Polymerizable liquid crystal compound, polymerizable composition, and phase difference film

Abstract

This application relates to the field of optical material preparation technology, and provides a polymerizable liquid crystal compound, a polymerizable composition, and a retardation film. By introducing sterically hindered substituent groups at appropriate positions along the short axis of the polymerizable liquid crystal compound's molecular structure, the compound exhibits excellent reverse wavelength dispersion after film formation. Furthermore, by introducing sterically hindered substituent groups at appropriate positions in the polymerizable liquid crystal compound's molecular structure, structural regularity is disrupted, resulting in excellent solubility of the compound. The retardation film fabricated using the above polymerizable liquid crystal compound is less prone to crystallization and alignment defects.

Description

Technical Field

[0001] This application relates to the field of optical material preparation technology, and in particular to a polymerizable liquid crystal compound, a polymerizable composition, and a phase retardation film. Background Technology

[0002] Optical films are a key component of modern display technology, affecting display brightness, sharpness, and viewing angle distortion. Among them, inverse wavelength dispersion (IRD) films, due to their unique optical properties, are widely used in polarizers of liquid crystal displays (LCDs) and organic light-emitting diode displays (OLEDs) for anti-reflection and viewing angle compensation. IRD generally refers to the relationship between the phase difference and wavelength at a positive viewing angle. It is typically expressed as the phase difference Re(450) at 450 nm and the phase difference Re(550) at 550 nm satisfying the following condition: Re(450) / Re(550) < 1.0.

[0003] Phase retardation films achieving reverse wavelength dispersion currently primarily utilize liquid crystal polymer materials, leveraging the material's birefringence to create a phase difference. Mainstream, these liquid crystal polymers typically use a pre-coating solution containing one or more polymerizable liquid crystal compounds, initiators, and solvents. To achieve a specific alignment of the liquid crystals, a functional alignment layer is required on the substrate. After coating the pre-coating solution onto the substrate containing the alignment layer, a heating and drying process is performed. Once the solvent evaporates, the liquid crystal compounds form a liquid crystal phase with a specific orientation (i.e., "alignment") under certain temperature conditions. Subsequently, a polymerization reaction is initiated by ultraviolet light to fix the liquid crystal alignment, resulting in a well-aligned, anisotropic polymer film with phase retardation optical properties—the phase retardation film.

[0004] Therefore, extensive research has been conducted on polymeric liquid crystal compounds or polymeric compositions containing them capable of forming phase reversal films with reverse wavelength dispersion. However, the disclosed compound structures (such as patent CN119592332B) have small volumes and short lengths of chromophores on their short axes, resulting in high Re(450) / Re(550) values, indicating insufficient reverse wavelength dispersion. Furthermore, these compounds have regular molecular structures, poor solubility, and are prone to crystallization and alignment defects during film formation. Summary of the Invention

[0005] The purpose of the embodiments in this specification is to provide a polymeric liquid crystal compound, a polymeric composition, and a phase reversal film to solve the problems of insufficient reverse wavelength dispersion, poor solubility, film crystallization, and numerous alignment defects in polymeric liquid crystal compounds in the prior art.

[0006] To achieve the above objectives, the embodiments in this specification adopt the following technical solutions: According to a first aspect of this application, a polymerizable liquid crystal compound is provided, the structure of which is represented by the following formula (1): L 1 -SP 1 -A 1 -B 1 -C 1 -D 1 -M 1 -Ar 1 -M 2 -GM 3 -Ar 2 -M 4 -D 2 -C 2 -B 2 -A 2 -SP 2 -L 2 Equation (1); In formula (1), G is selected from the groups represented by the following formulas (G-1) to (G-9): , where * represents the bonding position, and x in equation (G-9) represents an integer from 2 to 10; M 1 M 2 M 3 M 4 C 1 and C 2 Each of the following can be independently represented as -OCH2-, -CH2O-, -CO-, -COO-, -OCO-, -O-, -S-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH=CH-COO-, -CH=CH- OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO-C H2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=NN=CH-, -CF=CF-, or -C≡C-; Ar 1 and Ar 2 Each is independently selected from the aromatic rings represented by the following formula (Ar-1) or formula (Ar-2): ,or In the formulas (Ar-1) to (Ar-2), Q represents a straight-chain or branched alkyl group having 1 to 20 hydrogen atoms or carbon atoms; V 1 V 2 and V 3 Each of these groups independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 10 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a sulfonyl pentafluoride group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a methoxy group, an ethoxy group, a methoxycarbonyl group, an ethoxycarbonyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, or a thioisocyano group, wherein V 1 V 2 and V 3 At least one of them is not a hydrogen atom; W 1 Selected from , , , , , , ,or Among them, W 1 The hydrogen atom at any position on the aromatic ring may be replaced by one or more substituents U, wherein U is selected from straight-chain or branched alkyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, sulfonyl pentafluoride, nitro, cyano, isocyano, amino, hydroxyl, methoxy, ethoxy, mercapto, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, or thioisocyanate, having 1 to 20 carbon atoms; W 2 J is represented by the following formula (W-1): 1 -T 1 -* (W-1), Wherein, in the above formula (W-1): T 1 Represents a straight-chain alkylene group having 1 to 20 carbon atoms, wherein any one -CH2- or multiple non-adjacent -CH2- atoms can be independently replaced by -O-; J 1 Represents a hydrogen atom or a polymerizable group, wherein the polymerizable group is selected from the groups represented by the following formula (J-1) or formula (J-2): ,or ; D 1 and D 2 Each group is independently selected from the groups represented by formulas (D-1) to (D-5) below: ; B 1 and B 2Each can independently represent an aromatic ring with 6 or more carbon atoms that may have substituents; A 1 and A 2 Each of these can independently represent a single bond or -OCH2-, -CH2O-, -CO-, -COO-, -OCO-, -O-, -S-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH=CH-COO-, -CH=C H-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO- CH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=NN=CH-, -CF=CF-, or -C≡C-; SP 1 and SP 2 Each can independently represent a straight-chain or branched alkylene group having 1 to 20 carbon atoms, wherein any one -CH2- or multiple non-adjacent -CH2- can be independently replaced by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-; L 1 and L 2 Each of these independently represents a hydrogen atom or a polymeric group, wherein the polymeric group is selected from the groups represented by formula (J-1) or formula (J-2) above.

[0007] Optionally, V 1 V 2 and V 3 At least one of them is selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, or cyano; and / or, W 1 Selected from Among them, W 1The hydrogen atom at any position on the aromatic ring may be replaced by one or more substituents U, wherein U is selected from straight-chain or branched alkyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, sulfonyl pentafluoride, nitro, cyano, isocyano, amino, hydroxyl, methoxy, ethoxy, mercapto, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, or thioisocyano, having 1 to 20 carbon atoms.

