Liquid crystal compounds

Abstract

The present invention relates to novel polymerizable liquid crystals of formula (I), LCP mixtures containing these compounds, and their use for optical and electro-optical devices. TIFF2025531453000011.tif30165

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. As displays become thinner and thinner, the industry is demanding thinner optical LCP films that provide the desired optical or electro-optical effects.

[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 depending on the birefringence and thickness of the phase retarder. One of the biggest challenges in fabricating a phase retarder is to create a high-performance film with a small charge. By using liquid crystals with high birefringence, it is possible to achieve the required retardation value with a small amount of liquid crystal compound.

[0004] LCP materials with high birefringence could result in thin optical films.

[0005] Therefore, the objective of the present invention was to search for a new LCP material that has high birefringence and is applicable to optical films.

[0006] A first aspect of the present invention is a compound of formula (I) [ka] [In the formula, SP1 and SP2 each independently represent a group of formula -(CH2)p-, where p is an integer from 1 to 18, and one or more, in particular -CH2- groups, are unsubstituted or replaced by a group selected from the group consisting of -CH=CH-; -O-, -S-, -NR'-, -CO-, -COO-, -OOC-, -CONR'-, -OCOO- and -OCONR', with the proviso that firstly, the spacer group does not contain two adjacent heteroatoms, and secondly, when X1, X2, X3 and X4 are single bonds, p can also have the value 0; X1 and X2 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; R1, R2, R3 and R4 are each independently hydrogen, halogen, -OR5, -COOR5, -OCOR5, -CONR5, -OCOOR5, -OCONR5 and C1-C 18 alkyl groups, wherein R5 is C1-C 18 selected from the group consisting of alkyl, aryl, aralkyl and alkylaryl. The present invention provides a compound, preferably a liquid crystal, represented by the formula:

[0007] The spacer groups SP1 and SP2 are each, independently of one another, unsubstituted or substituted by one or more fluorine or chlorine atoms. A group without any substituents is preferred. Particularly preferred is that the integer p has a value of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, and even more particularly preferred is that the integer p has a value of 1, 2, 3, 4, 5, 6, 7 or 8. Furthermore, particularly preferred is that SP1 and SP2 are each, independently of one another, unsubstituted or represent a group of the formula -(CH2)p- in which one, two, three or four -CH2- groups are replaced by a group selected from the group consisting of -CH=CH-, -O-, -CO-, -COO-, -OOC-, -CONR'-, -OCOO- and -OCONR', especially -O-, -CO-, -COO-, -OOC- and -OCOO-.

[0008] The naphthalene groups in formula (I) are each independently unsubstituted or substituted with one or two substituents selected from the group consisting of fluorine or chlorine atoms, nitrile, C1-C6 alkyl, C1-C6 alkenyl, C1-C6 alkoxy and C1-C6 alkenyloxy. Preferably, each naphthalene group contains no more than one additional substituent. It is particularly preferred that the naphthalene group contains no additional substitution.

[0009] The groups X1 and X2 are each, independently of one another, preferably selected from the group consisting of -O-, -COO-, -OOC-, -OCOO-, and a single bond;

[0010] It is especially preferred that X1, X2, X3 and X4 are each independently selected from -O- or a single bond.

[0011] Preferred groups R1, R2, R3 and R4 are each independently selected from the group consisting of hydrogen, -OR5, -COOR5, -OCOR5, -OCOOR5, and C1-C6 alkyl groups, where R5 is selected from the group consisting of C1-C6 alkyl.

[0012] More preferred groups R1, R2, R3 and R4 are each independently selected from the group consisting of hydrogen, -OR5, -COOR5, -OCOR5, -OCOOR5, and C1-C6 alkyl groups; In particular, selected from the group consisting of hydrogen and -COOR5; where R5 is C1-C 18 alkyl, provided that at least one of R1, R2, R3 or R4 is hydrogen, particularly at least two of R1, R2, R3 or R4 are hydrogen, and more particularly at least three of R1, R2, R3 or R4 are hydrogen.

