Liquid crystal compound

Abstract

The present invention relates to polymerizable liquid crystal compounds of the following formula (I), LCP mixtures comprising these compounds and their use in optical and electro-optical devices: # imgabs0 #

Description

[0001] The present invention relates to substituted curable liquid crystals (LCPs) having high optical anisotropy and the use of such LCPs for preparing 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, such as for polarizers. Displays are becoming thinner and thinner. Therefore, the industry has an increasing demand for thinner optical LCP films that can provide the desired optical or electro-optical effects.

[0003] A retarder film is an optical element that changes the polarization state of light passing through the film. When light passes through a retarder, its polarization direction changes due to birefringence and the thickness of the retarder. One of the biggest problems in the preparation of retarders is to produce a high-performance film with a small filling amount. When using liquid crystals with high birefringence, the necessary retardation values ​​can be achieved with a small amount of liquid crystal compound.

[0004] LCP materials with high birefringence can be used for thin optical films.

[0005] Therefore, the task of the present invention is to find new LCP materials which have high birefringence and are suitable for optical films.

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

[0007]

[0008] in:

[0009] SP1 and SP2 each independently represent a group of the formula -(CH2)p-, wherein p is an integer from 1 to 18 and wherein one or more (especially -CH2-) groups are unsubstituted or substituted by a group selected from the group consisting of -CH=CH-, -O-, -S-, -NR'-, -CO-, -COO-, -OOC-, -CONR'-, -OCOO- and -OCONR', provided that: firstly, the spacer group does not contain two adjacent heteroatoms and secondly, when X1, X2, X3 and X4 are single bonds, p may also have the value of 0;

[0010] X1 and X2 are each independently selected from -O-, -S-, -NR'-, -CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR' and a single bond, wherein R' is selected from hydrogen, C1-C 18alkyl, BP1 and BP2 each independently represent a polymerizable group, R1, R2, R3 and R4 are independently selected from hydrogen, halogen, -OR5, -COOR5, -OCOR5, -CONR5, -OCOOR5, -OCONR5 and C1-C 18 Alkyl, wherein R5 is selected from C1-C 18 Alkyl, aryl, aralkyl and alkaryl.

[0011] The spacer groups SP1 and SP2 are independently of one another unsubstituted or substituted by one or more fluorine or chlorine atoms. Preference is given to groups in which no substituents are present. It is particularly preferred that the integer p has a value of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, and more particularly preferred that the integer p has a value of 1, 2, 3, 4, 5, 6, 7, 8. It is furthermore particularly preferred that SP1 and SP2 each independently represent a group of the formula -(CH2)p-, which is unsubstituted or in which one, two, three or four -CH2- groups are replaced by a group selected from -CH=CH-, -O-, -CO-, -COO-, -OOC-, -CONR'-, -OCOO- and -OCONR' and in particular by a group selected from -O-, -CO-, -COO-, -OOC- and -OCOO-.

[0012] The naphthyl groups in formula (I) are each independently unsubstituted or substituted by one or two substituents selected from fluorine or chlorine atoms, nitrile, C1-C6 alkyl, C1-C6 alkenyl, C1-C6 alkoxy and C1-C6 alkenyloxy. Preferably, each naphthyl group contains no more than one additional substituent. It is particularly preferred that the naphthyl group does not contain an additional substituent.

[0013] The radicals X1 and X2 are preferably selected independently of one another from -O-, -COO-, -OOC-, -OCOO- and a single bond;

[0014] It is particularly preferred that X1, X2, X3 and X4 are independently selected from -O- or a single bond.

[0015] Preferred radicals R1, R2, R3 and R4 are independently selected from hydrogen, -OR5, -COOR5, -OCOR5, -OCOOR5 and C1-C6-alkyl, where R5 is selected from C1-C6-alkyl.

[0016] More preferred radicals R1, R2, R3 and R4 are independently selected from hydrogen, -OR5, -COOR5, -OCOR5, -OCOOR5 and C1-C6 alkyl, in particular from hydrogen and -COOR5, wherein R5 is selected from C1-C 18Alkyl, provided that at least one of R1, R2, R3 or R4 is hydrogen, especially at least two of R1, R2, R3 or R4 are hydrogen, more especially at least three of R1, R2, R3 or R4 are hydrogen.