[0008] Optionally, T 1 Selected from -CH2CH2OCH2CH2OCH2CH2- or -CH2CH2OCH2CH2-; and / or, J 1 Selected from groups represented by formula (J-1) or formula (J-2).

[0009] Optionally, B 1 and B 2 It can be represented by the following formula (B-1): ; and / or, L 1 and L 2 Each group is independently selected from the groups represented by formula (J-1) or formula (J-2).

[0010] Optionally, the polymerizable liquid crystal compound is selected from the following structures:

[0011]

[0012]

[0013]

[0014]

[0015]

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023] .

[0024] According to a second aspect of this application, a polymerizable composition is provided, the polymerizable composition comprising the polymerizable liquid crystal compound described in the first aspect of this application.

[0025] Optionally, the polymerizable composition further comprises a polymerizable compound selected from the following structures: .

[0026] Optionally, the polymeric composition comprises 50 to 100 parts by weight of the polymeric liquid crystal compound and 0.1 to 50 parts by weight of the polymeric compound.

[0027] According to a third aspect of this application, a phase retardation film is provided, the phase retardation film comprising the polymeric composition described in the second aspect of this application.

[0028] Optionally, the phase difference Re(450) at a wavelength of 450 nm and the phase difference Re(550) at a wavelength of 550 nm satisfy the condition: Re(450) / Re(550) < 1.0.

[0029] The above-mentioned technical solutions adopted in this application can achieve the following beneficial effects: This application provides a polymerizable liquid crystal compound, a polymerizable composition, and a phase retardation film, by introducing V at a suitable position on the short axis of the polymerizable liquid crystal compound molecular structure. 1 V 2 V 3 The presence of sterically hindered substituents in the U-structure of this polymeric liquid crystal compound, after film formation, exhibits excellent reverse wavelength dispersion. Furthermore, by introducing V-structured substituents at appropriate positions within the molecular structure of the polymeric liquid crystal compound... 1 V 2 V 3The steric hindrance substituents in the U-structure disrupt the regularity of the molecular structure, resulting in excellent solubility of the polymeric liquid crystal compound. Phase reversal films fabricated using the polymeric liquid crystal compound provided in this application are less prone to crystallization and alignment defects. Detailed Implementation

[0030] To make the objectives, technical solutions, and advantages of this application clearer, the technical solutions of this application will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of them. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0031] In one embodiment of this application, a polymerizable liquid crystal compound is provided, which has the structure shown in formula (1): L 1 -SP 1 -A 1 -B 1 -C 1 -D 1 -M 1 -Ar 1 -M 2 -GM 3 -Ar 2 -M 4 -D 2 -C 2 -B 2 -A 2 -SP 2 -L 2 Equation (1).

[0032] In formula (1), G is selected from the groups represented by the following formulas (G-1) to (G-9): In equation (G-9), * represents the bonding position, and x represents an integer from 2 to 10. From the perspective of ease of obtaining raw materials and ease of synthesis, G is preferred. , , or , where * represents the bonding position.

[0033] M 1 M 2 M 3 M 4 C 1 and C 2Each of the following can be independently represented as -OCH2-, -CH2O-, -CO-, -COO-, -OCO-, -O-, -S-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH=CH-COO-, -CH=CH- OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO-CH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=NN=CH-, -CF=CF-, or -C≡C-. From the viewpoint of liquid crystal properties and ease of synthesis, M is preferred. 1 M 2 M 3 M 4 C 1 and C 2 Each can be independently represented as -OCH2-, -CH2O-, -COO-, -OCO-, or -O-CO-O-.

[0034] Ar 1 and Ar 2 Each is independently selected from the aromatic rings represented by the following formula (Ar-1) or formula (Ar-2): ,or In the formulas (Ar-1) to (Ar-2), Q represents a straight-chain or branched alkyl group having 1 to 20 hydrogen atoms or carbon atoms; V 1 V 2 and V 3 Each of these groups independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 10 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluoride sulfo group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a methoxy group, an ethoxy group, a methoxycarbonyl group, an ethoxycarbonyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, or a thioisocyanate group. From the viewpoint of improving reverse wavelength dispersibility and compound solubility, V is preferably... 1 V 2 and V 3 At least one of them is not a hydrogen atom. More preferably, V 1 V 2 and V 3At least one of the following is selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, or cyano. V is further preferred. 1 V 2 and V 3 At least one of them is selected from methyl, tert-butyl, methoxy, or methoxycarbonyl.

[0035] W 1 Selected from , , , , , , ,or Among them, W 1 Hydrogen atoms at any position on the aromatic ring can be replaced by one or more substituents U, where U is selected from straight-chain or branched alkyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, sulfonyl pentafluoride, nitro, cyano, isocyano, amino, hydroxyl, methoxy, ethoxy, mercapto, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, or thioisocyano. From the viewpoint of improving reverse wavelength dispersibility and compound solubility, W is preferred. 1 express .

[0036] W 2 J is represented by the following formula (W-1): 1 -T 1 -* (W-1), In the above equation (W-1), T 1 This refers to a straight-chain alkylene group having 1 to 20 carbon atoms, wherein any one -CH2- or multiple non-adjacent -CH2- atoms can be independently replaced with -O-. From the viewpoint of improving reverse wavelength dispersibility and compound solubility, T is preferred. 1 Selected from -CH2CH2OCH2CH2OCH2CH2- or -CH2CH2OCH2CH2-. J 1 Represents a hydrogen atom or a polymerizable group, wherein the polymerizable group is selected from the groups represented by the following formula (J-1) or formula (J-2): , Preferably, J 1 Selected from groups represented by formula (J-1) or formula (J-2).

[0037] D 1 and D 2 Each group is independently selected from the groups represented by formulas (D-1) to (D-5) below: From the perspective of ease of obtaining raw materials and ease of synthesis, D is the preferred choice. 1 and D 2 Each represents independently ,or .

[0038] B 1 and B 2 Each can independently represent an aromatic ring with 6 or more carbon atoms that may have substituents. From the viewpoint of ease of starting materials and ease of synthesis, B is preferred. 1 and B 2 express .

[0039] A 1 and A 2 Each of these can independently represent a single bond or -OCH2-, -CH2O-, -CO-, -COO-, -OCO-, -O-, -S-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH=CH-COO-, -CH=C H-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO- CH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=NN=CH-, -CF=CF-, or -C≡C-.