[0013] The radicals BP1 and BP2 are each, independently of one another, preferably selected from the group consisting of 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-, R6-Ph-CH=CH-COO-, R6-OOC-CH=CH-Ph-O- and 2-W-epoxyethyl, W represents hydrogen, chloride, aryl, or C1-C6 alkyl; R6 represents C1-C6 alkyl, provided that when R6 is attached to an aryl group, R6 may also represent hydrogen or C1-C6 alkoxy.

[0014] In particular, the groups BP1 and BP2 are each, independently of one another, preferably selected from the group consisting of CH2=CW-COO-, CH2=CH-O-, and CH2=CH-OOC-, in which W represents hydrogen, chloride, aryl or C1-C6 alkyl, preferably hydrogen or C1-C6 alkyl.

[0015] The term "alkyl" refers to C1-C 18 Alkyl, preferably C1-C 12 It should be understood to include alkyl, especially C1-C6 alkyl. The term alkyl includes achiral, branched or straight-chain, substituted or unsubstituted alkyl groups. Examples of alkyl groups that may be present in the compounds of the present invention include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, iso-pentyl, n-pentyl, n-hexyl, iso-hexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, n-nonyl, iso-nonyl, n-decyl, isodecyl, n-undecyl, iso-undecyl, n-dodecanoyl, iso-dodecanoyl, or 2-methylpropane, 2-methylbutane, 3-methylpentane, 2-methylhexane, 3-methylhexane.

[0016] The term "alkenyl" refers to C-C 18 Alkenyl, preferably C-C 12 It should be understood to include alkenyl, especially C1-C6 alkenyl. The term alkenyl includes achiral, branched or straight-chain, substituted or unsubstituted alkenyl groups in which the double bond is in the 2-position or higher. Examples of alkenyl groups that may be present in the compounds of the present invention include 2-propenyl, 3-butenyl, 3-isopentenyl, 4-pentenyl, 5-hexenyl, 4-isohexenyl, etc.

[0017] The term "alkoxy" refers to C-C 18 Alkoxy, preferably C-C 12It should be understood to include alkoxy, especially C1-C6 alkoxy. The term alkoxy includes achiral, branched or straight-chain, substituted or unsubstituted alkoxy groups. Examples of alkoxy groups that may be present in the compounds of the present invention include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxyl, iso-pentoxy, n-pentoxy, n-hexoxy, iso-hexoxy, n-heptoxy, iso-heptoxy, n-octoxy, iso-octoxy, n-nonoxy, iso-nonoxy, n-decoxy, isodecoxy, n-undecoxy, iso-undecoxy, n-dodecanoyl, iso-dodecanoyl, and the like.

[0018] The term "alkenyloxy" refers to C-C 18 Alkenyloxy, preferably C-C 12 It should be understood to include alkenyloxy, especially C1-C6 alkenyloxy. The term alkenyloxy includes achiral, branched or straight-chain, substituted or unsubstituted alkenyloxy groups in which the double bond is in the 2-position or higher. Examples of lower alkenyloxy groups that may be present in the compounds of the present invention include 2-propenyloxy, 3-butenyloxy, 4-pentenyloxy, 5-hexenyloxy, etc.

[0019] Substituents of "alkyl", "alkenyl", "alkoxy" and "alkenyloxy" include, for example, halogens such as fluorine, nitriles, C1-C 11 Alkoxy, trifluoromethyl, 4-(4-alkoxyoxyphenyl)benzonitrile.

[0020] The term "aryl" should be understood to include aromatic rings, preferably aromatic hydrocarbons, especially phenyl and naphthyl, most especially phenyl.

[0021] The term "aralkyl" refers to any monovalent radical derived from an alkyl radical by the replacement of one or more hydrogen atoms by an aryl group. This term should be understood to include phenethyl and the like.

[0022] The term "alkylaryl" should be understood to include methylphenyl, ethylphenyl, propylphenyl, and the like.

[0023] Halogen substituents as used in the present invention include fluorine, bromine, chlorine, iodine, especially fluorine.

