Liquid crystal compounds

Abstract

This invention relates to novel polymerizable liquid crystals of formula (I), LCP mixtures comprising these compounds, and their uses in optical and electro-optical devices. Compounds of formula (I):

Description

Technical Field

[0001] The present invention relates to alternative curable liquid crystals (LCPs) with high optical anisotropy and the use of such LCPs in the preparation of substantially uniform or patterned films, wherein the orientation of LCP molecules in the film can be controlled. Background Technology

[0002] In the display industry, optical LCP films are used to provide or enhance optical or electro-optic effects, such as in polarizers. Displays are becoming increasingly thinner. Therefore, the industry's demand for thinner optical LCP films (such as retardation films) is constantly growing to provide the required optical or electro-optic effects.

[0003] A phase retardation film is an optical element that alters 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 producing high-performance thin films at low cost. When using liquid crystals with high birefringence, the desired retardation value can be achieved with a small amount of liquid crystal compound.

[0004] Highly birefringent LCP materials can be used to prepare thin optical films, especially thin retardation films. Summary of the Invention

[0005] Therefore, the objective of this invention is to find novel LCP materials with high birefringence that are suitable for optical films.

[0006] A first aspect of the present invention provides a compound of formula (I), preferably a liquid crystal compound:

[0007]

[0008] in:

[0009] A and B each independently represent an aromatic group selected from the following unsubstituted or substituted carbocyclic or heterocyclic groups: a monocyclic ring of 5 or 6 atoms, two adjacent monocyclic rings of 5 or 6 atoms, a bicyclic system of 8, 9 or 10 atoms, or a tricyclic system of 13 or 14 atoms.

[0010] SP1, SP2, and SP3 each independently represent substituted or unsubstituted linear or branched C1-C chains. 18 Alkylene, wherein 1, 2, 3, 4 or more CH2, CH or C groups are not substituted or are substituted by groups selected from -CH=CH-, -C≡C-, -O-, -S-, -NR'CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR', provided that the spacer group does not contain two adjacent heteroatoms;

[0011] X1, X2, X3, and X4 are each independently selected from -O-, -S-, -NR'-, -CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR', and single bonds;

[0012] R' is selected from hydrogen, C1-C 18 alkyl;

[0013] BP1 and BP2 each represent polymerizable groups independently;

[0014] A1, A2, A3, and A4 are each independently selected from hydrogen, -OR, -COOR, -OCOR, -CONR, -OCOOR, -OCONR, and C1-C. 18 Alkyl groups, wherein:

[0015] R is selected from hydrogen; an aromatic group selected from the following unsubstituted or substituted carbocyclic or heterocyclic groups: a monocyclic ring of 5 or 6 atoms, two adjacent monocyclic rings of 5 or 6 atoms, a bicyclic system of 8, 9 or 10 atoms, or a tricyclic system of 13 or 14 atoms; a substituted or unsubstituted linear or branched C 1-18 Alkyl group, wherein 1, 2, 3, 4 or more CH2, CH or C groups are not substituted or are substituted by groups selected from -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 selected from hydrogen, C1-C 18 alkyl.

[0016] The preferred compound is that of formula (I), wherein:

[0017] A and B each independently represent 5, 6, 10, or 14 ring atoms.

[0018] Preferably, A and B each independently represent unsubstituted or substituted furan, benzene (especially phenylene), pyridine, triazine, pyrimidine, naphthalene, phenanthrene, biphenyl or tetrahydronaphthalene groups;

[0019] More preferably, A and B each independently represent unsubstituted or substituted naphthalene, phenanthrene, biphenyl or phenylene;

[0020] The optimal choices A and B each independently represent unsubstituted or substituted naphthalene, biphenyl, or phenylene;

[0021] The preferred option is that A is an unsubstituted or substituted phenylene and B is an unsubstituted or substituted naphthalene.

[0022] SP1, SP2, and SP3 each independently represent substituted or unsubstituted linear or branched C1-C chains. 18 Alkylene, preferably C1-C 12 Alkylene, more preferably C1-C 10 Alkylene, most preferably C1-C8 alkylene, and especially preferably C1-C6 alkylene, and even more preferably C3-C6 alkylene, wherein 1, 2, 3, 4 or more CH2, CH or C groups are not substituted or are substituted by groups selected from -CH=CH-, -C≡C-, -O-, -S-, -NR'CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR'.

[0023] The condition is that the spacer group does not contain two adjacent heteroatoms; preferably, one, two, three, four or more CH2, CH or C groups are not substituted.

[0024] X1, X2, X3, and X4 are each independently selected from -O-, -S-, -NR'-, -CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR', and single bonds; where R' is selected from hydrogen, C1-C 18 Alkyl, preferably C1-C6 alkyl, more preferably methyl or ethyl;

[0025] Preferably, X1, X2, X3 and X4 are each independently selected from -O-, -CO-, -COO-, -OOC-, -OCOO- and single bonds, and more preferably, X1, X2, X3 and X4 are each independently selected from -O-, -COO-, -OOC- and single bonds;

[0026] BP1 and BP2 each independently represent polymerizable groups; preferably, BP1 and BP2 are each independently selected from 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, wherein:

[0027] W represents hydrogen, chlorine, phenyl, or C1-C6 alkyl.

[0028] R 3 It represents C1-C6 alkyl, under the condition that R 3 When attached to an aryl group, it can also represent hydrogen or C1-C6 alkoxy;

[0029] Specifically, groups BP1 and BP2 are each preferably selected independently from CH2=CW-COO-, CH2=CH-O-, and CH2=CH-OOC-.

[0030] in:

[0031] W represents hydrogen, chlorine, aryl or C1-C6 alkyl, preferably hydrogen or C1-C6 alkyl, especially methyl or ethyl;

[0032] A1, A2, A3, and A4 are each independently selected from hydrogen, -OR, -COOR, -OCOR, -CONR, -OCOOR, -OCONR, and C1-C. 18 Alkyl groups, preferably C1-C 12 Alkyl, more preferably C1-C 10 Alkyl groups, most preferably C1-C8 alkyl groups, and especially preferably C1-C6 alkyl groups, and even more preferably C3-C6 alkyl groups.

[0033] R is selected from hydrogen, substituted or unsubstituted straight-chain or branched C₂. 1-18 Alkyl groups, preferably C1-C 12 Alkyl, more preferably C1-C 10 Alkyl groups, most preferably C1-C8 alkyl groups, and especially preferably C1-C6 alkyl groups, and even more preferably C3-C6 alkyl groups; preferably, 1, 2, 3, 4 or more CH2, CH or C groups are not substituted or are substituted by groups selected from -CH=CH-, -C≡C-, -O-, -S-, -NR'CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR'.