[0017] The groups BP1 and BP2 are preferably 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-, R6-Ph-CH=CH-COO-, R6-OOC-CH=CH-Ph-O- and 2-W-ethylene oxide, where W represents hydrogen, chlorine, aryl or C1-C6 alkyl and R6 represents C1-C6 alkyl, provided that when R6 is attached to an aryl group, it may also represent hydrogen or a C1-C6 alkoxy group.

[0018] In particular, the radicals BP1 and BP2 are preferably independently selected from CH2=CW-COO-, CH2=CH-O- and CH2=CH-OOC-, where W represents hydrogen, chlorine, aryl or C1-C6-alkyl, preferably hydrogen or C1-C6-alkyl.

[0019] The term "alkyl" should be understood to include C1-C 18 Alkyl, preferably C1-C 12 Alkyl and especially C1-C6 alkyl. The term "alkyl" includes achiral, branched or straight-chain, substituted or unsubstituted alkyl. Examples of alkyl that may be present in the compounds of the invention include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, isopentyl, n-pentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl, or 2-methylpropane, 2-methylbutane, 3-methylpentane, 2-methylhexane, 3-methylhexane.

[0020] The term "alkenyl" should be understood to include C1-C 18 Alkenyl, preferably C1-C 12 Alkenyl and especially C1-C6 alkenyl. The term "alkenyl" includes achiral, branched or linear, substituted or unsubstituted alkenyl, wherein the double bond is located at the 2 position or further away. Examples of alkenyl 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.

[0021] The term "alkoxy" should be understood to include C1-C 18 Alkoxy, preferably C1-C 12Alkoxy and especially C1-C6 alkoxy. Alkoxy includes achiral, branched or straight-chain, substituted or unsubstituted alkoxy. Examples of alkoxy that may be present in the compounds of the invention include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, isopentyl, n-pentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl, etc.

[0022] The term "alkenyloxy" should be understood to include C1-C 18 Alkenyloxy, preferably C1-C 12 Alkenyloxy and especially C1-C6 alkenyloxy. The term "alkenyloxy" includes achiral, branched or linear, substituted or unsubstituted alkenyloxy groups, wherein the double bond is located at the 2nd position or further away. 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, and the like.

[0023] Substituents of "alkyl", "alkenyl", "alkoxy" and "alkenyloxy" are, for example, halogen, such as fluorine, nitrile, C1-C 11 Alkoxy, trifluoromethyl, 4-(4-alkoxyphenyl)benzonitrile.

[0024] The term "aryl" is understood to include aromatic rings, preferably aromatic hydrocarbons, especially phenyl and naphthyl, more especially phenyl.

[0025] The term "aralkyl" refers to any monovalent group obtained by replacing one or more hydrogen atoms of an alkyl group with an aryl group. It should be understood that it includes phenethyl and the like.

[0026] The term "alkaryl" is understood to include methylphenyl, ethylphenyl, propylphenyl, and the like.

[0027] Halogen substituents useful in the present invention include fluorine, bromine, chlorine, iodine, especially fluorine.

[0028] Preferably, the present invention provides a compound of the following formula (I), preferably a liquid crystal compound:

[0029]

[0030] in:

[0031] SP1 and SP2 each independently represent a group of formula -(CH2)p-, wherein 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 -CH=CH-, -O-, -CO-, -COO-, -OOC- and -OCOO-, provided that: firstly, the spacer group does not contain two adjacent heteroatoms, and secondly, when X1 and X2 are single bonds, p may also have a value of 0;

[0032] X1 and X2 are each independently selected from -O-, -CO-, -COO-, -OOC-, -OCOO- and a single bond;