[0024] Preferably, the present invention provides a compound of formula (I) [ka] [In the formula, SP1 and SP2 each independently represent a group of formula -(CH2)p-, where p is an integer of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, and the group of formula -(CH2)p- is unsubstituted; or one, two, three or four -CH2- groups are replaced by a group selected from the group consisting of -CH=CH-, -O-, -CO-, -COO-, -OOC- and -OCOO-, provided that, first, the spacer group does not contain two adjacent heteroatoms, and second, when X1 and X2 are single bonds, p can also have a value of 0; X1 and X2 are each independently selected from the group consisting of -O-, CO-, -COO-, -OOC-, -OCOO-, and a single bond; BP1 and BP2 each independently 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-, R6 -OOC-CH=CH-Ph-O- and 2-W-epoxyethyl, W represents hydrogen, chloride, aryl, or C1-C6 alkyl; R6 represents C1-C6 alkyl, provided that when R6 is attached to an aryl group, R6 may also represent hydrogen or C1-C6 alkoxy; R1, R2, R3 and R4 are each independently selected from the group consisting of hydrogen, -OR5, -COOR5, -OCOR5, -OCOOR5, and a C1-C6 alkyl group, where R5 is a C1-C6 alkyl group. 12 Alkyl, preferably C1-C 12 alkyl, more preferably methyl, ethyl, propyl, isopropyl, butyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl]. The present invention provides a compound, preferably a liquid crystal, represented by the formula:

[0025] Starting materials are commercially available or readily prepared and are well known to those skilled in the art.

[0026] As used within the context of this application, an LCP material refers to a liquid crystal material comprising liquid crystal monomers and / or liquid crystal oligomers and / or liquid crystal polymers and / or crosslinked liquid crystals. When a 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 exposure to actinic light (preferably including UV light). An LCP material may contain only one type of liquid crystal compound, but may also contain additional polymerizable and / or non-polymerizable compounds, not all of which need be liquid crystal compounds. Additionally, LCP materials may contain additives such as, 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, such as phenol derivatives, e.g., 4-ethoxyphenol or 2,6-di-tert-butyl-4-methylphenol (BHT), leveling agents; dispersants; polymer binders and / or monomeric compounds that can be converted into 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, e.g., 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, especially dichroic dyes.

[0027] 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 compound of formula (I) with one or more additional components. Organic solvents may be used in the preparation of these mixtures.

[0028] Therefore, a second aspect of the present invention provides an LCP mixture comprising a compound of formula (I) and one or more additional components.

[0029] The LCP mixture may also include a suitable organic solvent.

[0030] 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).

[0031] 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).

[0032] A 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 dichroic dyes 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 dichroic dye used per 100 parts by mass of the liquid crystal mixture is 0.01 to 40 parts by mass, preferably 0.05 to 15 parts by mass.

[0033] 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 present invention or an LCP mixture according to the third aspect of the present invention onto a substrate.

[0034] Therefore, a third aspect of the present invention provides a method of forming an LCP network comprising forming an LCP layer comprising a compound of formula (I) and polymerizing the layer.

[0035] The LCP mixtures according to the third aspect of the invention may also be used in a similar manner in the manufacture of LCP networks.

[0036] The present invention also includes, in a fourth aspect thereof, a crosslinked LCP network comprising a compound of formula (I) in crosslinked form.

[0037] Crosslinked LCP networks comprising a mixture according to the third aspect of the invention in crosslinked form may also be included in this aspect of the invention.

[0038] 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.

[0039] 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.

[0040] A sixth aspect of the present invention provides an optical or electro-optical device comprising a compound of formula (I) in a crosslinked state.

[0041] Optical or electro-optical devices comprising an LCP liquid crystal mixture according to the third aspect of the invention in a crosslinked state are also included in this aspect of the invention.

[0042] 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, the support can be an object with a complex surface. In principle, the support can be made of any material. Preferably, the support includes plastic, glass, or metal, or is a silicon wafer. If the support is flexible, it is preferably a plastic or metal foil. Preferably, the surface of the support is flat. In some applications, the support can include topographical surface structures, such as microstructures such as microlenses or microprisms, or structures that exhibit abrupt changes in shape, such as rectangular structures. Preferably, the support is transparent.

[0043] The support may be moving 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 onto 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 then wound as a free-standing film without the support.

[0044] The support may have additional layers, such as organic layers, dielectric layers, or metal layers. The layers can have various functions. For example, an organic layer can be coated as a primer layer to enhance the compatibility of the coated material with the support. The metal layer can serve as an electrode when used in an electro-optical device such as a display, or can function as 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 containing an OLED layer structure. The support may also be a retarder film, a polarizer, such as a polarizing film or sheet polarizer, or a reflective polarizer, such as the commercially available Vikuity™ DBEF film.