[0034] The condition is that the spacer group does not contain two adjacent heteroatoms, and preferably:

[0035] R is selected from hydrogen, or substituted or unsubstituted linear or branched C from the above preferred range. 1-18 Alkyl group, wherein one or two CH2, CH or C groups are not substituted;

[0036] Preferably, A3 and A4 are the same, and A1 and A2 are the same or different.

[0037] More preferably, the compound of formula (I) is preferred, wherein:

[0038] A and B each independently represent naphthalene, biphenyl, or phenylene, which are either unsubstituted or substituted, and

[0039] The preferred choice is that A is phenylene and B is naphthalene, which are either unsubstituted or substituted;

[0040] SP1, SP2, and SP3 are the same; or SP1 and SP2 are the same but different from SP3; wherein SP1, SP2, and SP3 represent substituted or unsubstituted linear or branched C1-C. 10 Alkylene, most preferably C1-C8 alkylene, and especially preferably C1-C6 alkylene, and even more preferably C3-C6 alkylene.

[0041] In this case, 1, 2, 3, 4 or more CH2, CH or C groups are not substituted or are substituted by groups selected from -CH=CH-, -C≡C-, -O-, -S-, -NR'CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR'.

[0042] The condition is that the spacer group does not contain two adjacent heteroatoms; preferably, one, two, three, four or more CH2, CH or C groups are not substituted.

[0043] X1, X2, X3, and X4 are the same; or X1 and X2 are the same but different from X3 and X4; wherein X1, X2, X3, and X4 are selected from -O-, -S-, -NR'-, -CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR', and single bonds; wherein R' is selected from hydrogen, C1-C 18 Alkyl groups, preferably C1-C6 alkyl groups, more preferably methyl or ethyl;

[0044] Preferably, X1, X2, X3 and X4 are each independently selected from -O-, -CO-, -COO-, -OOC-, -OCOO- and single bonds, and more preferably, X1, X2, X3 and X4 are each independently selected from -O-, -COO-, -OOC- and single bonds;

[0045] BP1 and BP2 are each independently selected from CH2=CW-COO-, CH2=CH-O-, and CH2=CH-OOC-.

[0046] in:

[0047] W represents hydrogen, chlorine, aryl or C1-C6 alkyl, preferably hydrogen or C1-C6 alkyl, especially methyl or ethyl;

[0048] A1, A2, A3, and A4 are each independently selected from hydrogen, -OR, -COOR, -OCOR, and Cl-C. 18 Alkyl groups, preferably C1-C 12 Alkyl, more preferably C1-C 10 Alkyl groups, most preferably C1-C8 alkyl groups, and especially preferably C1-C6 alkyl groups, and even more preferably C3-C6 alkyl groups.

[0049] R is selected from hydrogen, substituted or unsubstituted straight-chain or branched C₂. 1-18 Alkyl groups, preferably C1-C 12 Alkyl, more preferably C1-C 10 Alkyl groups, most preferably C1-C8 alkyl groups, and especially preferably C1-C6 alkyl groups, and even more preferably C3-C6 alkyl groups; preferably, 1, 2, 3, 4 or more CH2, CH or C groups are not substituted or are substituted by groups selected from -CH=CH-, -C≡C-, -O-, -S-, -NR'CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR'.

[0050] The condition is that the spacer group does not contain two adjacent heteroatoms, and preferably:

[0051] R is selected from hydrogen, or substituted or unsubstituted linear or branched C from the above preferred range. 1-18 Alkyl group, wherein one or two CH2, CH or C groups are not substituted;

[0052] Preferably, A3 and A4 are the same, and A1 and A2 are the same or different.

[0053] In the context of this invention, the expression "aromatic group of carbocyclic or heterocyclic ring" preferably means 5, 6, 10 or 14 ring atoms, such as furan, benzene, pyridine, triazine, pyrimidine, naphthalene, phenanthrene, biphenyl or tetrahydronaphthalene unit, preferably naphthalene, phenanthrene, biphenyl or phenylene, more preferably naphthalene, biphenyl or phenylene, and most preferably phenylene.

[0054] In the context of this invention, the expression "substituted carbocyclic or heterocyclic aromatic group" means, for example, an unsubstituted or mono- or polysubstituted group. 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, wherein the alkyl residue preferably has 1-20 carbon atoms, and more preferably 1-10 carbon atoms. Preferred polar groups are nitro, cyano, or carboxyl groups, and / or cyclic, linear, or branched C1-C1 groups. 18 Alkyl groups, which are unsubstituted, monosubstituted, or polysubstituted. C1-C 18 Preferred substituents for the alkyl group are methyl, fluorine, and / or chlorine, wherein one or more (preferably non-adjacent) CH2 groups can be independently replaced by a linking group. Preferably, the linking group is selected from -O-, -CO-, -COO-, and / or -OCO-.

[0055] In the context of this invention, the expression "a monocyclic ring of 5 or 6 atoms" means, for example, furan, benzene (preferably phenylene), pyridine, or pyrimidine.

[0056] Bicyclic systems with 8, 9, or 10 atoms are, for example, naphthalene, biphenyl, or tetrahydronaphthalene.

[0057] A tricyclic system with 13 or 14 atoms is, for example, phenanthrene.

[0058] As used in the context of this invention, the term "phenylene" preferably refers to 1,2-, 1,3-, or 1,4-phenylene, which may optionally be substituted. Preferably, the phenylene is 1,3- or 1,4-phenylene. 1,4-phenylene is particularly preferred.

[0059] The term "halogen" refers to a chlorine, fluorine, bromine, or iodine substituent, preferably a chlorine or fluorine substituent.

[0060] As used in the context of this invention, alkyl, alkoxy, alkylcarbonyloxy, acryloyloxyalkoxy, acryloyloxyalkyl, acryloyloxyalkylene, alkyloxycarbonyloxy, alkylacryloyloxy, methacryloyloxyalkoxy, methacryloyloxyalkyl, methacryloyloxyalkylene, alkylmethacryloyloxy, alkylmethacryloyloxy, alkylvinyl, alkylvinyloxy, and alkylallyloxy and alkylene, together with their alkyl residues or their alkylene residues, represent cyclic, linear, or branched substituted or unsubstituted alkyl or alkylene groups in which one or more (preferably non-adjacent) -CH2- groups can be replaced by a linking group; wherein the term "linking group" as used in the context of this invention is preferably selected from -O-, -CO, -CO-O-, -O-CO-, ... -NR1-, -NR1-CO-, -CO-NR1-, NR1-CO-O-, -O-CO-NR1-, -NR1-CO-NR1-, -CH=CH-, -C≡C-, -O-CO-O- and -Si(CH3)2-O-Si(CH3)2-, and where:

[0061] R1 represents a hydrogen atom or a C1-C6 alkyl group;

[0062] The condition is that the oxygen atoms of the linking group are not directly connected to each other.