[0040] SP 1 and SP 2 Each can independently represent a straight-chain or branched alkylene group having 1 to 20 carbon atoms, wherein any one -CH2- or multiple non-adjacent -CH2- can be independently replaced by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-.

[0041] L 1 and L 2Each element independently represents a hydrogen atom or a polymeric group, wherein the polymeric group is selected from the groups represented by formula (J-1) or formula (J-2) above. Preferably, L... 1 and L 2 Each group is independently selected from the groups represented by formula (J-1) or formula (J-2).

[0042] As the compound represented by general formula (1), it is particularly preferred to be the compound represented by the following formulas (R-1) to (R-23):

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055] .

[0056] There are no particular limitations on the method of manufacturing the polymeric liquid crystal compound represented by formula (1) of the present invention. It can be manufactured by appropriately combining known organic synthesis reactions (such as nucleophilic substitution reaction, esterification reaction, condensation reaction, Schiff base formation reaction, deprotection reaction, etc.) recorded in Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, etc., according to its structure.

[0057] In one embodiment of this application, a polymerizable composition is provided, which is a polymerizable composition containing the above-mentioned polymerizable liquid crystal compound. In addition to containing the above-mentioned polymerizable liquid crystal compound, it may also contain other polymerizable compounds, photopolymerization initiators, stabilizers, other additives and / or solvents, as described below.

[0058] In addition to the aforementioned polymerizable liquid crystal compounds, the polymerizable compositions of the present invention may also contain other polymerizable compounds that do not exhibit reverse wavelength dispersion, thereby adjusting wavelength dispersion, increasing crosslinking density, adjusting refractive index, inducing chiral phases, and reducing costs. Specifically, polymerizable compounds represented by the following formulas (N-1) to (N-12) are preferred: .

[0059] In a specific embodiment of the present invention, the polymeric composition comprises, by weight, 50 to 100 parts of the polymeric liquid crystal compound and 0.1 to 50 parts of the polymeric compound. For example, in the polymeric composition of the present invention, the weight parts of the polymeric liquid crystal compound can be 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, or any value between these numbers; and the weight parts of the polymeric compound can be 0.1 parts, 0.5 parts, 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, or any value between these numbers.

[0060] To form a crosslinked network through photoinitiated polymerization, a photoinitiator is generally required in the polymerizable composition. Examples of suitable photoinitiators for this invention include benzophenones, acetophenones, and benzoyl ketals. Furthermore, some brand-name initiators such as BASF OXE-01, OXE-02, OXE-03, OXE-04, and OXE-05 can also be added as photoinitiators. One photoinitiator can be used, or two or more photoinitiators can be used simultaneously. Relative to the polymerizable composition of this application, the photoinitiator accounts for 0.1% to 10% by mass, preferably 0.2% to 8% by mass, and more preferably 1% to 7% by mass, of the total mass of the polymerizable composition.

[0061] To improve its storage stability, a stabilizer is generally required in the polymeric composition. Suitable stabilizers for this invention include, for example, hydroquinone derivatives, hydroquinone monoalkyl ethers, tert-butylcatechol derivatives, pyrogallol derivatives, thiophenol derivatives, nitro compounds, β-naphthylamine derivatives, β-naphthol derivatives, and nitroso compounds. The amount of stabilizer added relative to the total mass of the polymeric composition is preferably 0.005% to 1% by mass, more preferably 0.01% to 0.8% by mass, and even more preferably 0.02% to 0.5% by mass. One stabilizer can be used, or two or more stabilizers can be used simultaneously. As a stabilizer, 2,6 di-tert-butyl-p-cresol (BHT).

[0062] In actual coating production processes, other additives can be added as needed to ensure solution leveling, photocrosslinking efficiency, etc. For example, additives suitable for the compositions of the present invention may include one or more combinations of leveling and defoaming agents and chain transfer agents. The leveling and defoaming agents may be at least one of the following: BYK-300, BYK-306, BYK-358, BYK-354, BYK-515, BYK-3560, BYK-3566 (purchased from BYK Corporation); MEGAFACE F-554, F-556 (purchased from DIC Corporation); and Zonyl FS-520, Zonyl 8857A (purchased from DuPont Corporation). The amount of additive used is preferably 0.005% to 5% by mass, more preferably 0.01% to 3% by mass, and even more preferably 0.02% to 1% by mass, relative to the total mass of the polymerizable composition.

[0063] In actual coating production processes, solvents are required to facilitate the coating process. Solvents suitable for the compositions of this invention mainly include benzenes, ketones, ethers, esters, halogenated hydrocarbons, and highly polar solvents. Benzene solvents mainly include: toluene, ethylbenzene, xylene, chlorobenzene, and anisole; ketone solvents mainly include: acetone, methyl ethyl ketone, 3-pentanone, cyclopentanone, cyclohexanone, and isophorone; ether solvents mainly include: 1,4-dioxane and tetrahydrofuran; ester solvents mainly include: ethyl acetate, butyl acetate, and propylene glycol methyl ether acetate; halogenated hydrocarbon solvents mainly include: dichloromethane, chloroform, and 1,2-dichloroethane; highly polar solvents mainly include: methanol, ethanol, isopropanol, n-butanol, tert-butanol, propylene glycol methyl ether, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, ethanolamine, and acetonitrile. You can use one solvent alone, or you can use two or more solvents at the same time.

[0064] According to another embodiment of this application, a phase retardation film is provided, which comprises a polymer product formed by polymerizing the above-described polymeric composition. The phase difference Re(450) at a wavelength of 450 nm and the phase difference Re(550) at a wavelength of 550 nm satisfy the following condition: Re(450) / Re(550) < 1.0.

[0065] The present invention will be further described below with reference to specific embodiments, but the present invention is not limited to the following embodiments. The technical solutions provided by the embodiments of this application are described in detail below.

[0066] The following describes the manufacturing method using compounds represented by formulas (R-1)~(R-5), (R-7), (R-8), (R-10), and (R-11) as examples.

[0067] Example 1: Preparation of the compound represented by formula (R-1)

[0068]

[0069] trans-1,4-bis(methanesulfonyloxymethyl)cyclohexane (10 g, 33.3 mmol), 3-tert-butyl-2,5-dihydroxybenzaldehyde (14.2 g, 73.2 mmol), and potassium phosphate (15.5 g, 73.2 mmol) were dissolved in 100 mL of N,N-dimethylformamide and reacted at 80 °C for 8 hours, then allowed to return to room temperature. Dichloromethane was added, followed by washing with water and then with saturated brine. The mixture was separated and the organic phase was concentrated. The resulting mixture was subjected to column chromatography and crystallization to give 10.8 g of a white solid compound R-1a, in 65% yield.