[0045] The LCP mixture can be applied to a substrate by any suitable method, such as extrusion, casting, molding, 2D or 3D printing, or coating. Suitable coating methods include spin coating, blade coating, knife coating, kiss-roll coating, die coating, dipping, brushing, bar casting, 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, and flexographic coating. Suitable printing methods include silkscreen printing, relief printing, such as flexographic printing, jet printing, intaglio printing, such as direct gravure or offset gravure printing, lithographic printing, such as offset printing, or stencil printing, such as screen printing.

[0046] The layer of the LCP mixture need not cover the entire surface of the substrate, but rather may be applied in a pattern, for example by printing, or may be treated after deposition to have a patterned configuration, for example by photolithographic methods.

[0047] 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 treatment. For example, when a plastic substrate is used as the support, the support can be aligned on its surface by a 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 a support specifically designed for alignment performance. The layer can be further treated to have a directional microstructure on its surface by brushing or, for example, imprinting. If the thin layer contains a photoalignment material, alignment can be created by exposing it to alignment light.

[0048] To define the orientation pattern of the liquid crystal in the LCP layer, the alignment surface of the substrate can exhibit a pattern of alignment directions. Preferably, an alignment layer containing a photo-alignable material is used for this purpose, and the alignment pattern is generated by selective exposure to alignment light of different polarization planes.

[0049] 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. [Example]

[0050] 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 Pd(PPh3)2Cl2: Bis(triphenylphosphine)palladium dichloride DMAP: 4-dimethylaminopyridine NMP: N-methyl-2-pyrrolidone CuI: Copper iodide MgSO4: Magnesium sulfate

[0051] 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 to isotropic phase

[0052] Example 1: Preparation of 3-[(6-bromo-2-naphthyl)oxy]-propan-1-ol, Compound 1 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 hours. 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 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 1 was obtained as an off-white solid.

[0053] Example 2: Preparation of 6-[(6-bromo-2-naphthyl)oxy]-hexan-1-ol, Compound 2 The title compound 2 is prepared according to the process for compound 1 described in Example 1, except that 3-chloropropanol is replaced with 6-chlorohexanol.

[0054] Example 3: Preparation of 3-[(6-(2-trimethylsilylethynyl)-2-naphthyl)oxy]-propan-1-ol, Compound 3 Bis(triphenylphosphine)palladium(II) chloride (2.1 g, 2.99 mmol), CuI (799 mg, 4.195 mmol), and 3-[(6-bromo-2-naphthyl)oxy]-propan-1-ol (compound 1) are placed in 83.4 ml of triethylamine. The mixture is stirred at 25 °C for 15 minutes, and (trimethylsilyl)acetylene (11.77 g, 119.8 mmol) is added. The suspension is stirred at 80 °C for 2 hours, after which a solution of HCl is added dropwise. The mixture is stirred for 30 minutes, then filtered through hyflosilica 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 MgSO 4 . After concentrating 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.

[0055] Example 4: Preparation of 6-[(6-(2-trimethylsilylethynyl)-2-naphthyl)oxy]-hexan-1-ol, Compound 4 The title compound 4 is prepared according to the process for compound 3 described in Example 3, except that 3-[(6-bromo-2-naphthyl)oxy]-propan-1-ol (compound 1) is replaced with 6-[(6-bromo-2-naphthyl)oxy]-hexan-1-ol (compound 2).

[0056] Example 5 Preparation of 3-[(6-ethynyl-2-naphthyl)oxy]-propan-1-ol, Compound 5 To a solution of compound 3 in 135 ml of methanol, 12.4 g (89.79 mmol) of potassium carbonate is added in portions. After stirring at room temperature for 1 hour, the reaction mixture is filtered through hyflo / silica and then washed three times with 25 ml of methanol. The solution is then poured into an aqueous solution of HCl and then extracted with ethyl acetate. The combined organic layers are dried over MgSO4. After concentration under vacuum, 10.84 g of compound 5 is obtained as a yellowish solid.