[0063] Additionally, the alkyl residue is, for example, C1-C. 18 Alkyl groups, especially C1-C 12 Alkyl groups, preferably C1-C 10 Alkyl, more preferably C1-C8 alkyl, and most preferably C1-C6 alkyl. Accordingly, alkylene is, for example, C1-C6. 18 Alkylenes, especially C1-C 12 Alkylene, preferably C1-C10 Alkylene, more preferably C1-C8 alkylene, and most preferably C1-C6 alkylene.

[0064] In the context of this invention, the following definition of alkyl groups applies similarly to alkylene groups.

[0065] C1-C6 alkyl groups are, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, or hexyl.

[0066] C1-C8 alkyl groups include, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, and octyl.

[0067] C1-C 10 Alkyl groups include, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl.

[0068] C1-C12 alkyl groups include, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl.

[0069] C1-C 18 Alkyl groups include, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, and octadecyl.

[0070] The alkyl and alkylene substituents are preferably hydroxyl, ether, ester, or halogen (e.g., fluorine and / or chlorine).

[0071] Preferably, the present invention provides a compound of formula (II), and more preferably a liquid crystal compound:

[0072]

[0073] in:

[0074] BP1, BP2, SP1, SP2, SP3, X1, X2, X3, X4, A1, and A2 have the same meanings and preferences as given above.

[0075] A preferred embodiment of the present invention relates to a compound of formula (II), preferably a liquid crystal compound, wherein:

[0076] A1 and A2 are the same, and the preferred choice is -OR, -COOR, -OCOR, and C1-C. 18 Alkyl groups, preferably C1-C 12 Alkyl, more preferably C1-C 10Alkyl groups, most preferably C1-C8 alkyl groups, and especially preferably C1-C6 alkyl groups, and even more preferably C3-C6 alkyl groups.

[0077] Or, A1 can be selected from hydrogen, -OR, -COOR, -OCOR, and Cl-C. 18 Alkyl groups, preferably C1-C 12 Alkyl, more preferably C1-C 10 Alkyl groups, most preferably C1-C8 alkyl groups, and especially preferably C1-C6 alkyl groups, and even more preferably C3-C6 alkyl groups.

[0078] A2 is hydrogen.

[0079] The starting materials are commercially available or can be readily prepared and are well known to those skilled in the art.

[0080] As used in the context of this application, LCP material refers to a liquid crystal material comprising liquid crystal monomers and / or liquid crystal oligomers and / or liquid crystal polymers and / or cross-linked liquid crystals. In the case of a liquid crystal material containing liquid crystal monomers, these monomers can typically polymerize after anisotropy has been generated in the LCP material, for example, due to contact with an alignment layer. Polymerization can be initiated by heat treatment or by exposure to photochemical light, preferably including UV light. LCP materials may contain only a single type of liquid crystal compound, but may also contain other polymerizable and / or non-polymerizable compounds, wherein not all compounds must be liquid crystal compounds. In addition, LCP materials may contain additives, including but not limited to antioxidants, initiators (e.g., 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 (e.g., phenol derivatives, such as 4-ethoxyphenol or 2,6-di-tert-butyl-4-methylphenol (BHT)), lubricants, dispersants, polymer binders, and / or monomeric compounds that can be polymerized into polymer binders; or In the case of emulsion coatings and printing inks, this includes dispersing agents (such as those disclosed in U.S. Patent No. 5,798,147), hydrophobic agents, binders, flow improvers, defoamers, degassing agents, diluents, additives, colorants, dyes and pigments, curing inhibitors (such as hydroquinone, p-tert-butylcatechol, 2,6-di-tert-butyl-p-methylphenol, phenothiazine, N-phenyl-2-naphthylamine, or photooriented monomers or oligomers or polymers as described in EP1090325B), chiral additives, and isotropic or anisotropic fluorescent and / or non-fluorescent dyes (especially dichroic dyes).

[0081] It should be understood that the compounds of the present invention can be used to prepare LCP mixtures. Such mixtures can be prepared by mixing a compound of formula (I) with one or more additional components. Organic solvents can also be used to prepare these mixtures.

[0082] Therefore, a second aspect of the invention provides an LCP mixture comprising a compound of formula (I) and one or more additional components.

[0083] LCP mixtures may also contain suitable organic solvents.

[0084] Examples of solvents that can be used to prepare 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), γ-butyrolactone (BL), propylene glycol monoacetate, propylene glycol diacetate, dipropylene glycol monomethyl ether, and dimethyl sulfoxide (DMSO).

[0085] The 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).

[0086] Dichroic dyes are dyes whose absorbance varies between the long and short axes of the molecule. Dichroic dyes preferably absorb visible light. Examples of dichroic dyes include azo dyes, acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, and anthraquinone dyes. These dichroic dyes can be used alone or in combination. The amount of dichroic dye used is 0.01-40 parts by weight, preferably 0.05-15 parts by weight, relative to 100 parts by weight of the liquid crystal mixture.

[0087] The compounds of the present invention can also be used to form an LCP layer by casting the LCP compound of the first aspect of the present invention or the LCP mixture of the second aspect of the present invention onto a substrate.

[0088] Therefore, a third aspect of the present invention provides a method for forming an LCP network (preferably an LCP membrane), comprising:

[0089] Forming an LCP layer, said LCP layer comprising a compound of formula (I) or preferably an LCP mixture comprising a compound of formula (I), and

[0090] The LCP layer is then polymerized.

[0091] In a fourth aspect, the invention further includes a crosslinked and / or polymerized LCP network (preferably an LCP membrane) comprising a compound of formula (I) or an LCP mixture in the form of a crosslinked and / or polymerized compound.

[0092] The birefringence of the LCP network (preferably an LCP film) is preferably in the range of 0.28-0.45 (±0.01-0.02), more preferably in the range of 0.30-0.40 (±0.01), most preferably in the range of 0.31-0.40 (±0.01), and especially most preferably in the range of 0.33-0.40 (±0.01). The birefringence (Δn) is obtained by measuring the determined retardation (here, 550 nm) and thickness using an ellipsometer according to the formula (Δn = retardation / thickness). The thickness of the sample is measured using a contact profiler.

[0093] The fifth aspect of the present invention provides the use of the compound of formula (I) in the preparation of optical or electro-optical devices.

[0094] The use of the liquid crystal mixture of the third aspect of the present invention in the preparation of optical or electro-optical devices is also included in this aspect of the present invention.

[0095] A sixth aspect of the present invention provides an optical device or electro-optic device comprising a compound of formula (I) in a cross-linked state.