[0070] Compound R-1a (10.8 g, 21.7 mmol), trans-4-[4-(6-acryloyloxyhexyloxy)phenoxycarbonyl]cyclohexanecarboxylic acid (19 g, 45.6 mmol), and 4-dimethylaminopyridine (0.52 g, 4.3 mmol) were dissolved in 300 mL of dichloromethane. N,N'-diisopropylcarbodiimide (5.74 g, 45.6 mmol) was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 12 hours. The resulting mixture was subjected to column chromatography and crystallization to give 22.3 g of a white solid, compound R-1b, in 79% yield.

[0071] Compound R-1b (22.3 g, 17.2 mmol), compound R-1c (11.2 g, 37.8 mmol), and racemic camphorsulfonic acid (7.9 g, 34.4 mmol) were dissolved in 200 mL of chloroform. The reaction was carried out at 70 °C for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to give 24 g of white solid compound R-1d, in 75% yield.

[0072] Compound R-1d (24 g, 12.9 mmol) and N,N-diisopropylethylamine (6.66 g, 51.6 mmol) were dissolved in 200 mL of dichloromethane. Acryloyl chloride (4.67 g, 51.6 mmol) was slowly added dropwise under an ice-water bath, and the reaction was allowed to proceed to room temperature for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to give 19.9 g of white solid compound R-1, in 79% yield. 1 H NMR (500 MHz, CDCl3) δ 7.91 (s, 2H), 7.72-7.63 (m, 4H), 7.54-7.51 (m, 2H), 7.36-7.32 (m, 2H), 7.19-7.15 (m, 2H), 7.01-6.86 (m, 10H), 6.44-6.35 (m, 4H), 6.17-6.07 (m, 4H), 5.85-5.75 (m, 4H), 4.52-4.37 (m, 4H), 4.22-4.16 (m, 8H), 3.95(t, J = 6.4 Hz, 4H), 3.88-3.77 (m, 8H), 3.67-3.59 (m, 12H), 2.77-2.58 (m, 4H), 2.45-2.22 (m, 12H), 1.95-1.60 (m, 22H), 1.55-1.43 (m, 8H), 1.39 (s, 18H).

[0073] Example 2: Preparation of the compound represented by formula (R-2)

[0074] Trans-1,4-cyclohexanedicarboxylic acid (5 g, 29 mmol), 3-tert-butyl-2,5-dihydroxybenzaldehyde (11.85 g, 61 mmol), and 4-dimethylaminopyridine (0.71 g, 5.8 mmol) were dissolved in 150 mL of dichloromethane. N,N'-diisopropylcarbodiimide (7.69 g, 61 mmol) was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 12 hours. The resulting mixture was subjected to column chromatography and crystallization to give 12.2 g of a white solid compound R-2a, in 80% yield.

[0075] Compound R-2a (12.2 g, 23.3 mmol), trans-4-[4-(6-acryloyloxyhexyloxy)phenoxycarbonyl]cyclohexanecarboxylic acid (20.5 g, 48.9 mmol), and 4-dimethylaminopyridine (0.57 g, 4.7 mmol) were dissolved in 300 mL of dichloromethane. N,N'-diisopropylcarbodiimide (6.17 g, 48.9 mmol) was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 12 hours. The resulting mixture was subjected to column chromatography and crystallization to give 27.4 g of white solid compound R-2b, in 89% yield.

[0076] Compound R-2b (27.4 g, 20.7 mmol), compound R-1c (13.5 g, 45.5 mmol), and racemic camphorsulfonic acid (9.6 g, 41.4 mmol) were dissolved in 200 mL of chloroform. The reaction was carried out at 70 °C for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to give 29.2 g of white solid compound R-2c, in 75% yield.

[0077] Compound R-2c (29.2 g, 15.5 mmol) and N,N-diisopropylethylamine (8 g, 62 mmol) were dissolved in 200 mL of dichloromethane. Acryloyl chloride (5.61 g, 62 mmol) was slowly added dropwise under an ice-water bath, and the mixture was allowed to return to room temperature for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to give 28.1 g of white solid compound R-2, in 91% yield. 1 H NMR (500 MHz, CDCl3) δ 7.74 (s, 2H), 7.72-7.63 (m, 6H), 7.36-7.32 (m, 2H), 7.19-7.15 (m, 2H), 7.13 (d, J= 2.8 Hz, 2H), 7.01-6.95 (m, 4H), 6.92-6.86 (m, 4H), 6.44-6.35(m, 4H), 6.17-6.06 (m, 4H), 5.85-5.75 (m, 4H), 4.52-4.37 (m, 4H), 4.22-4.16(m, 8H), 3.95 (t, J = 6.4 Hz, 4H), 3.85 (t, J = 5.8 Hz, 4H), 3.67-3.59 (m,12H), 2.77-2.67 (m, 4H), 2.65-2.58 (m, 2H), 2.47-2.32 (m, 12H), 1.84-1.68 (m,20H), 1.55-1.50 (m, 4H), 1.49-1.44 (m, 4H), 1.38 (s, 18H).

[0078] Example 3: Preparation of the compound represented by formula (R-3)

[0079] (trans,trans)-[1,1'-bicyclohexane]-4,4'-dicarboxylic acid (6 g, 23.6 mmol), 3-tert-butyl-2,5-dihydroxybenzaldehyde (9.63 g, 49.6 mmol), and 4-dimethylaminopyridine (0.58 g, 4.7 mmol) were dissolved in 150 mL of dichloromethane. N,N'-diisopropylcarbodiimide (6.25 g, 49.6 mmol) was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 12 hours. The resulting mixture was subjected to column chromatography and crystallization to give 11 g of a white solid compound R-3a, in 77% yield.

[0080] Compound R-3a (11 g, 18.1 mmol), trans-4-[4-(6-acryloyloxyhexyloxy)phenoxycarbonyl]cyclohexanecarboxylic acid (15.9 g, 38.1 mmol), and 4-dimethylaminopyridine (0.44 g, 3.62 mmol) were dissolved in 300 mL of dichloromethane. N,N'-diisopropylcarbodiimide (4.8 g, 38.1 mmol) was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 12 hours. The resulting mixture was subjected to column chromatography and crystallization to give 21 g of white solid compound R-3b, in 82% yield.

[0081] Compound R-3b (21 g, 14.9 mmol), compound R-1c (9.75 g, 32.8 mmol), and racemic camphorsulfonic acid (6.92 g, 29.8 mmol) were dissolved in 200 mL of chloroform. The reaction was carried out at 70 °C for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to give 24.5 g of white solid compound R-3c, in 84% yield.