[0057] Example 6: Preparation of 6-[(6-ethynyl-2-naphthyl)oxy]-hexan-1-ol, Compound 6 The title compound 6 is prepared according to the process for compound 5 described in Example 5, except that 3-[(6-(2-trimethylsilylethynyl)-2-naphthyl)oxy]-propan-1-ol is replaced with 6-[4-(2-trimethylsilylethynyl)phenoxy]-hexan-1-ol.

[0058] Example 7: Preparation of methyl 2,5-diiodobenzoate, compound 7 2,5-Diiodobenzoic acid (15.0 g, 40.11 mmol) was dissolved in methanol (40 ml). After adding H2SO4 (concentrated, 4 ml), the clear, colorless solution was heated to reflux for 6 hours. The reaction mixture was allowed to cool to ambient temperature and poured onto ice. Extraction with ethyl acetate and evaporation of the solvent gave the title compound 7, which was dried under vacuum at 40 °C (14.93 g, 38.48 mmol).

[0059] Example 8: Preparation of hexyl 2,5-diiodobenzoate, compound 8 The title compound 8 is prepared according to the process for compound 7 described in Example 7, except that methanol is replaced with n-hexanol.

[0060] Example 9: Preparation of methyl 2,5-bis[2-[6-(6-hydroxyhexoxy)-2-naphthyl]ethynyl]benzoate, Compound 9 Under a N2 atmosphere, 6-[(6-ethynyl-2-naphthyl)oxy]-hexan-1-ol (compound 6) (4.5 g, 16.77 mmol), methyl 2,5-diiodobenzoate (compound 7) (3.25 g, 8.38 mmol), Pd(PPh3)2Cl2 (0.59 g, 0.84 mmol), CuI (0.318 g, 1.67 mmol), and triphenylphosphine (0.438 g, 1.67 mmol) are suspended in triethylamine (60 ml). The mixture is stirred at 60 °C for 6 h. After cooling to ambient temperature, the mixture is poured into ice water (50 ml) and acidified to pH 1 with HCl. The precipitate is filtered off, and the residue is recrystallized from acetonitrile (130 ml) to give the title compound (4.91 g, 7.34 mmol) as a beige solid.

[0061] Example 10: Preparation of hexyl 2,5-bis[2-[6-(6-hydroxyhexoxy)-2-naphthyl]ethynyl]benzoate, Compound 10 The title compound 10 is prepared according to the process for compound 9 described in Example 9, except that methyl 2,5-diiodobenzoate (compound 7) is replaced with hexyl 2,5-diiodobenzoate (compound 8).

[0062] Example 11: Preparation of methyl 2,5-bis[2-[6-(3-hydroxypropoxy)-2-naphthyl]ethynyl]benzoate, Compound 11 The title compound 11 is prepared according to the process for compound 9 described in Example 9, except that 6-[(6-ethynyl-2-naphthyl)oxy]-hexan-1-ol (compound 6) is replaced with 3-[(6-ethynyl-2-naphthyl)oxy]-propan-1-ol (compound 5).

[0063] Example 12: Preparation of hexyl 2,5-bis[2-[6-(3-hydroxypropoxy)-2-naphthyl]ethynyl]benzoate, Compound 12 The title compound 12 is prepared according to the process for compound 19 described in Example 19, except that 6-[(6-ethynyl-2-naphthyl)oxy]-hexan-1-ol (compound 6) is replaced with 3-[(6-ethynyl-2-naphthyl)oxy]-propan-1-ol (compound 5) and methyl 2,5-diiodobenzoate is replaced with hexyl 2,5-diiodobenzoate (compound 8).