[0096] Optical devices or electro-optical devices comprising the cross-linked state of LCP liquid crystal mixtures of the third aspect of the present invention are also included in this aspect of the present invention.

[0097] The LCP mixture can be applied to a support. The support can be rigid or flexible and can have any form or shape. For example, it may be an object with a complex surface. In principle, it can be composed of any material. Preferably, the support includes plastic, glass, or metal, or a silicon wafer. When the support is flexible, it is preferable that the support is plastic or metal foil. Preferably, the surface of the support is flat. For some applications, the support may include topographic surface structures, such as microstructures like microlenses or microprisms, or structures exhibiting abrupt shape changes, such as rectangular structures. Preferably, the support is transparent.

[0098] The support can be movable during the deposition of the LCP mixture. For example, layers of the LCP mixture can be produced by depositing the material composition onto a moving flexible foil (preferably plastic or metal) using a continuous roll-to-roll process. The resulting film can then be wound onto a roll together with the support foil, or the film can be peeled off from the support and then wound as a freestanding film without the support.

[0099] The support may have additional layers, such as organic layers, dielectric layers, or metal layers. These layers may have different functions; for example, an organic layer may be coated as a primer layer, which increases the compatibility of the material to be coated with the support. Metal layers may serve as electrodes, for example, when used in electro-optic devices such as displays, or may function as reflectors. The support may also be an optical element or device with certain functions, such as a substrate for LCDs, which may include, for example, thin-film transistors, electrodes, or color filters. In another example, the support is a device containing an OLED layer structure. The support may also be a retardation film, a polarizer (e.g., a polarizing film or sheet polarizer), or a reflective polarizer (e.g., the commercially available Vikuity). TM DBEF membrane).

[0100] LCP mixtures can be applied to the support by any suitable method, such as extrusion, casting, molding, 2D or 3D printing, or coating. Suitable coating methods include, for example, spin coating, blade coating, kiss roll coating, die coating, dip coating, brush coating, bar casting, roller coating, flow coating, line coating, spray coating, dip coating, curtain coating, air knife coating, reverse roller coating, gravure coating, Meyer bar coating, slot die (extrusion) coating, roller coating, and flexographic coating. Suitable printing methods include screen printing, letterpress printing such as flexographic printing, jet printing, gravure printing such as direct gravure printing or offset gravure printing, lithography such as offset printing, or stencil printing such as screen printing.

[0101] The LCP mixture layer does not necessarily have to cover the entire surface of the support. Instead, the layer can be applied in a patterned form, for example by printing, or it can be processed after deposition to have a pattern, for example by photolithography.

[0102] The alignment of LCPs can be achieved by any known means for aligning liquid crystals. For example, the support can have an alignment surface, meaning that the surface has the ability to align liquid crystals. The support may already provide alignment without further processing. For example, if a plastic substrate is used as the support, alignment can be provided on the surface due to the manufacturing process (e.g., extrusion or stretching of the substrate). Alignment capability can also be generated by brushing the support or imprinting oriented microstructures. Alternatively, a thin layer of material specifically designed for alignment properties can be coated onto the support. This layer can be further brushed or processed to have oriented microstructures on the surface, for example, by imprinting. If the thin layer contains a photo-orientable material, alignment can be generated by exposing it to alignment light.

[0103] The alignment surface of the substrate can be patterned with alignment directions to define the alignment pattern of the liquid crystal in the LCP layer. Preferably, an alignment layer containing a photo-alignable material is used for this purpose, and the alignment pattern is generated by selectively exposing alignment light to different polarization planes.

[0104] In this invention, the novel compounds of Formula I have been found to have high birefringence. Furthermore, the compounds of Formula I can be oriented via alignment layers, and are preferably photo-aligning materials used at low energies, providing a more energy-efficient and economical method. Moreover, it has been surprisingly found that the compounds of Formula I exhibit very good alignment quality without any crystallization.

[0105] The invention will now be described with reference to the following non-limiting embodiments. These embodiments are provided by way of illustration only. Variations of these embodiments falling within the scope of the invention will be apparent to those skilled in the art. Example

[0106] Definitions used in the embodiments

[0107] 1 H NMR: 1 H nuclear magnetic resonance spectrum

[0108] DMSO-d6: Deuterated dimethyl sulfoxide

[0109] 300MHz: 300 megahertz

[0110] m: multiplet, d: doublet, dd: double doublet, t: triplet, s: singlet

[0111] DMF: Dimethylformamide

[0112] HCl: hydrochloric acid

[0113] CH2Cl2: Dichloromethane

[0114] THF: Tetrahydrofuran

[0115] NMP: N-methyl-2-pyrrolidone

[0116] CuI: Cuprous iodide

[0117] MgSO4: Magnesium sulfate

[0118] In the following embodiments, the thermally induced phase is abbreviated as follows:

[0119] T (Cr-N) The transformation temperature from the crystalline phase to the nematic phase.

[0120] T (N-I) Transformation temperature from nematic phase to isotropic phase

[0121] 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]hexyloxy]benzoate, compound 1.

[0122]

[0123] Preparation of 3-[(6-ethynyl-2-naphthyl)oxy]propane-1-ol, compound 2

[0124]

[0125] 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 was heated at 80 °C for 18 h. The solution was then cooled and poured into 400 mL of water / HCl solution. The resulting precipitate was filtered off and washed twice with 200 mL of water. The residue was further purified by rapid column chromatography using a silica gel with a 1:1 mixture of hexane and ethyl acetate to give 22.47 g. Recrystallization from heptane / ethyl acetate (10:1) yielded 18.6 g of compound 2 as a grayish-white solid.

[0126] Preparation of 3-[[6-(2-trimethylsilylethynyl)-2-naphthyl]oxy]propane-1-ol, compound 3

[0127]

[0128] Bis(triphenylphosphine)palladium(II) chloride (2.1 g, 2.99 mmol), CuI (799 mg, 4.195 mmol), and compound 2 were placed in 83.4 mL of triethylamine. The mixture was stirred at 25 °C for 15 min, and (trimethylsilyl)acetylene (11.77 g, 119.8 mmol) was added. After stirring the suspension at 80 °C for 2 h, HCl solution was added dropwise. The mixture was stirred for 30 min, filtered through Hyflo / silica gel, and washed three times with 100 mL of ethyl acetate. The solution was extracted with ethyl acetate. The combined organic layers were washed with 5 mL of water and dried over MgSO4. After concentrating the solvent under vacuum, the residue was purified by rapid column chromatography using a silica gel with a 1:1 mixture of hexane and ethyl acetate to give 13.41 g of compound 3.