[0033] BP1 and BP2 are 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-,

[0034] CH2=CH-Ph-, CH2=CH-Ph-O-, R 3 -Ph-CH=CH-COO-, R 6 -OOC-CH=CH-Ph-O- and 2-W-oxirane, wherein W represents hydrogen, chlorine, aryl or C1-C6 alkyl, and R6 represents C1-C6 alkyl, provided that when R6 is attached to aryl, it may also represent hydrogen or C1-C6 alkoxy;

[0035] R1, R2, R3 and R4 are independently selected from hydrogen, -OR5, -COOR5, -OCOR5, -OCOOR5, and C1-C6 alkyl, wherein R5 is C1-C 12 Alkyl, preferably C1-C 12 The alkyl group is more preferably methyl, ethyl, propyl, isopropyl, butyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl.

[0036] The starting materials are either commercially available or can be readily prepared by, and are familiar to, those skilled in the art.

[0037] LCP materials in the present application refer to liquid crystal materials, which include liquid crystal monomers and / or liquid crystal oligomers and / or liquid crystal polymers and / or cross-linked liquid crystals. If the liquid crystal material includes liquid crystal monomers, these monomers can be polymerized, usually after anisotropy has been generated in the LCP material, for example due to contact with an orientation layer. Polymerization can be initiated by heat treatment or exposure to actinic light (preferably including UV light). LCP materials can contain only a single type of liquid crystal compound, but can also contain additional polymerizable and / or non-polymerizable compounds, not all of which must be liquid crystal compounds. In addition, the LCP material may contain additives, including but not limited to: antioxidants, initiators (e.g., photoinitiators), promoters, 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 converted into polymer binders by polymerization, or In the case of emulsion coatings and printing inks, these include dispersing aids (for example, as disclosed in U.S. Pat. No. 5,798,147), hydrophobing agents, binders, flow improvers, defoamers, deaerators, diluents, auxiliaries, colorants, dyes and pigments, curing inhibitors (for example, hydroquinone, p-tert-butylcatechol, 2,6-di-tert-butyl-p-methylphenol, phenothiazine, N-phenyl-2-naphthylamine or photo-alignment monomers or oligomers or polymers as described in EP1090325B), chiral additives, isotropic or anisotropic fluorescent and / or non-fluorescent dyes (particularly dichroic dyes).

[0038] 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 the compounds of formula (I) with one or more additional components. Organic solvents can also be used in the preparation of these mixtures.

[0039] Thus, a second aspect of the present invention provides an LCP mixture comprising a compound of formula (I) and one or more further components.

[0040] The LCP mixture may also contain a suitable organic solvent.

[0041] 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).

[0042] 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).

[0043] Dichroic dye refers to a dye whose molecules have different absorbances in the major axis direction and the minor axis direction. 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. Relative to 100 parts by mass of the liquid crystal mixture, the amount of the dichroic dye is 0.01-40 parts by mass, preferably 0.05-15 parts by mass.

[0044] 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 third aspect of the present invention onto a substrate.

[0045] Thus, 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 cross-linking the layer.

[0046] The LCP mixture of the third aspect of the invention may also be used in a similar manner to produce an LCP network.

[0047] In a fourth aspect of the invention, the present invention also comprises a crosslinked LCP network comprising a compound of formula (I) in crosslinked form.

[0048] Crosslinked LCP networks comprising the mixture of the third aspect of the invention in crosslinked form may also be comprised in this aspect of the invention.

[0049] The fifth aspect of the present invention provides use of a compound of formula (I) in the preparation of an optical or electro-optical device.

[0050] This aspect of the invention also includes the use of the liquid crystal mixture of the third aspect of the invention in the preparation of an optical or electro-optical device.

[0051] A sixth aspect of the present invention provides an optical or electro-optical device comprising the compound of formula (I) in a cross-linked state.

[0052] This aspect of the invention also includes an optical or electro-optical device comprising the LCP liquid crystal mixture of the third aspect of the invention in a cross-linked state.

[0053] 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 can be an object with a complex surface. In principle, it can be composed of any material. Preferably, the support comprises plastic, glass or metal, or is a silicon wafer. If the support is flexible, the support is preferably 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 such as microlenses or microprisms, or structures that exhibit sudden changes in shape, such as rectangular structures. Preferably, the support is transparent.