[0082] Compound R-3c (24.5 g, 12.5 mmol) and N,N-diisopropylethylamine (6.43 g, 49.8 mmol) were dissolved in 200 mL of dichloromethane. Acryloyl chloride (4.51 g, 49.8 mmol) was slowly added dropwise under an ice-water bath, and the reaction was allowed to return to room temperature for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to give 21.2 g of white solid compound R-3, in 82% yield. 1 H NMR (500 MHz, CDCl3) δ 7.71 (s, 2H), 7.69-7.61 (m, 6H), 7.35-7.31 (m, 2H), 7.18-7.14 (m, 2H), 7.11 (d, J = 2.8 Hz, 2H), 7.01-6.95 (m, 4H), 6.92-6.86 (m, 4H), 6.44-6.35 (m, 4H), 6.17-6.06 (m, 4H), 5.85-5.75 (m, 4H), 4.47-4.40 (m, 4H),4.22-4.16 (m, 8H), 3.94 (t, J = 6.5 Hz, 4H), 3.85 (t, J = 5.8 Hz, 4H), 3.67-3.58 (m, 12H), 2.74-2.51 (m, 6H), 2.39-2.22 (m, 12H), 1.97-1.91 (m, 4H), 1.83-1.56 (m, 20H), 1.54-1.42 (m, 8H), 1.38 (s, 18H), 1.27-1.12 (m, 6H).

[0083] Example 4 Preparation of the compound represented by formula (R-4)

[0084] Terephthalic acid (20 g, 120.4 mmol), 3-tert-butyl-2,5-dihydroxybenzaldehyde (49.1 g, 252.8 mmol), and 4-dimethylaminopyridine (1.4 g, 12 mmol) were dissolved in 500 mL of dichloromethane. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (48.5 g, 252.8 mmol) was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 8 hours. The resulting mixture was subjected to column chromatography and crystallization to give 50 g of a white solid compound R-4a, in 80% yield.

[0085] Compound R-4a (45 g, 86.8 mmol), trans-4-[4-(6-acryloyloxyhexyloxy)phenoxycarbonyl]cyclohexanecarboxylic acid (76.2 g, 18.2 mmol), and 4-dimethylaminopyridine (1.06 g, 8.68 mmol) were dissolved in 1 L of dichloromethane. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (49.9 g, 260.4 mmol) was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 4 hours. The resulting mixture was subjected to column chromatography to give 59.2 g of colorless colloidal compound R-4b, in 52% yield.

[0086] Compound R-4b (10 g, 7.58 mmol), compound R-1c (4.73 g, 15.9 mmol), and racemic camphorsulfonic acid (1.06 g, 0.45 mmol) were dissolved in 50 mL of chloroform. The reaction was carried out at 50 °C for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 12 g of white solid compound R-4c, in 84% yield.

[0087] Compound R-4c (12 g, 6.39 mmol) and N,N-diisopropylethylamine (2.47 g, 19.2 mmol) were dissolved in 50 mL of dichloromethane. Acryloyl chloride (1.74 g, 19.2 mmol) was slowly added dropwise under an ice-water bath, and the reaction was allowed to proceed to room temperature for 3 hours. The resulting mixture was subjected to column chromatography and crystallization to give 8.7 g of white solid compound R-4, in 69% yield. 1 H NMR (400 MHz, CDCl3) δ 8.43 (s, 4H), 7.87 (d, J = 2.8 Hz, 2H), 7.79 (s, 2H), 7.68-7.63 (m,4H), 7.37-7.29 (m, 4H), 7.18-7.12 (m, 2H), 6.99 (d, J = 8.9 Hz, 4H), 6.89 (d, J= 9.0 Hz, 4H), 6.44-6.34 (m, 4H), 6.17-6.05 (m, 4H), 5.84-5.74 (m, 4H), 4.55-4.35 (m, 4H), 4.23-4.15 (m, 8H), 3.95 (t, J = 6.4 Hz, 4H), 3.87 (t, J = 5.7 Hz,4H), 3.69-3.60 (m, 12H), 2.81-2.73 (m, 2H), 2.67-2.60 (m, 2H), 2.45-2.35 (m,8H), 1.85-1.68 (m, 16H), 1.56-1.45 (m, 8H), 1.41 (s, 18H).

[0088] Example 5 Preparation of the compound represented by formula (R-5)

[0089] Compound R-2b (10 g, 7.55 mmol), compound R-5a (4.86 g, 16.6 mmol), and racemic camphorsulfonic acid (1.75 g, 7.55 mmol) were dissolved in 300 mL of chloroform. The reaction was carried out at 50 °C for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 13 g of white solid compound R-5b, in 92% yield.

[0090] Compound R-5b (13 g, 6.93 mmol) and N,N-diisopropylethylamine (2.68 g, 20.79 mmol) were dissolved in 300 mL of dichloromethane. Acryloyl chloride (1.88 g, 20.79 mmol) was slowly added dropwise under an ice-water bath, and the reaction was allowed to proceed to room temperature for 3 hours. The resulting mixture was subjected to column chromatography and crystallization to give 6.6 g of white solid compound R-5, in 48% yield. 1 H NMR (400MHz, CDCl3) δ 7.77-7.62 (m, 6H), 7.47 (s, 2H), 7.38-7.32 (m, 2H), 7.21-7.15(m, 2H), 7.14 (d, J = 2.7 Hz, 2H), 6.98 (d, J = 9.0 Hz, 4H), 6.88 (d, J= 9.0Hz, 4H), 6.44-6.34 (m, 4H), 6.17-6.05 (m, 4H), 5.85-5.76 (m, 4H), 4.38-4.25(m, 4H), 4.18 (t, J = 6.6 Hz, 4H), 4.11 (t, J = 6.7 Hz, 4H), 3.94 (t, J = 6.4Hz, 4H), 2.75-2.65 (m, 4H), 2.64-2.54 (m, 2H), 2.45-2.30 (m, 12H), 1.84-1.60 (m, 28H), 1.56-1.31 (m, 42H).

[0091] Example 6 Preparation of the compound represented by formula (R-7)

[0092] Trans-1,4-cyclohexanedicarboxylic acid (12.19 g, 70.8 mmol), 3-methoxy-2,5-dihydroxybenzaldehyde (25 g, 148.7 mmol), and 4-dimethylaminopyridine (0.86 g, 7.08 mmol) were dissolved in 300 mL of dichloromethane. N,N'-diisopropylcarbodiimide (18.7 g, 148.7 mmol) was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 12 hours. The resulting mixture was subjected to column chromatography and crystallization to give 28 g of a white solid compound R-7a, in 84% yield.