[0129] Preparation of 3-[(6-ethynyl-2-naphthyl)oxy]propane-1-ol, compound 4

[0130]

[0131] 12.4 g (89.79 mmol) of potassium carbonate was aliquoted into several portions and added to a solution of compound 3 in 135 mL of methanol. After stirring at room temperature for 1 h, the reaction mixture was filtered through a Hyflo / silica filter and washed three times with 25 mL of methanol. The solution was then poured into an aqueous HCl solution and extracted with ethyl acetate. The combined organic layers were dried over MgSO4. After concentration under vacuum, 10.84 g of compound 4 was given as a pale yellow solid.

[0132] Preparation of propyl 5-iodo-2-[6-(4-iodo-2-propoxycarbonyl-phenoxy)hexyloxy]benzoate, compound 5

[0133]

[0134] A mixture of 9.24 g (30.18 mmol) of propyl 2-hydroxy-5-iodobenzoate, 5.42 g (39.24 mmol) of potassium carbonate, 601 mg (3.62 mmol) of potassium iodide, and 3.68 g (15.09 mmol) of 1,6-dibromobutane in 35 mL of DMF was heated at 80 °C for 5 h. The solution was then cooled and poured into 400 mL of water / HCl solution. The resulting precipitate was filtered off and washed twice with 50 mL of water. Purification was performed by recrystallization in acetonitrile to give 9.44 g of compound 5 as a grayish-white solid.

[0135] Preparation of propyl 5-[2-[6-(3-hydroxypropoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(3-hydroxypropoxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexyloxy]benzoate, compound 6

[0136]

[0137] Bis(triphenylphosphine)palladium(II) chloride (202 mg, 0.288 mmol), CuI (109 mg, 0.576 mmol), propyl 5-iodo-2-[6-(4-iodo-2-propoxycarbonyl-phenoxy)hexyloxy]benzoate (4 g, 5.765 mmol), and 8.02 mL of triethylamine (57.65 mmol) were placed in 40 mL of DMF. The mixture was stirred at 25 °C for 15 min, and 3-[(6-ethynyl-2-naphthyl)oxy]propane-1-ol (2.87 g, 12.68 mmol) was added. After stirring the suspension at room temperature for 8 h, HCl solution was added, and the mixture was stirred for 30 min. The reaction mixture was filtered through Hyflo / silica and washed three times with 100 mL of ethyl acetate. The solution was extracted with ethyl acetate. The combined organic layers were washed with water and dried over MgSO4. After the solvent was concentrated under vacuum, the residue was purified by rapid column chromatography using a silica gel with a 1:1 mixture of hexane and ethyl acetate to give 4.33 g of compound 6.

[0138] Preparation of propyl benzoate 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]hexyloxy]benzoate, Compound 1

[0139] 4.33 g (4.859 mmol) of compound 6 was added to 45 mL of THF and 2.65 g (26.24 mmol) of triethylamine, along with 118.7 mg (0.97 mmol) of 4-dimethylaminopyridine. The solution was cooled to 0 °C and acryloyl dichloride (2.2 g, 24.29 mmol) was added dropwise. The solution was then allowed to return to room temperature and stirred for 18 hours. The residue was purified by rapid column chromatography using a silica gel with a 1:1 mixture of hexane and ethyl acetate to give 1.2 g of a grayish-white solid, compound 1.

[0140] 1H NMR (400MHz, 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).

[0141] Liquid crystal phase transition: Compound 1 was observed using a polarizing microscope under a cross-polarizer to determine its phase transition temperature. The results showed that as the temperature increased, the crystalline phase reached 105.8℃ (T0). (Cr-N) The phase transforms into a nematic phase, while the isotropic phase transforms at 125.7℃ (T). (N-I) )Appear.

[0142] Example 2: Preparation of propyl benzoate 5-[2-[6-(6-prop-2-enoyloxyhexyloxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(6-prop-2-enoyloxyhexyloxy)-2-naphthyl]ethynyl]phenoxy]hexyloxy]benzoate, compound 7

[0143]

[0144] Preparation of 6-[(6-bromo-2-naphthyl)oxy]hexane-1-ol, compound 8a

[0145]

[0146] Compound 8a was prepared according to the method described in Compound 2 of Example 1, except that 3-chloropropanol was replaced with 3-bromohexanol.

[0147] Preparation of 6-[[6-(2-trimethylsilylethynyl)-2-naphthyl]oxy]hexane-1-ol, compound 8b

[0148]

[0149] Compound 8b was prepared according to the method described in Compound 3 of Example 1, except that Compound 2 was replaced with Compound 8a.

[0150] Preparation of 6-[(6-ethynyl-2-naphthyl)oxy]hexane-1-ol, compound 9

[0151]

[0152] Compound 9 was prepared according to the method described in Compound 4 of Example 1, except that Compound 3 was replaced with Compound 8b.

[0153] Preparation of 1-(6-chlorohexyloxy)-4-iodobenzene, compound 10

[0154]

[0155] To a solution of 4-iodophenol (25 g, 113.6 mmol) in 250 mL of THF, 6-chlorohexanol (19.4 g, 142 mmol) and triphenylphosphine (37.25 g, 142 mmol) were added. The mixture was cooled to 0 °C and 250 mL of THF containing diisopropyl azodicarbonate (28.72 g, 142 mmol) was added dropwise. After the addition, the reaction was cooled to room temperature and stirred for 18 h. The solution was then concentrated under vacuum and the residue was purified by rapid column chromatography using a silica gel with a 1:4 mixture of hexane and ethyl acetate to give 35.4 g of a grayish-white solid, compound 10.

[0156] Preparation of propyl 5-iodo-2-[6-(4-iodophenoxy)hexyloxy]benzoate, compound 11

[0157]

[0158] A mixture of 12.05 g (39.37 mmol) propyl 2-hydroxy-5-iodobenzoate, 7.07 g (51.18 mmol) potassium carbonate, 784 mg (4.73 mmol) potassium iodide, and 40 mL DMF was added dropwise to 50 mL DMF containing 20 g (50.06 mmol) 1-(6-chlorohexyloxy)-4-iodobenzene. After heating at 80 °C for 18 h, the solution was cooled and poured into 400 mL of water / HCl solution. The resulting precipitate was filtered off and purified by rapid chromatography using a silica gel with a 9:1 mixture of hexane and ethyl acetate to give 23.3 g of a pale yellow solid, compound 11.

[0159] Preparation of propyl 5-[2-[6-(6-hydroxyhexyloxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(6-hydroxyhexyloxy)-2-naphthyl]ethynyl]phenoxy]hexyloxy]benzoate, compound 12

[0160]

[0161] Compound 12 was prepared according to the method described in Compound 6 of Example 1, except that Compound 5 was replaced with Compound 11.