[0054] During the deposition of the LCP mixture, the support may be moved. 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 plastic or metal). The resulting film may then be wound on a reel together with the support foil, or the film may be released from the support and then wound as a self-supporting film without the need for a support.

[0055] The support may have additional layers, such as an organic layer, a dielectric layer or a metal layer. These layers may have different functions, for example, an organic layer may be applied as a primer layer, which increases the compatibility of the material to be applied with the support. The metal layer may be used as an electrode, for example when used in an electro-optical device such as a display, or may have the function of a reflector. The support may also be an optical element or device with certain functions, such as a substrate for an LCD, which may, for example, include a thin film transistor, an electrode or a color filter. In another example, the support is a device including an OLED layer structure. The support may also be a delay film, a polarizer (such as a polarizing film or a sheet polarizer), a reflective polarizer (such as the commercially available Vikuity TM DBEF film).

[0056] The LCP mixture can be applied to the support by any suitable method, such as extrusion, casting, molding, 2D or 3D printing or coating. Suitable coating methods are, for example, spin coating, scraper coating, knife coating, contact roller coating, die coating, dip coating, brush coating, rod coating, roller coating, flow coating, line coating, spray coating, dip coating, curtain coating, air knife coating, reverse roller coating, gravure coating, metering rod (Meyer rod) coating, slot die (extrusion) coating, roller coating, flexographic coating. Suitable printing methods include screen printing, relief printing (such as flexographic printing), inkjet printing, gravure printing (such as direct gravure printing or offset gravure printing), lithography (such as offset printing) or stencil printing (such as screen printing).

[0057] The layer of LCP mixture does not necessarily have to cover the entire surface of the support. Instead, the layer can also be applied in the form of a pattern, for example by printing, or can be processed after deposition to have the form of a pattern, for example by photolithographic methods.

[0058] The orientation of LCP can be achieved by any known liquid crystal orientation method. For example, the support can have an orientation surface, which means that the surface has the ability to orient the liquid crystal. The support can provide orientation without further treatment. For example, if a plastic substrate is used as a support, it can provide orientation on the surface due to the manufacturing method (such as extrusion or stretching of the substrate). Orientation ability can also be generated by brushing the support or embossing an oriented microstructure. Alternatively, a thin layer of material can be coated on the support, wherein the material is specially designed for orientation performance. The layer can be further brushed or otherwise treated to have an oriented microstructure on the surface, such as by embossing. If the thin layer contains a photo-orientable substance, orientation can be generated by exposure to oriented light.

[0059] The orientation surface of the substrate may present a pattern of orientation directions to define the orientation pattern of the liquid crystals in the LCP layer. Preferably, an orientation layer comprising a photo-orientable substance is used for this purpose and the orientation pattern is generated by selective exposure to orientation light of different polarization planes.

[0060] The present invention will be described below with reference to the following non-limiting examples. These examples are for illustrative purposes only. For those skilled in the art, various variations of these examples will fall within the scope of the present invention. Example

[0061] The definitions used in the examples are as follows.

[0062] 1 HNMR: 1 H NMR spectroscopy

[0063] DMSO-d6: deuterated dimethyl sulfoxide

[0064] 300MHz: 300 MHz

[0065] M: multiplet; d: doublet; dd: doublet of doublets; t: triplet; s: singlet

[0066] DMF: dimethylformamide

[0067] HCl: hydrochloric acid

[0068] Pd(PPh3)2Cl2: Bis(triphenylphosphine)palladium dichloride

[0069] DMAP: 4-dimethylaminopyridine

[0070] NMP: N-methyl-2-pyrrolidone

[0071] CuI: Copper iodide

[0072] MgSO4: magnesium sulfate

[0073] In the following examples, the thermotropic phases are abbreviated as follows:

[0074] ·T (Cr-N) : Transition temperature from crystalline phase to nematic phase

[0075] ·T (N-I) : Transition temperature from nematic phase to isotropic phase

[0076] Example 1: Preparation of 3-[(6-bromo-2-naphthyl)oxy]-propan-1-ol, compound 1

[0077] 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 out and washed twice with 200 ml of water. The residue was further purified by silica gel flash column chromatography using a 1:1 hexane / ethyl acetate mixture to obtain 22.47 g. After recrystallization from heptane / ethyl acetate (10:1), 18.6 g of compound 1 was obtained as an off-white solid.