[0093] Compound R-7a (28 g, 59.3 mmol), trans-4-[4-(6-acryloyloxyhexyloxy)phenoxycarbonyl]cyclohexanecarboxylic acid (54.6 g, 130.5 mmol), and 4-dimethylaminopyridine (0.72 g, 5.93 mmol) were dissolved in 500 mL of dichloromethane. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (34 g, 177.9 mmol) was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 4 hours. The resulting mixture was subjected to column chromatography and crystallization to give 41.2 g of white solid compound R-7b, in 55% yield.

[0094] Compound R-7b (41.2 g, 32.36 mmol), compound R-1c (20.2 g, 67.96 mmol), and racemic camphorsulfonic acid (0.75 g, 3.23 mmol) were dissolved in 300 mL of chloroform. The reaction was carried out at 50 °C for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 53.4 g of white solid compound R-7c, in 90% yield.

[0095] Compound R-7c (53.4 g, 29.15 mmol) and N,N-diisopropylethylamine (15.04 g, 116.6 mmol) were dissolved in 300 mL of dichloromethane. Acryloyl chloride (10.55 g, 116.6 mmol) was slowly added dropwise under an ice-water bath, and the reaction was allowed to proceed to room temperature for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 39 g of white solid compound R-7, in 69% yield. 1 H NMR (400 MHz, CDCl3) δ 7.84-7.60 (m, 8H), 7.36-7.32 (m, 2H), 7.19-7.15 (m, 2H), 7.13-7.10 (m, 2H), 6.99 (d, J = 8.9 Hz, 4H), 6.88 (d, J = 9.0 Hz, 4H), 6.43-6.35 (m, 4H), 6.17-6.05 (m, 4H), 5.84-5.74 (m, 4H), 4.52-4.38 (m, 4H), 4.22-4.13 (m, 8H), 3.97-3.89 (m, 8H), 3.74-3.52 (m, 18H), 2.78-2.58 (m, 6H), 2.43-2.29 (m, 12H), 1.84-1.66 (m, 20H), 1.54-1.42 (m, 8H).

[0096] Example 7 Preparation of the compound represented by formula (R-8)

[0097] Trans-1,4-cyclohexanedicarboxylic acid (13.46 g, 78.2 mmol), 3-methyl-2,5-dihydroxybenzaldehyde (25 g, 164.3 mmol), and 4-dimethylaminopyridine (0.95 g, 7.82 mmol) were dissolved in 300 mL of dichloromethane. N,N'-diisopropylcarbodiimide (20.7 g, 164.3 mmol) was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 12 hours. The resulting mixture was subjected to column chromatography and crystallization to give 22 g of a white solid compound R-8a, in 64% yield.

[0098] Compound R-8a (22 g, 50 mmol), trans-4-[4-(6-acryloyloxyhexyloxy)phenoxycarbonyl]cyclohexanecarboxylic acid (46 g, 110 mmol), and 4-dimethylaminopyridine (0.61 g, 5 mmol) were dissolved in 500 mL of dichloromethane. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (28.76 g, 150 mmol) was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 4 hours. The resulting mixture was subjected to column chromatography and crystallization to give 37.4 g of white solid compound R-8b, in 60% yield.

[0099] Compound R-8b (10 g, 8.06 mmol), compound R-1c (5.03 g, 16.9 mmol), and racemic camphorsulfonic acid (0.75 g, 3.22 mmol) were dissolved in 300 mL of chloroform. The reaction was carried out at 50 °C for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 8.5 g of white solid compound R-8c, in 59% yield.

[0100] Compound R-8c (8.5 g, 4.72 mmol) and N,N-diisopropylethylamine (1.83 g, 14.16 mmol) were dissolved in 300 mL of dichloromethane. Acryloyl chloride (1.28 g, 14.16 mmol) was slowly added dropwise under an ice-water bath, and the reaction was allowed to return to room temperature for 1 hour. The resulting mixture was subjected to column chromatography to give 4.5 g of a colorless oily compound R-8, in 50% yield. 1 H NMR (400 MHz, CDCl3) δ 8.02 (s, 2H), 7.76 (d, J = 7.9 Hz, 2H), 7.69 (d, J = 7.9 Hz, 2H), 7.60(d, J = 2.6 Hz, 2H), 7.39-7.36 (m, 2H), 7.23-7.19 (m, 2H), 7.03 (d, J= 2.5 Hz, 2H), 6.99 (d, J = 8.9 Hz, 4H), 6.88 (d, J = 9.0 Hz, 4H), 6.43-6.35 (m, 4H), 6.17-6.05 (m, 4H), 5.84-5.74 (m, 4H), 4.59-4.51 (m, 4H), 4.22-4.13 (m, 8H), 3.97-3.89 (m, 8H), 3.67-3.55 (m, 12H), 2.78-2.58 (m, 6H), 2.43-2.28 (m, 12H), 2.19 (s, 6H), 1.84-1.67 (m, 20H), 1.54-1.43 (m, 8H).

[0101] Example 8 Preparation of the compound represented by formula (R-10)

[0102] Compounds R-2a (8.3 g, 15.84 mmol), R-10a (14.26 g, 31.68 mmol), and 4-dimethylaminopyridine (0.19 g, 1.58 mmol) were dissolved in 500 mL of dichloromethane. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (9.11 g, 47.52 mmol) was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 4 hours. The resulting mixture was subjected to column chromatography to give 15 g of a colorless oily compound R-10b, in 68% yield.

[0103] Compound R-10b (15 g, 10.8 mmol), compound R-1c (6.74 g, 22.7 mmol), and racemic camphorsulfonic acid (0.75 g, 3.24 mmol) were dissolved in 500 mL of chloroform. The reaction was carried out at 50 °C for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 5 g of brown solid compound R-10c, with a yield of 24%.

[0104] Compound R-10c (5 g, 2.57 mmol) and N,N-diisopropylethylamine (1.33 g, 10.28 mmol) were dissolved in 200 mL of dichloromethane. Acryloyl chloride (0.93 g, 10.28 mmol) was slowly added dropwise under an ice-water bath, and the reaction was allowed to proceed to room temperature for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 3 g of white solid compound R-10, in 57% yield. 1H NMR (400MHz, CDCl3) δ 7.76 (s, 2H), 7.73-7.63 (m, 6H), 7.36-7.32 (m, 2H), 7.17 (m,2H), 7.13 (d, J = 2.7 Hz, 2H), 6.99 (d, J = 9.0 Hz, 4H), 6.91 (d, J = 9.1 Hz,4H), 6.46-6.35 (m, 4H), 6.19-6.05 (m, 4H), 5.85-5.75 (m, 4H), 4.50-4.40 (m,4H), 4.36-4.30 (m, 4H), 4.23-4.17 (m, 4H), 4.15-4.09 (m, 4H), 3.90-3.83 (m,8H), 3.78-3.68 (m, 12H), 3.67-3.57 (m, 12H), 2.78-2.66 (m, 4H), 2.65-2.57 (m,2H), 2.42-2.32 (m, 12H), 1.84-1.69 (m, 12H), 1.38 (s, 18H).