[0162] Preparation of propyl benzoate 5-[2-[6-(6-prop-2-enoyloxyhexyloxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(6-prop-2-enoyloxyhexyloxy)-2-naphthyl]ethynyl]phenoxy]hexyloxy]benzoate, compound 7

[0163] Compound 7 was prepared according to the method described in Compound 1 of Example 1, except that Compound 6 was replaced with Compound 12.

[0164] 1 H NMR (400MHz, 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).

[0165] Liquid crystal phase transition: T (Cr-N) 83.3℃; T (N-I) 146.3℃

[0166] Example 3: Preparation of methyl 2-[6-[2-methoxycarbonyl-4-[2-[6-(11-prop-2-enoyloxyundecyloxy)-2-naphthyl]ethynyl]phenoxy]hexyloxy]-5-[2-[6-(11-prop-2-enoyloxyundecyloxy)-2-naphthyl]ethynyl]benzoate, compound 14

[0167]

[0168] Preparation of 11-[(6-bromo-2-naphthyl)oxy]undecane-1-ol, compound 15

[0169]

[0170] Compound 15 was prepared according to the method described in Compound 2 of Example 1, except that 3-chloropropanol was replaced with 11-bromoundecanool.

[0171] Preparation of 11-[[6-(2-trimethylsilylethynyl)-2-naphthyl]oxy]undecane-1-ol, compound 16

[0172]

[0173] Compound 16 was prepared according to the method described in Compound 3 of Example 1, except that Compound 2 was replaced with Compound 15.

[0174] Preparation of 11-[(6-ethynyl-2-naphthyl)oxy]undecane-1-ol, compound 17

[0175]

[0176] Compound 17 was prepared according to the method described in Compound 4 of Example 1, except that Compound 3 was replaced with Compound 16.

[0177] Preparation of methyl 5-iodo-2-[6-(4-iodo-2-methoxycarbonyl-phenoxy)hexyloxy]benzoate, compound 18

[0178]

[0179] Compound 18 was prepared according to the method described in Compound 5 of Example 1, except that propyl 2-hydroxy-5-iodobenzoate was replaced with methyl 2-hydroxy-5-iodobenzoate.

[0180] Preparation of methyl 5-[2-[6-(11-hydroxyundecyloxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(11-hydroxyundecyloxy)-2-naphthyl]ethynyl]-2-methoxycarbonyl-phenoxy]hexyloxy]benzoate, compound 19

[0181]

[0182] Compound 19 was prepared according to the method described in Compound 6 of Example 1, except that Compound 5 was replaced with Compound 18.

[0183] Preparation of methyl 2-[6-[2-methoxycarbonyl-4-[2-[6-(11-prop-2-enoyloxyundecyloxy)-2-naphthyl]ethynyl]phenoxy]hexyloxy]-5-[2-[6-(11-prop-2-enoyloxyundecyloxy)-2-naphthyl]ethynyl]benzoate, compound 14

[0184] Compound 14 was prepared according to the method described in Compound 1 of Example 1, except that Compound 6 was replaced with Compound 19.

[0185] 1H NMR(400MHz,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).

[0186] Liquid crystal phase transition: T (Cr-N) 110.6℃; T (N-I) 120.8℃

[0187] Example 4: Preparation of propyl benzoate 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]hexyloxy]benzoate, compound 20

[0188]

[0189] Preparation of 5-[(6-bromo-2-naphthyl)oxy]pentan-1-ol, compound 21

[0190]

[0191] Compound 21 was prepared according to the method described in Compound 2 of Example 1, except that 3-chloropropanol was replaced with 5-bromopentanol.

[0192] Preparation of 5-[[6-(2-trimethylsilylethynyl)-2-naphthyl]oxy]pentan-1-ol, compound 22

[0193]

[0194] Compound 22 was prepared according to the method described in Compound 3 of Example 1, except that Compound 2 was replaced with Compound 21.

[0195] Preparation of 5-[(6-ethynyl-2-naphthyl)oxy]pentane-1-ol, compound 23

[0196]

[0197] Compound 23 was prepared according to the method described in Compound 4 of Example 1, except that Compound 3 was replaced with Compound 22.

[0198] Preparation of propyl benzoate of 5-[2-[6-(5-hydroxypentoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(5-hydroxypentoxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexyloxy]benzoate, compound 24

[0199]

[0200] Compound 24 was prepared according to the method described in Compound 6 of Example 1, except that Compound 4 was replaced with Compound 23.

[0201] Preparation of propyl benzoate of 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]hexyloxy]benzoate, compound 20

[0202] Compound 20 was prepared according to the method described in Compound 1 of Example 1, except that Compound 6 was replaced with Compound 24.

[0203] 1 H NMR (400MHz, 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)

[0204] Liquid crystal phase transition: T (Cr-N) 123℃; T (N-I) 126.9℃

[0205] Example 5: Preparation of propyl benzoate 5-[2-[6-(6-prop-2-enoyloxyhexyloxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[5-(6-prop-2-enoyloxyhexyloxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexyloxy]benzoate, compound 25

[0206]

[0207] Preparation of propyl 5-[2-[6-(6-hydroxyhexyloxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(6-hydroxyhexyloxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexyloxy]benzoate, compound 26

[0208]

[0209] Compound 26 was prepared according to the method described in Compound 6 of Example 1, except that Compound 4 was replaced with Compound 9.

[0210] Preparation of propyl benzoate of 5-[2-[6-(6-prop-2-enoyloxyhexyloxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[5-(6-prop-2-enoyloxyhexyloxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexyloxy]benzoate, compound 25

[0211] Compound 25 was prepared according to the method described in Compound 1 of Example 1, except that Compound 6 was replaced with Compound 26.

[0212] 1 H NMR (400MHz, 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)

[0213] Liquid crystal phase transition: T (Cr-N) 103.5℃; T (N-I) 117℃

[0214] Example 6: Preparation of propyl benzoate 5-[2-[6-(6-prop-2-enoyloxyhexyloxy)-2-naphthyl]ethynyl]-2-[4-[4-[2-[6-(6-prop-2-enoyloxyhexyloxy)-2-naphthyl]ethynyl]phenoxy]butoxy]benzoate, compound 30

[0215]

[0216] Preparation of propyl 5-iodo-2-[4-(4-iodophenoxy)butoxy]benzoate, compound 31

[0217]

[0218] Compound 31 was prepared according to the method described in Compound 11 of Example 2, except that 1-(6-chlorohexyloxy)-4-iodobenzene was replaced with 1-(6-chlorobutoxy)-4-iodobenzene.

[0219] Preparation of propyl 5-[2-[6-(6-hydroxyhexyloxy)-2-naphthyl]ethynyl]-2-[4-[4-[2-[6-(6-hydroxyhexyloxy)-2-naphthyl]ethynyl]phenoxy]butoxy]benzoate, compound 32

[0220]

[0221] Compound 32 was prepared according to the method described in Compound 12 of Example 2, except that Compound 11 was replaced with Compound 31.