[0078] Example 2: Preparation of 6-[(6-bromo-2-naphthyl)oxy]-hexan-1-ol, Compound 2

[0079] The title compound 2 was prepared as described for compound 1 in Example 1, except that 3-chloropropanol was replaced with 6-chlorohexanol.

[0080] Example 3: Preparation of 3-[(6-(2-trimethylsilylethynyl)-2-naphthyl)oxy]-propan-1-ol, Compound 3

[0081] 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 were placed in 83.4 ml of triethylamine. The mixture was stirred at 25 ° C for 15 minutes and (trimethylsilyl)acetylene (11.77 g, 119.8 mmol) was added. After the suspension was stirred at 80 ° C for 2 hours, HCl solution was added dropwise. The mixture was stirred for 30 minutes, then filtered through diatomaceous earth and washed three times with 100 ml of ethyl acetate. The solution was extracted with ethyl acetate. The combined organic layer was washed with 5 ml of water and dried with MgSO4. After concentrating the solvent under vacuum, the residue was purified by silica gel flash chromatography using a 1:1 hexane / ethyl acetate mixture to obtain 13.41 g of compound 3.

[0082] Example 4: Preparation of 6-[(6-(2-trimethylsilylethynyl)-2-naphthyl)oxy]-hexan-1-ol, Compound 4

[0083] The title compound 4 was prepared according to the method described for compound 3 in Example 3, except that 3-[(6-bromo-2-naphthyl)oxy]-propan-1-ol compound 1 was replaced by 6-[(6-bromo-2-naphthyl)oxy]-hexan-1-ol compound 2.

[0084] Example 5: Preparation of 3-[(6-ethynyl-2-naphthyl)oxy]-propan-1-ol, compound 5

[0085] 12.4 g (89.79 mmol) potassium carbonate was added in batches to a solution of compound 3 in 135 ml of methanol. After stirring at room temperature for 1 hour, the reaction mixture was filtered through diatomaceous earth (Hyflo) / silicon dioxide and then washed 3 times with 25 ml of methanol. The solution was then poured into an aqueous solution of HCl and extracted with ethyl acetate. The combined organic layers were dried over MgSO4. After vacuum concentration, 10.84 g of compound 5 was obtained as a light yellow solid.

[0086] Example 6: Preparation of 6-[(6-ethynyl-2-naphthyl)oxy]-hexan-1-ol, Compound 6

[0087] Title compound 6 was prepared as described for compound 5 in Example 5, except that 3-[(6-(2-trimethylsilylethynyl)-2-naphthyl)oxy]-propan-1-ol was replaced with 6-[4-(2-trimethylsilylethynyl)phenoxy]-hexan-1-ol.

[0088] Example 7: Preparation of methyl 2,5-diiodobenzoate, compound 7

[0089] 2.5-Diiodobenzoic acid (15.0 g, 40.11 mmol) was dissolved in methanol (40 ml). After adding concentrated H2SO4 (4 ml), the clear colorless solution was heated to reflux for 6 hours. The reaction mixture was cooled to ambient temperature and poured on 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).

[0090] Example 8: Preparation of 2,5-diiodobenzoic acid hexyl ester, compound 8

[0091] The title compound 8 was prepared according to the procedure described for compound 7 in Example 7, except that methanol was replaced by n-hexanol.

[0092] Example 9: Preparation of methyl 2,5-bis[2-[6-(6-hydroxyhexyloxy)-2-naphthyl]ethynyl]benzoate, compound 9

[0093] Under 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) were suspended in triethylamine (60 ml). The mixture was stirred at 60°C for 6 hours. After cooling to ambient temperature, the mixture was poured into ice water (50 ml) and acidified to pH 1 with HCl. The precipitate was filtered off and the residue was recrystallized from acetonitrile (130 ml) to give the title compound (4.91 g, 7.34 mmol) as a beige solid.