[0105] Example 9 Preparation of the compound represented by formula (R-11)

[0106] Compound R-2a (4 g, 7.63 mmol), compound R-11a (7.86 g, 16.02 mmol), and 4-dimethylaminopyridine (0.09 g, 0.76 mmol) were dissolved in 100 mL of dichloromethane. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (4.37 g, 22.89 mmol) was slowly added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 12 hours. The resulting mixture was subjected to column chromatography to give 6.3 g of a colorless oily compound R-11b, in 56% yield.

[0107] Compound R-11b (6.3 g, 4.29 mmol), compound R-1c (2.68 g, 9.01 mmol), and racemic camphorsulfonic acid (0.1 g, 0.43 mmol) were dissolved in 100 mL of chloroform. The reaction was carried out at 50 °C for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 6 g of white solid compound R-11c, in 69% yield.

[0108] Compound R-11c (6 g, 2.96 mmol) and N,N-diisopropylethylamine (1.53 g, 11.84 mmol) were dissolved in 100 mL of dichloromethane. Acryloyl chloride (1.07 g, 11.84 mmol) was slowly added dropwise under an ice-water bath, and the reaction was allowed to proceed to room temperature for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 4.8 g of white solid compound R-11, in 76% yield. 1 H NMR (400 MHz, CDCl3) δ 7.76 (s, 2H), 7.72-7.64 (m, 6H), 7.36-7.32 (m, 2H), 7.24(d, J = 8.5 Hz, 4H), 7.20-7.12 (m, 4H), 7.02 (d, J = 8.4 Hz, 4H), 6.46-6.35 (m,4H), 6.18-6.05 (m, 4H), 5.88-5.75 (m, 4H), 4.50-4.40 (m, 4H), 4.38-4.27 (m,12H), 4.23-4.17 (m, 4H), 3.86 (t, J = 5.7 Hz, 4H), 3.68-3.58 (m, 12H), 2.94(t, J = 7.0 Hz, 4H), 2.78-2.60 (m, 14H), 2.45-2.31 (m, 12H), 1.83-1.70 (m, 12H), 1.38 (s, 18H).

[0109] Comparative Example 1: Compound represented by formula (X-1)

[0110] Comparative Example 2 Compound represented by formula (X-2)

[0111] Comparative Example 3 Compound represented by formula (X-3)

[0112] Test methods and test results: I. Solubility The solubility of the compounds represented in Examples 1 to 9 and Comparative Examples 1 to 3 was determined using the methods shown below. The results are shown in Table 1 below.

[0113] Specifically, 1 g of a polymerizable liquid crystal compound (the compound described in Table 1 below) and 4 g of cyclohexanone were weighed into a 30 mL sample vial to form a mixture. The resulting mixtures correspond to Examples 10-18 and Comparative Examples 4-6 shown in Table 1, respectively. The mixtures were thoroughly sonicated at room temperature and allowed to stand for 10 minutes. If the mixture was clear and transparent with no visible insoluble matter, the process was considered complete, and the solubility was determined to be 20% or higher. If there was residual solubility, 5 g of cyclohexanone was added, and the mixture was thoroughly sonicated at room temperature. After standing for 10 minutes, the mixture was again observed to be clear and transparent with no visible insoluble matter. If the mixture was again observed to be clear and transparent with no visible insoluble matter, the process was considered complete, and the solubility was determined to be 10% to 20%. If there was still residual solubility, another 10 g of cyclohexanone was added, and the mixture was thoroughly sonicated at room temperature. After standing for 10 minutes, the mixture was again observed to be clear and transparent with no visible insoluble matter. If the mixture was again observed to be clear and transparent with no visible insoluble matter, the process was considered complete, and the solubility was determined to be 5% to 10%. If there was still residual solubility, the solubility was determined to be less than 5%.

[0114] In Table 1: A: Solubility is over 20%; B: Solubility is 10% to 20%; C: Solubility is 5% to 10%; D: Solubility is less than 5%.

[0115] Note: The solubility percentage (X%) mentioned in this article means the number of grams of compound contained in 100 grams of the mixture (g / 100 g mixture).

[0116] Table 1

[0117] II. Wavelength Dispersion Photoaligning agent HSPA-252B (manufactured by Osaka Organics) was uniformly coated onto a glass surface using a spin coater (2300 rpm, 10 s). Drying was performed at 120 °C. After cooling to room temperature, the surface was irradiated with 10 mJ of polarized ultraviolet light at 313 nm to obtain a glass substrate with an alignment layer. On the glass substrate with the alignment layer, the polymerizable composition solution described in Table 2 was uniformly coated onto each substrate using a spin coater (600 rpm, 30 s), and dried at 100 °C to evaporate the solvent. Subsequently, the substrate was cooled to room temperature, and the film surface with the composition was irradiated with a mercury lamp under a nitrogen atmosphere with a total energy of 1500 mJ / cm². 2 That is, a phase difference film is obtained, and the phase difference films formed correspond to Examples 19-27 and Comparative Examples 7-9 shown in Table 3.

[0118] Table 2

[0119] For the fabricated retardation film, the phase difference at various wavelengths was measured using an Axoscan polarization meter. The phase difference Re(450) at 450 nm and the phase difference Re(550) at 550 nm were recorded. The Re(450) / Re(550) ratio was calculated and evaluated according to the following criteria. The results are shown in Table 3 below, where a smaller Re(450) / Re(550) ratio indicates better inverse wavelength dispersion.

[0120] In Table 3: A: Re(450) / Re(550) is less than or equal to 0.84; B: Re(450) / Re(550) is greater than 0.84 and less than or equal to 0.87; C: Re(450) / Re(550) is greater than 0.87 and less than or equal to 0.9; D: Re(450) / Re(550) is greater than 0.9.

[0121] III. Orientation Defects The number of alignment defects on the fabricated phase retardation film was visually confirmed using an optical microscope, and evaluated according to the following evaluation criteria. The results are shown in Table 3 below.

[0122] In Table 3: A: No defects; B: 1 to 10; C: 11 to 100; D: The entire surface has alignment defects (>100).