[0222] Preparation of propyl benzoate of 5-[2-[6-(6-prop-2-enoyloxyhexyloxy)-2-naphthyl]ethynyl]-2-[4-[4-[2-[6-(6-prop-2-enoyloxyhexyloxy)-2-naphthyl]ethynyl]phenoxy]butoxy]benzoate, compound 30

[0223] Compound 30 was prepared according to the method described in Compound 1 of Example 1, except that Compound 6 was replaced with Compound 31.

[0224] 1 H NMR (400MHz, 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)

[0225] Liquid crystal phase transition: T (Cr-N) 85.1℃; T (N-I) 158.3℃

[0226] Example 7: Preparation of ethyl benzoate 2-[6-[2-ethoxycarbonyl-4-[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]phenoxy]hexyloxy]-5-[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]benzoate, compound 33

[0227]

[0228] Preparation of ethyl 2-[6-(2-ethoxycarbonyl-4-iodo-phenoxy)hexyloxy]-5-iodo-benzoate, compound 34

[0229]

[0230] Compound 34 was prepared according to the method described in Compound 5 of Example 1, except that propyl 2-hydroxy-5-iodobenzoate was replaced with ethyl 2-hydroxy-5-iodobenzoate.

[0231] Preparation of ethyl 2-[6-[2-ethoxycarbonyl-4-[2-[6-(3-hydroxypropoxy)-2-naphthyl]ethynyl]phenoxy]hexyloxy]-5-[2-[6-(3-hydroxypropoxy)-2-naphthyl]ethynyl]benzoate, compound 35

[0232]

[0233] Compound 35 was prepared according to the method described in Compound 6 of Example 1, except that Compound 5 was replaced with Compound 34.

[0234] Preparation of ethyl 2-[6-[2-ethoxycarbonyl-4-[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]phenoxy]hexyloxy]-5-[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]benzoate, compound 33

[0235] Compound 33 was prepared according to the method described in Compound 1 of Example 1, except that Compound 6 was replaced with Compound 35.

[0236] 1 H NMR (400MHz, 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(d d,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)

[0237] Liquid crystal phase transition: T (Cr-N) 123.5℃; T (N-I) 143℃

[0238] Example 8: Preparation of an alignment layer using photoalignment materials

[0239] A photoalignment composition (with a solid content of 3% in cyclopentanone, as described in patent publication WO2012 / 085048: Photoactive polymeric material used as an alignment layer for liquid crystals) was spin-coated onto a glass substrate. The film was dried at 180°C for 10 minutes, resulting in a film thickness of approximately 100 nm. The film was then exposed to alignment light of 250 mJ / cm². 2Quasi-linearly polarized UV (LPUV) light (280-320nm). The polarization plane is 0° relative to the reference edge on the substrate.

[0240] Example 9: Preparation of Compound 1 film

[0241] By using 13.552 w% of compound 1, 0.140 w% of 2,6-di-tert-butyl-4-methylphenol, and 0.280 w% of... 369 ( The chemical structure of 369 is 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1), 0.028 w%. A 14.0 wt% solution was prepared by mixing 378 (a solvent-free silicone leveling agent) in cyclopentanone and stirring thoroughly at room temperature until the solid was completely dissolved. The polymer solution was spin-coated onto a glass plate having the alignment layer of Example 8 to form a liquid crystal film. The film was dried on a temperature-controlled hot plate at 108°C for 1 minute. The sample was cooled to room temperature (20-25°C) and then photopolymerized by irradiation with a mercury lamp under a N2 atmosphere for approximately 2 minutes to fix the alignment state of the liquid crystal.

[0242] The membrane obtained in Example 9 exhibits a very well oriented nematic mesophase at room temperature.

[0243] Example 10: Preparation of Compound 25 film

[0244] By using 14.775 w% compound 25, 0.075 w% 2,6-di-tert-butyl-4-methylphenol, and 0.150 w% 369 was mixed in cyclopentanone and stirred thoroughly at room temperature until the solid was completely dissolved to prepare a 15.0 w% solution. The above polymer solution was spin-coated onto a glass plate having the alignment layer of Example 8 to form a liquid crystal film. The film was dried on a temperature-controlled hot plate at 110°C for 5 min. The sample was cooled to room temperature and then photopolymerized by irradiation with ultraviolet light using a mercury lamp for about 2 min at room temperature (20-25°C) and under a N2 atmosphere to fix the alignment state of the liquid crystal.

[0245] The membrane obtained in Example 10 exhibits a very well-oriented nematic mesophase at room temperature.

[0246] Example 11: Preparation of Compound 4 film

[0247] By using 7.3875 w% compound 4, 0.0375 w% 2,6-di-tert-butyl-4-methylphenol, and 0.075 w% 369 was mixed in cyclopentanone and stirred thoroughly at room temperature until the solid was completely dissolved to prepare a 7.5 w% solution. The above polymer solution was spin-coated onto a glass plate having the alignment layer of Example 8 to form a liquid crystal film. The film was dried on a temperature-controlled hot plate at 120°C for 5 min. The sample was cooled to room temperature and then photopolymerized by irradiating it with ultraviolet light using a mercury lamp for about 2 min at room temperature and under a N2 atmosphere to fix the alignment state of the liquid crystal.

[0248] The membrane obtained in Example 11 exhibits an oriented nematic mesophase with moderate alignment quality at room temperature.

[0249] Example 12: Preparation of Compound 7 film

[0250] By using 14.370 w% compound 7, 0.300 w% 2,6-di-tert-butyl-4-methylphenol, and 0.300 w% A 15 wt% solution was prepared by mixing 369 in cyclopentanone / 3-dioxolane 60 / 40 and stirring thoroughly at room temperature until the solid was completely dissolved. The polymer solution was spin-coated onto a glass plate having the alignment layer of Example 8 to form a liquid crystal film. The film was dried on a temperature-controlled hot plate at 130°C for 5 min. The sample was cooled to room temperature and then photopolymerized by irradiation with ultraviolet light using a mercury lamp for approximately 2 min at room temperature (20-25°C) under a N2 atmosphere to fix the alignment state of the liquid crystal.

[0251] The membrane obtained in Example 12 exhibits a very well oriented nematic mesophase at room temperature.