[0094] Example 10: Preparation of 2,5-bis[2-[6-(6-hydroxyhexyloxy)-2-naphthyl]ethynyl]benzoic acid hexyl ester, compound 10

[0095] The title compound 10 was prepared according to the method described for compound 9 in Example 9, except that methyl 2,5-diiodobenzoate (compound 7) was replaced with hexyl 2,5-diiodobenzoate (compound 8).

[0096] Example 11: Preparation of methyl 2,5-bis[2-[6-(3-hydroxypropoxy)-2-naphthyl]ethynyl]benzoate, Compound 11

[0097] The title compound 11 was prepared according to the method described for compound 9 in Example 9, except that 6-[(6-ethynyl-2-naphthyl)oxy]-hexan-1-ol (compound 6) was replaced by 3-[(6-ethynyl-2-naphthyl)oxy]-propan-1-ol (compound 5).

[0098] Example 12: Preparation of 2,5-bis[2-[6-(3-hydroxypropoxy)-2-naphthyl]ethynyl]benzoic acid hexyl ester, compound 12

[0099] Title compound 12 was prepared according to the method described for compound 19 in Example 19, except that 6-[(6-ethynyl-2-naphthyl)oxy]-hexan-1-ol (compound 6) was replaced with 3-[(6-ethynyl-2-naphthyl)oxy]-propan-1-ol (compound 5) and methyl 2,5-diiodobenzoate was replaced with hexyl 2,5-diiodobenzoate (compound 8).

[0100] Example 13: Preparation of methyl 2,5-bis[2-[6-(6-prop-2-enoyloxyhexyloxy)-2-naphthyl]ethynyl]benzoate, Compound 13

[0101]

[0102] Methyl 2,5-bis[2-[6-(6-hydroxyhexyloxy)-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, 2-acryloyl chloride (3.98 g, 44.0 mmol) was added dropwise, and then DMAP (0.179 g, 1.47 mmol) was added. The reaction mixture was stirred at 0-5°C for 2 hours. After the reaction mixture was poured into ice water, it was extracted with ethyl acetate. Evaporation and recrystallization in acetonitrile gave the title compound (1.71 g, 2.2 mmol) as a beige solid.

[0103] Liquid crystal phase transition: Compound 13 was observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, when the temperature was increased, the crystalline phase changed at 85°C (T (Cr-N) ) transforms into a nematic phase, while the isotropic phase appears at 190℃ (T (N-I) ).

[0104] 1HNMR (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).

[0105] Example 14: Preparation of 2,5-bis[2-[6-(6-prop-2-enoyloxyhexyloxy)-2-naphthyl]ethynyl]benzoic acid hexyl ester, compound 14

[0106]

[0107] The title compound 14 was prepared as described for compound 13 in Example 13, but with the proviso that methyl 2,5-bis[2-[6-(6-hydroxyhexyloxy)-2-naphthyl]ethynyl]benzoate (compound 9) was replaced with hexyl 2,5-bis[2-[6-(6-hydroxyhexyloxy)-2-naphthyl]ethynyl]benzoate (compound 10). Purification by flash chromatography on silica gel using ethyl acetate / heptane (mixture 1:1) gave the title compound (1.16 g, 1.37 mmol, 22%) as a beige solid.

[0108] Liquid crystal phase transition: Compound 14 was observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, when the temperature was increased, the crystalline phase changed at 60°C (T (Cr-N) ) and the isotropic phase appears at 115℃ (T (N-I) ).

[0109] 1 HNMR (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).

[0110] Example 15: Preparation of methyl 2,5-bis[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]benzoate, Compound 15

[0111]

[0112] The title compound 15 was prepared according to the method described for compound 13 in Example 13, but with the proviso that methyl 2,5-bis[2-[6-(6-hydroxyhexyloxy)-2-naphthyl]ethynyl]benzoate (compound 9) was replaced with methyl 2,5-bis[2-[6-(3-hydroxypropoxy)-2-naphthyl]ethynyl]benzoate (compound 11). Purification by flash chromatography on silica gel using ethyl acetate gave the title compound (2.75 g, 3.97 mmol, 94%) as a slightly yellow solid.