[0064] Example 13: Preparation of methyl 2,5-bis[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]benzoate, Compound 13 [ka] Methyl 2,5-bis[2-[6-(6-hydroxyhexoxy)-2-naphthyl]ethynyl]benzoate (compound 9) (4.91 g, 7.34 mmol) was suspended in 100 ml of tetrahydrofuran and N,N-dimethylaniline (3.56 g, 29.4 mmol) was added. The mixture was cooled to 0 °C, and 2-propenoyl chloride (3.98 g, 44.0 mmol) was added dropwise, followed by DMAP (0.179 g, 1.47 mmol). The reaction mixture was stirred at 0-5 °C for 2 h. The reaction mixture was poured into ice water and extracted with ethyl acetate. Evaporation and recrystallization in acetonitrile yielded the title compound (1.71 g, 2.2 mmol) as a beige solid. Liquid crystal phase transition: Compound 13 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 appeared at 85°C (T (Cr-N) ) changes to a nematic phase, and the isotropic phase changes to (N-I) ) appears. 1 H NMR (300MHz) in DMSO-d6: 8.16 (s, 1H), 8.10 (m, 2H), 7.87 (m, 4H), 7.78 (m, 2H), 7.58 (m, 2H), 7.37 (m, 2H), 7.23 (m, 2H), 6.32 (m, 2H), 6.17 (m, 2H), 5.92 (m, 2H), 4.11 (m, 8H), 3.97 (s, 3H), 1.80 (m, 4H), 1.66 (m, 4H), 1.45 (m, 8H)

[0065] Example 14: Preparation of hexyl 2,5-bis[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]benzoate, Compound 14 [ka] The title compound 14 is prepared according to the process for compound 13 described in Example 13, except that methyl 2,5-bis[2-[6-(6-hydroxyhexoxy)-2-naphthyl]ethynyl]benzoate (compound 9) is replaced with hexyl 2,5-bis[2-[6-(6-hydroxyhexoxy)-2-naphthyl]ethynyl]benzoate (compound 10). Purification by silica gel flash chromatography using ethyl acetate / heptane (1:1 mixture) provides the title compound (1.16 g, 1.37 mmol, 22%) as a beige solid. Liquid crystal phase transition: Compound 14 is observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, as the temperature increases, the crystalline phase changes from 60°C (T (Cr-N) ) changes to a nematic phase, and the isotropic phase changes to (N-I) ) appears in Super. 1 H NMR (300MHz) in DMSO-d6: 8.17 (m, 1H), 8.09 (s, 1H), 8.06 (d, 1H), 7.86 (m, 4H), 7.78 (m, 2H), 7.57 (m, 2H), 7.37 (m, 2H), 7.22 (m, 2H), 6.32 (m, 2H), 6.16 (m, 2H), 5.92 (m, 2H), 4.36 (m, 2H), 4.13 (m, 8H), 1.80 (m, 4H), 1.66 (m, 4H), 1.45 (m, 12H), 1.19 (m, 4H), 0.76 (t, 3H)

[0066] Example 15: Preparation of methyl 2,5-bis[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]benzoate, Compound 15 [ka] The title compound 15 is prepared according to the process for compound 13 described in Example 13, except that methyl 2,5-bis[2-[6-(6-hydroxyhexoxy)-2-naphthyl]ethynyl]benzoate (compound 9) is replaced with methyl 2,5-bis[2-[6-(3-hydroxypropoxy)-2-naphthyl]ethynyl]benzoate (compound 11). Purification by silica gel flash chromatography using ethyl acetate provides the title compound (2.75 g, 3.97 mmol, 94%) as a yellowish solid. Liquid crystal phase transition: Compound 15 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 79°C (T (Cr-N) ) changes to a nematic phase, and the isotropic phase changes to (N-I) ) appears in Super. 1 H NMR (300MHz) in DMSO-d6: 8.16 (s, 1H), 8.11 (s, 1H), 8.08 (d, 1H), 7.87 (m, 4H), 7.78 (m, 2H), 7.59 (m, 2H), 7.40 (m, 2H), 7.23 (m, 2H), 6.35 (m, 2H), 6.20 (m, 2H), 5.95 (m, 2H), 4.32 (m, 4H), 4.21 (m, 4H), 3.96 (s, 3H), 2.16 (m, 4H)

