV light using a mercury lamp under a N2 atmosphere at room temperature of 20-25°C for approximately 2 minutes to fix the alignment state of the liquid crystal.

[0107] The resulting film of Example 14 exhibited a very well oriented nematic mesophase at room temperature.

[0108] Example 15: The retardation at 550 nm of the samples described in Examples 9, 10, 11, 12, and 14 is measured by an ellipsometer. The thickness of the samples is measured by a stylus step gauge. The birefringence (Δn) is obtained from the determined retardation and thickness values ​​according to the formula (Δn=retardation / thickness). The values ​​are listed in Table 1.

[0109] [Table 1]

[0110] The films of Examples 9, 10, 11, 12, and 14 have high birefringence in the range of 0.31 to 0.39. These new LCPs can be used to make phase retarder optical films as quarter wave plates (QWPs) and half wave plates (HWPs). Retarder transmits light and changes its polarization state, and are widely used in various display applications or security elements. The particularly high birefringence of these new LCPs results in a significant thickness reduction of the retarder films.

[0111] As an example, Table 2 shows the thicknesses required to obtain a quarter-wave plate (λ / 4) retarder (QWP) and a half-wave plate (λ / 2) retarder (HWP) at 550 nm for Examples 9, 10, 11, 12 and 14 using Compounds 1, 25, 14, 7, 30, respectively.

[0112] [Table 2]

Claims

1. Formula (I): 【Chemical 36】 [wherein A and B are each independently of the other a non-substituted or substituted carbocyclic or heterocyclic aromatic group selected from a monocyclic ring of 5 or 6 atoms, two adjacent monocyclic rings of 5 or 6 atoms, a bicyclic ring system of 8, 9 or 10 atoms, or a tricyclic ring system of 13 or 14 atoms; SP １ 、 SP ２ and SP ３ are each independently a substituted or unsubstituted linear or branched C １ -C １８ alkylene group, where one, two, three or four or more CH- ２ , CH or C groups may be replaced by a group selected from the group consisting of -CH=CH-, -C≡C-, -O-, -S-, -NR'CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR', provided that the spacer group does not contain two adjacent heteroatoms; X １ , X ２ , X ３ and X ４ are each independently selected from the group consisting of -O-, -S-, -NR'-, -CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR' and a single bond; R' is hydrogen, C １ -C １８ selected from the group consisting of an alkyl group; BP １ and BP ２ each independently represents a polymerizable group, A １ 、 A ２ 、 A ３ and A ４ are each independently selected from the group consisting of hydrogen, -OR, -COOR, -OCOR, -CONR, -OCOOR, -OCONR and C １ -C １８ alkyl groups, where R is a non-substituted or substituted carbocyclic or heterocyclic aromatic group selected from hydrogen, a monocyclic ring of 5 or 6 atoms, two adjacent monocyclic rings of 5 or 6 atoms, a bicyclic ring system of 8, 9 or 10 atoms, or a tricyclic ring system of 13 or 14 atoms; a substituted or non-substituted straight-chain or branched C １－１８ alkyl group selected from the group consisting of, wherein one, two, three or four or more CH- ２ , CH or C groups may be replaced by a group selected from the group consisting of -CH=CH-, -C≡C-, -O-, -S-, -NR'CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR', provided that the spacer group does not contain two adjacent heteroatoms, wherein R'' is hydrogen, C １ -C １８ alkyl group selected from the group consisting of] a compound represented by.

2. BP １ and BP ２ are each independently selected from the group consisting of CH ２ =C(Ph)-, CH ２ =CW-COO-, CH ２ =CH-COO-Ph-, CH ２ =CW-CO-NH-, CH ２ =CH-O-, CH ２ =CH-OOC-, Ph-CH=CH-, CH ２ =CH-Ph-, CH ２ =CH-Ph-O-, R ３ -Ph-CH=CH-COO-, R ３ -OOC-CH=CH-Ph-O- and 2-W-epoxyethyl, where W is hydrogen, chloride, phenyl or C １ -C ６ represents alkyl, and R ３ represents C １ -C ６ alkyl, provided that when R ３ is attached to an aryl group, R ３ may be hydrogen or C １ -C ６ alkoxy, the compound according to claim 1.

3. SP １ , SP ２ and SP ３ are each independently a substituted or unsubstituted linear or branched C １ -C １２ alkylene group, wherein one, two, three or four or more CH- ２ , CH or C groups may be replaced by a group selected from the group consisting of -CH=CH-, -C≡C-, -O-, -S-, -NR'CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR', provided that the spacer group does not contain two adjacent heteroatoms, the compound according to claim 1.

4. Group X １ , X ２ , X ３ and X ４ is, independently of one another, selected from the group consisting of -O-, -COO-, -OOC-, -OCOO-, and a single bond, the compound according to claim 1.

5. Group A １ and A ２ are each independently selected from the group consisting of hydrogen, -OR, -COOR, and -OCOR, where R is C １ -C １８ alkyl and; furan, benzene, phenylene; pyridine, triazine, pyrimidine, naphthalene, phenanthrene, biphenylene or tetralin group, which may be substituted, the compound according to claim 1.

6. An LCP mixture comprising the compound of formula (I) according to Claim 1.

7. An LCP network comprising the compound according to Claim 1 or the mixture according to Claim 6 in a polymerized form.

8. A method of forming an LCP network, comprising: forming an LCP layer comprising the compound of formula (I) according to Claim 1 or the LCP mixture according to Claim 6, and polymerizing the LCP layer.

9. Use of the compound according to Claim 1 or the mixture according to Claim 6 in the manufacture of an optical or electro-optical device.

10. An optical or electro-optical device comprising the compound according to Claim 1 or the mixture according to Claim 6.

11. An optical or electro-optical device comprising the network according to Claim 7.

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