[0113] Liquid crystal phase transition: Compound 15 was observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, when the temperature was increased, the crystalline phase changed at 79°C (T (Cr-N) ) and the isotropic phase appears above 200°C (T (N-I) ).

[0114] 1 HNMR (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).

[0115] Example 16: Preparation of 2,5-bis[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]benzoic acid hexyl ester, compound 16

[0116]

[0117] The title compound 16 was prepared as described for compound 13 in Example 13, but with the proviso that methyl 2,5-bis[2-[6-(6-hydroxyhexyloxy)-2-naphthyl]ethynyl]benzoate (compound 9) was replaced with hexyl 2,5-bis[2-[6-(3-hydroxypropoxy)-2-naphthyl]ethynyl]benzoate (compound 12). Purification by flash chromatography on silica gel using ethyl acetate gave the title compound (2.48 g, 3.25 mmol, 92%) as a yellow solid.

[0118] Liquid crystal phase transition: Compound 16 was observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, when the temperature was increased, the crystalline phase changed at 123°C (T (Cr-N) ) and the isotropic phase appears at 163℃(T (N-I) ).

[0119] 1 HNMR (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).

[0120] Example 17: Preparation of an alignment layer using a photo-alignment material

[0121] A photo-alignment composition (a photo-alignment material with a solid content of 3% in cyclopentanone as described in patent publication WO2012 / 085048, a photoactive polymer material used as an alignment layer for liquid crystal) was spin-coated on a glass substrate. The film was dried at 180°C for 10 minutes, and the resulting film thickness was about 100 nm. The film was then exposed to alignment light, which was collimated and linearly polarized ultraviolet (LPV) light (280-320 nm) with an intensity of 500 mJ / cm 2 The polarization plane is at 0° relative to a reference edge on the substrate.

[0122] Example 18: Preparation of optical film from compound 16

[0123] A 15.0 wt% solution was prepared as follows: 14.775 wt% of compound 16, 0.150 wt% of 369 (chemical structure is 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1), 0.075wt% 123 (chemical structure is bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate) was mixed in cyclopentanone and stirred thoroughly at room temperature until the solid was completely dissolved. The above polymer solution was spin-coated on a glass plate with an orientation 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 with UV light using a mercury lamp for about 2 minutes at room temperature under a N2 atmosphere to fix the orientation state of the liquid crystal.

[0124] The resulting films exhibited a very well oriented nematic mesophase at room temperature.

[0125] Example 19: Preparation of optical film from compound 15

[0126] A 15.0 wt% solution was prepared as follows: 14.775 wt% of compound 15, 0.150 wt% of 369 (chemical structure is 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1), 0.075wt% 123 (chemical structure is bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate) was mixed in cyclopentanone and stirred thoroughly at room temperature until the solid was completely dissolved. The above polymer solution was spin-coated on a glass plate with the orientation layer of Example 1 to form a liquid crystal film. The film was dried on a temperature-controlled hot plate at 100-120° C. for 1-5 minutes. The sample was cooled to room temperature and then photopolymerized by irradiating with UV light for about 2 minutes using a mercury lamp at room temperature under N2 atmosphere to fix the orientation state of the liquid crystal.

[0127] The resulting films exhibited a very poorly oriented nematic mesophase at room temperature.

[0128] Example 20: Preparation of optical film from compound 14

[0129] A 15.0 wt% solution was prepared as follows: 14.775 wt% of compound 14, 0.150 wt% of 369 (chemical structure is 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1), 0.075wt% 123 (chemical structure is bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate) was mixed in cyclopentanone and stirred thoroughly at room temperature until the solid was completely dissolved. The above polymer solution was spin-coated on a glass plate with the orientation 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 with UV light for about 2 minutes using a mercury lamp at room temperature in a N2 atmosphere to fix the orientation state of the liquid crystal.