[0067] Example 16: Preparation of hexyl 2,5-bis[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]benzoate, Compound 16 [ka] The title compound 16 is prepared according to the process for compound 13 described in Example 13, except that methyl 2,5-bis[2-[6-(6-hydroxyhexoxy)-2-naphthyl]ethynyl]benzoate (compound 9) is replaced with hexyl 2,5-bis[2-[6-(3-hydroxypropoxy)-2-naphthyl]ethynyl]benzoate (compound 12). Purification by silica gel flash chromatography using ethyl acetate provides the title compound (2.48 g, 3.25 mmol, 92%) as a yellow solid. Liquid crystal phase transition: Compound 16 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 123°C (T (Cr-N) ) to a nematic phase, and the isotropic phase at 163°C (T (N-I) ) appears. 1 H NMR (300MHz) in DMSO-d6: 8.17 (s, 1H), 8.10 (s, 1H), 8.06 (d, 1H), 7.87 (m, 4H), 7.79 (m, 2H), 7.58 (m, 2H), 7.40 (m, 2H), 7.24 (m, 2H), 6.36 (m, 2H), 6.20 (m, 2H), 5.95 (m, 2H), 4.32 (m, 6H), 4.22 (m, 4H), 2.16 (m, 4H), 1.73 (m, 2H), 1.39 (m, 2H), 1.19 (m, 4H), 0.75 (t, 3H)

[0068] Example 17: Preparation of alignment layer using photoalignment material A photoalignment composition (a photoalignment material of 3% solids in cyclopentanone as described in Patent Publication WO2012 / 085048: a photoactive polymer material is used as the alignment layer for the liquid crystal) is spin-coated onto a glass substrate. The film is dried at 180°C for 10 minutes, resulting in a film thickness of approximately 100 nm. The film is then exposed to 500 mJ / cm of parallel linearly polarized UV (LPUV) light (280-320 nm) as alignment light. 2 The plane of polarization is at 0° relative to the reference edge on the substrate.

[0069] Example 18: Preparation of optical films from compound 16 A 15.0 wt% solution was prepared by mixing 14.775 wt% Compound 16, 0.150 wt% Irgacure® 369 (having the chemical structure 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1), and 0.075 wt% Tinuvin® 123 (having the chemical structure bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate) in cyclopentanone and thoroughly stirring at room temperature until the solids were completely dissolved. The polymer solution was spin-coated onto a glass plate with the alignment layer of Example 17 to form a liquid crystal film. The film was dried on a temperature-controlled hot plate at 148°C for 1 minute. The sample was cooled to room temperature and then photopolymerized by irradiating it with UV light using a mercury lamp under a N2 atmosphere at room temperature for approximately 2 minutes to fix the alignment state of the liquid crystal.

[0070] The resulting film exhibited a very well-oriented nematic mesophase at room temperature.

[0071] Example 19: Preparation of optical films from compound 15 A 15.0 wt% solution was prepared by mixing 14.775 wt% Compound 15, 0.150 wt% Irgacure® 369 (having the chemical structure 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1), and 0.075 wt% Tinuvin® 123 (having the chemical structure bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate) in cyclopentanone and thoroughly stirring at room temperature until the solids were completely dissolved. The polymer solution was spin-coated onto a glass plate equipped with the alignment layer of Example 1 to form a liquid crystal film. The film was dried on a temperature-controlled hotplate at 100-120°C for 1-5 minutes. The sample was then cooled to room temperature and then photopolymerized by irradiating it with UV light using a mercury lamp under a N2 atmosphere at room temperature for approximately 2 minutes to fix the alignment state of the liquid crystal.

[0072] The resulting film exhibited a very poorly aligned nematic mesophase at room temperature.

[0073] Example 20: Preparation of optical films from compound 14 A 15.0 wt% solution was prepared by mixing 14.775 wt% Compound 14, 0.150 wt% Irgacure® 369 (having the chemical structure 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1), and 0.075 wt% Tinuvin® 123 (having the chemical structure bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate) in cyclopentanone and thoroughly stirring at room temperature until the solids were completely dissolved. The polymer solution was spin-coated onto a glass plate with the alignment layer of Example 1 to form a liquid crystal film. The film was dried on a temperature-controlled hot plate at 80°C for 1 minute and then at 100°C for 1 minute. The sample was cooled to room temperature and then photopolymerized by irradiating it with UV light using a mercury lamp under a N2 atmosphere at room temperature for approximately 2 minutes to fix the alignment state of the liquid crystal.

[0074] The resulting film exhibited a very well-oriented nematic mesophase at room temperature.