[0252] Example 13: Preparation of Compound 20 film

[0253] By using 14.520 w% compound 20, 0.150 w% 2,6-di-tert-butyl-4-methylphenol, and 0.300 w% 369 and 0.030 wt%. 378 was mixed in cyclopentanone and stirred thoroughly at room temperature until the solid was completely dissolved to prepare a 15 w% solution. The above polymer solution was spin-coated onto a glass plate having the alignment layer of Example 8 to form a liquid crystal film. The film was dried on a temperature-controlled hot plate at 108°C for 1 min. The sample was cooled to room temperature and then photopolymerized by irradiation with ultraviolet light using a mercury lamp for about 2 minutes at room temperature (20-25°C) under a N2 atmosphere to fix the alignment state of the liquid crystal.

[0254] The membrane obtained in Example 13 exhibits a very well oriented nematic mesophase at room temperature.

[0255] Example 14: Preparation of Compound 30 film

[0256] By using 14.520 w% compound 30, 0.150 w% 2,6-di-tert-butyl-4-methylphenol, and 0.300 w% A 15 wt% solution was prepared by mixing 369 and 0.030 wt% Tego Flow 0.300 in cyclopentanone and stirring thoroughly at room temperature until the solid was completely dissolved. The polymer solution was spin-coated onto a glass plate having the alignment layer of Example 8 to form a liquid crystal film. The film was dried on a temperature-controlled hot plate at 148°C for 5 min. The sample was cooled to room temperature and then photopolymerized by irradiation with ultraviolet light using a mercury lamp for approximately 2 min at room temperature (20-25°C) under a N2 atmosphere to fix the alignment state of the liquid crystal.

[0257] The membrane obtained in Example 14 exhibits a very well oriented nematic mesophase at room temperature.

[0258] Example 15

[0259] The retardation at 550 nm of the samples described in Examples 9, 10, 11, 12, and 14 was measured using an ellipsometry. The thickness of the samples was measured using a contact profiler. The birefringence (Δn) was obtained from the measured retardation and thickness values ​​according to the formula (Δn = retardation / thickness). The values ​​are listed in Table 1.

[0260] Table 1

[0261]

[0262]

[0263] The films of Examples 9, 10, 11, 12, and 14 exhibit high birefringence in the range of 0.31–0.39. These novel LCPs can be used to fabricate phase retardation optical films such as quarter-wave plates (QWPs) and half-wave plates (HWPs). Retarders transmit light and alter its polarization state, and are widely used in various display applications or security components. The exceptionally high birefringence of these novel LCPs allows for a significant reduction in the thickness of retarder films.

[0264] As an example, Table 2 shows the required thicknesses for obtaining quarter-wave plate (λ / 4) retarder (QWP) and half-wave plate (λ / 2) retarder (HWP) at 550 nm using compounds 1, 25, 14, 7 and 30, respectively, used in Examples 9, 10, 11, 12 and 14.

[0265] Table 2

[0266] Example Required thickness (nm) for QWP at 550nm HWP Required Thickness (nm) at 550nm 9 353 706 10 444 888 11 430 860 12 382 764 14 393 786

Claims

1. Compounds of formula (I): in: A is phenylene, and B is naphthyl; SP1, SP2, and SP3 each independently represent substituted or unsubstituted linear or branched C1-C chains. 18 Alkylene, wherein 1, 2, 3, 4 or more CH2, CH or C groups are not substituted or are substituted by groups selected from -CH=CH-, -C≡C-, -O-, -S-, -NR'CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR', provided that the spacer group does not contain two adjacent heteroatoms, and wherein the C1-C 18 The substituents of the alkylene group are selected from hydroxyl, ether, ester and halogen groups; X1, X2, X3, and X4 are each independently selected from -O-, -S-, -NR'-, -CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR', and single bonds; R' is selected from hydrogen, C1-C 18 alkyl; BP1 and BP2 each represent polymerizable groups independently; A1, A2, A3, and A4 are each independently selected from hydrogen, -OR, -COOR, -OCOR, -CONR, -OCOOR, -OCONR, and C1-C. 18 Alkyl groups, wherein: R is selected from hydrogen; the aromatic group is selected from the following unsubstituted or substituted carbocyclic or heterocyclic groups: a monocyclic ring of 5 or 6 atoms, two adjacent monocyclic rings of 5 or 6 atoms, a bicyclic system of 8, 9 or 10 atoms, or a tricyclic system of 13 or 14 atoms, wherein the substituent of the aromatic group of the carbocyclic or heterocyclic group is selected from halogen, hydroxyl, acryloyloxy, alkylacryloyloxy, alkoxy, alkylcarbonyloxy, alkyloxycarbonyloxy, alkyloxocarbonyloxy, vinyl, vinyloxy and / or allyloxy groups; substituted or unsubstituted linear or branched C 1-18 Alkyl group, wherein 1, 2, 3, 4 or more CH2, CH or C groups are not substituted or are substituted by groups selected from -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 selected from hydrogen and C1-C 18 Alkyl groups, and the C1-C groups thereof 18 The substituents of the alkyl group are selected from hydroxyl, ether, ester and halogen groups.

2. The compound according to claim 1, wherein BP1 and BP2 are each independently selected from 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, wherein: W represents hydrogen, chlorine, phenyl, or C1-C6 alkyl, and R 3 It represents C1-C6 alkyl, under the condition that R 3 When attached to an aryl group, it can also represent hydrogen or C1-C6 alkoxy.

3. The compound according to any one of claims 1-2, wherein SP1, SP2 and SP3 each independently represent a substituted or unsubstituted linear or branched C1-C1 chain. 12 Alkylene, wherein 1, 2, 3, 4 or more CH2, CH or C groups are not substituted or are substituted by groups selected from -CH=CH-, -C≡C-, -O-, -S-, -NR'CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR', provided that the spacer group does not contain two adjacent heteroatoms, and wherein the C1-C 12 The substituents of the alkylene group are selected from hydroxyl, ether, ester and halogen groups.

4. The compound according to any one of claims 1-2, wherein the groups X1, X2, X3 and X4 are each independently selected from -O-, -COO-, -OOC-, -OCOO- and single bonds.

5. The compound according to any one of claims 1-2, wherein groups A1 and A2 are each independently selected from hydrogen, -OR, -COOR, -OCOR, furan, benzene, pyridine, triazine, pyrimidine, naphthalene, phenanthrene, biphenyl, or tetrahydronaphthalene, wherein R is selected from C1-C2. 18 alkyl.

6. An LCP mixture comprising any one of claims 1-5.

7. An LCP network comprising a compound of any one of claims 1-5 in polymeric form or a mixture of claims 6.

8. A method for forming an LCP network, comprising: Forming an LCP layer comprising a compound of formula (I) according to any one of claims 1-5 or an LCP mixture according to claim 6, and The LCP layer is then polymerized.

9. Use of the compound of any one of claims 1-5 or the mixture of claim 6 in the manufacture of optical or electro-optical devices.

10. An optical or electro-optical device comprising the compound of any one of claims 1-5, the mixture of claim 6, or the network of claim 7.

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