[0130] The resulting films exhibited a very well oriented nematic mesophase at room temperature.

[0131] Example 21: Preparation of optical film from compound 13

[0132] A 15.0 wt% solution was prepared as follows: 14.775 wt% of compound 13, 0.150 wt% of 369 (chemical structure is 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1), 0.075wt% 123 (chemical structure is bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate) was mixed in cyclopentanone and stirred thoroughly until the solid was completely dissolved at room temperature. The above polymer solution was spin-coated on a glass plate with the orientation 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 with UV light using a mercury lamp at room temperature for about 2 minutes in a N2 atmosphere to fix the orientation state of the liquid crystal.

[0133] The resulting films exhibited a very well oriented nematic mesophase at room temperature.

[0134] Embodiment 22

[0135] The samples described in Example 18, Example 20, and Example 21 were measured for retardation at 550 nm using an ellipsometer. The thickness of the samples was measured by a contact profilometer. 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.

[0136] Table 1

[0137] Example Thickness [nm] Retardation at 550nm [nm] △n at 550nm 18 (Compound 16) 540±30 234.7 0.44±0.01 20 (Compound 14) 660±30 284.3 0.43±0.01 21 (Compound 13) 750±30 294.9 0.39±0.02

[0138] The films of Examples 18, 20, and 21 have very high birefringence of more than 0.38. These new LCPs can be used to prepare phase-delay optical films, such as quarter-wave plates (QWPs) and half-wave plates (HWPs). Retarder films can transmit light and change its polarization state and are widely used in various display applications or security elements. The particularly high birefringence of these new LCPs can significantly reduce the thickness of the retarder film.

[0139] As an example, Table 2 shows the thicknesses required for compound 16, compound 14, and compound 13 used in Examples 18, 20, and 21, respectively, to obtain a quarter-wave plate (λ / 4) retarder (QWP) and a half-wave plate (λ / 2) retarder (HWP) at 550 nm.

[0140] Table 2

[0141]

[0142] For Examples 18, 20 and 21, the required thickness of the quarter wave plate (λ / 4) retarder (QWP) is very low and below 400 nm.

Claims

1. A compound of the following formula (I): in: SP1 and SP2 each independently represent a group of formula -(CH2)p-, wherein p is an integer from 1 to 18, wherein one, two, three or four -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', provided that: firstly, the spacer group does not contain two adjacent heteroatoms, and secondly, when X1, X2, X3 and X4 are single bonds, p may also be 0; X1 and X2 are each independently selected from -O-, -S-, -NR'-, -CO-, -COO-, -OOC-, -CONR'-, -OCOO-, -OCONR' and a single bond, wherein R' is selected from hydrogen, C1-C 18 alkyl; BP1 and BP2 each independently represent a polymerizable group; R1, R2, R3 and R4 are independently selected from hydrogen, -OR5, -COOR5, -OCOR5, -CONR5, -OCOOR5, -OCONR5 and C1-C 18 Alkyl, wherein R5 is selected from C1-C 18 Alkyl, aryl, aralkyl and alkaryl.

2. The compound according to claim 1, wherein BP1 and BP2 are 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-oxirane, wherein W represents hydrogen, chlorine, aryl or C1-C6 alkyl, and R 3 represents a C1-C6 alkyl group, provided that: when R 3 When attached to an aryl group, it may also represent hydrogen or a C1-C6 alkoxy group.

3. The compound according to any one of claims 1 to 3, wherein the integer p of the groups SP1 and SP2 each independently has a value of 1 to 12.

4. A compound according to any one of the preceding claims, wherein the radicals R1, R2, R3 and R4 are independently selected from hydrogen, -OR5, -COOR5, -OCOR5, -OCOOR5 and C1-C6 alkyl, wherein R5 is selected from C1-C 12 Alkyl, provided that at least one of R1, R2, R3 or R4 is hydrogen.

5. A compound according to any one of the preceding claims, wherein at least two of R1, R2, R3 or R4 are hydrogen.

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

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

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

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

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