[0075] Example 21: Preparation of optical films from compound 13 A 15.0 wt% solution was prepared by mixing 14.775 wt% Compound 13, 0.150 wt% Irgacure® 369 (having the chemical structure 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1), and 0.075 wt% Tinuvin® 123 (having the chemical structure bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate) in cyclopentanone and thoroughly stirring at room temperature until the solids were completely dissolved. The polymer solution was spin-coated onto a glass plate with the alignment layer of Example 1 to form a liquid crystal film. The film was dried on a temperature-controlled hot plate at 80°C for 1 minute and then at 100°C for 1 minute. 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 for approximately 2 minutes to fix the alignment state of the liquid crystal.

[0076] The resulting film exhibited a very well-oriented nematic mesophase at room temperature.

[0077] Example 22: The retardation at 550 nm of the samples described in Example 18, Example 20, and Example 21 is measured by an ellipsometer. The thickness of the sample is measured by a stylus step gauge. From the retardation and thickness values ​​determined, the birefringence (Δn) is obtained according to the formula (Δn=retardation / thickness). The values ​​are listed in Table 1.

[0078] [Table 1]

[0079] The films of Examples 18, 20, and 21 have very high birefringence, exceeding 0.38. These new LCPs can be used to fabricate phase retarder optical films as quarter-wave plates (QWPs) and half-wave plates (HWPs). Retarder films transmit light and change its polarization state, and are widely used in various display applications or security devices. The particularly high birefringence of these new LCPs allows for significant thickness reduction of the retarder films.

[0080] As an example, Table 2 shows the thicknesses required to obtain a quarter-wave retarder (λ / 4) (QWP) and a half-wave retarder (λ / 2) (HWP) at 550 nm when compounds 16, 14, and 13 are used in Examples 18, 20, and 21, respectively.

[0081] [Table 2]

[0082] For Examples 18, 20 and 21, the required thickness of the quarter wave plate (λ / 4) retarder (QWP) is very thin, below 400 nm.

Claims

1. Formula (I) 【Chemistry 7】 [In the formula, SP １ and SP ２ are each independently of one another a group of the formula -(CH ２ )p-, where p is an integer of 1 to 18 and has 1, 2, 3, or 4 —CH ２ - group is unsubstituted or is replaced by a group selected from the group consisting of -CH=CH-, -O-, -S-, -NR'-, -CO-, -COO-, -OOC-, -CONR'-, -OCOO- and -OCONR', provided that first, the spacer group does not contain two adjacent heteroatoms, and second, X １ , X ２ , X ３ and X ４ is a single bond, then p may also have a value of 0; X １ and X ２ 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 alkyl groups; BP １ and BP ２ each independently represents a polymerizable group, R １ , R ２ , R ３ and R ４ are each independently hydrogen, -OR ５ , -COOR ５ , -OCOR ５ , -CONR ５ , -OCOOR ５ , -OCONR ５ and C １ -C １８ alkyl groups, wherein R ５ is C １ -C １８ selected from the group consisting of alkyl, aryl, aralkyl and alkylaryl. A compound represented by the formula:

2. BP １ and BP ２ are each independently 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, W is hydrogen, chloride, aryl or C １ -C ６ represents alkyl, R ３ But C １ -C ６ represents alkyl, provided that R ３ When is attached to an aryl group, R ３ is also hydrogen or C １ -C ６ 2. The compound of claim 1, which may represent alkoxy.

3. base SP １ and SP ２ The compound according to any one of claims 1 to 3, wherein the integers p are each independently a value from 1 to 12.

4. group R １ , R ２ , R ３ and R ４ are each independently hydrogen, -OR ５ , -COOR ５ , -OCOR ５ , -OCOOR ５ , and C １ -C ６ alkyl, wherein R ５ But C １ -C １２ alkyl, provided that at least one R １ , R ２ , R ３ or R ４ 10. A compound according to any one of the preceding claims, wherein is hydrogen.

5. At least two R １ , R ２ , R ３ or R ４ 10. A compound according to any one of the preceding claims, wherein is hydrogen.

6. An LCP mixture comprising a compound of formula (I).

7. An LCP network comprising a compound according to any one of claims 1 to 6 or a mixture according to claim 7 in crosslinked or polymerized form.

8. Use of a compound according to any one of claims 1 to 6 or a mixture according to claim 6 in the manufacture of an optical or electro-optical device.

9. An optical or electro-optical device comprising a compound according to any one of claims 1 to 6, a mixture according to claim 7 or a network according to claim 7.

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