[0123] IV. Crystallization The fabricated phase retardation films were visually examined using an optical microscope to confirm the crystallization pattern on the screen, and evaluated according to the following criteria. The results are shown in Table 3 below.

[0124] In Table 3: A: No crystallization; B: Localized, minor crystallization; C: Extensive crystallization; D: Dense crystallization across the entire surface.

[0125] Table 3

[0126] The polymerizable liquid crystal compound provided by this invention has significantly improved solubility, and the resulting phase retardation film has excellent reverse wavelength dispersion. At the same time, alignment defects and crystallization problems are significantly improved.

[0127] Specifically, compared to compounds X-1 to X-3 in Comparative Examples 4-6, the solubility of the polymeric liquid crystal compounds provided in Examples 10-18 of this invention is fundamentally improved. For example, under the same test conditions, the polymeric liquid crystal compounds (such as R-1, R-3, R-7, R-8, R-10, R-11) provided in Examples 10, 12, and 15-18 achieved a solubility rating of A (>20%), indicating that they are easily soluble and can form high-concentration, storage-stable coating solutions. In contrast, the solubility of comparative example compounds X-1 and X-2 was only D (<5%). This superior solubility greatly broadens the coating process window, allowing for the preparation of solutions with higher solid content, which helps to obtain more uniform film layers and improve coating quality. This is directly attributed to the fact that the steric substituents introduced into the molecular structure of the compounds in this invention effectively disrupt the regularity of the molecular structure and significantly improve their solubility in organic solvents.

[0128] All the polymerizable liquid crystal compounds provided in this invention (Examples 19-27) achieved the highest rating of A (Re(450) / Re(550) ≤ 0.84) in the reverse wavelength dispersion evaluation after film formation, demonstrating extremely excellent and stable reverse wavelength dispersion characteristics. In contrast, the comparative compound X-1 to X-3 only achieved a rating of C or D in this evaluation, and their optical performance could not meet the requirements of high-end display devices. This is mainly due to the introduction of steric groups at the short axis sites of the compound's molecular structure, thereby achieving ideal reverse wavelength dispersion characteristics.

[0129] Regarding alignment defects, the polymerizable liquid crystal compounds provided by this invention show significant improvement in alignment defects after film formation. Compounds in Examples 19-21 and 24-27 (such as R-1~R-3, R-7, R-8, R-10, R-11, etc.) received a Grade A (no defects) rating, and the rest received a Grade B (very few defects). Comparative example compounds X-1 and X-2, however, exhibited a Grade D (alignment defects occur on the entire surface), and comparative example compound X-3 was a Grade C (numerous defects).

[0130] In the crystallinity test, the polymerizable liquid crystal compounds provided by the present invention also performed excellently after film formation. In particular, the compounds in Examples 19-21 and 24-27 (such as R-1~R-3, R-7, R-8, R-10, R-11, etc.) all obtained Grade A (no crystallization) evaluation. Although some advantages of the polymeric liquid crystal compounds and the phase retardation films formed therefrom shown in Examples 1-9 have been described by way of example only, it is reasonable to expect, based on their structure-property relationships, that other compounds covered by general formula (1) also possess the same or corresponding technical effects.

[0131] This invention provides a highly soluble polymerizable liquid crystal compound for forming a retardation film with excellent reverse wavelength dispersion. By using a polymerizable composition containing the polymerizable liquid crystal compound of this application, the generation of crystallization and alignment defects during the manufacturing process of the retardation film can be suppressed. The inventors have conducted in-depth research and discovered that by introducing V at appropriate positions along the short axis of the polymerizable liquid crystal compound's molecular structure… 1 V 2 V 3 Or, sterically hindered substituents with a U-structure, such as alkyl, alkoxy, or alkoxycarbonyl groups, can lead to excellent reverse wavelength dispersibility in the film-forming properties of the compound. Furthermore, by introducing V-shaped substituents into the molecular structure of polymerizable liquid crystal compounds... 1 V 2 V 3 The steric hindrance substituents in the U-structure disrupt the regularity of the molecular structure, resulting in excellent solubility of the polymeric liquid crystal compound. Phase reversal films fabricated using polymeric compositions containing the above-mentioned polymeric liquid crystal compounds are less prone to crystallization and alignment defects.

[0132] The above description is merely an embodiment of this application and is not intended to limit the scope of this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the scope of the claims of this application.

Claims

1. A polymerizable liquid crystal compound, characterized in that, The structure of the polymeric liquid crystal compound is represented by the following formula (1): L 1 -SP 1 -A 1 -B 1 -C 1 -D 1 -M 1 -Ar 1 -M 2 -G-M 3 -Ar 2 -M 4 -D 2 -C 2 -B 2 -A 2 -SP 2 -L 2 Formula (1); In formula (1), G is selected from the groups represented by the following formulas (G-1) to (G-9): , where * represents the bonding position, and x in equation (G-9) represents an integer from 2 to 10; M 1 、M 2 、M 3 、M 4 、C 1 及C 2 each independently represents -OCH2-, -CH2O-, -CO-, -COO-, -OCO-, -O-, -S-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO-CH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=N-N=CH-, -CF=CF-, or -C≡C-; Ar 1 and Ar 2 Each is independently selected from the aromatic rings represented by the following formula (Ar-1) or formula (Ar-2): ,or In the formulas (Ar-1) to (Ar-2), Q represents a straight-chain or branched alkyl group having 1 to 20 hydrogen atoms or carbon atoms; V 1 V 2 and V 3 Each of these groups independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 10 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a sulfonyl pentafluoride group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a methoxy group, an ethoxy group, a methoxycarbonyl group, an ethoxycarbonyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, or a thioisocyano group, wherein V 1 V 2 and V 3 At least one of them is not a hydrogen atom; W 1 Selected from , , , , , , ,or Among them, W 1 The hydrogen atom at any position on the aromatic ring can be replaced by one or more substituents U, wherein U is selected from straight-chain or branched alkyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, sulfopentafluoride, nitro, cyano, isocyano, amino, hydroxyl, methoxy, ethoxy, mercapto, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, or thioisocyanate, having 1 to 20 carbon atoms. W 2 J is represented by the following formula (W-1): 1 -T 1 -* (W-1), Wherein, in the above formula (W-1): T 1 Represents a straight-chain alkylene group having 1 to 20 carbon atoms, wherein any one -CH2- or multiple non-adjacent -CH2- atoms can be independently replaced by -O-; J 1 Represents a hydrogen atom or a polymerizable group, wherein the polymerizable group is selected from the groups represented by the following formula (J-1) or formula (J-2): ,or ; D 1 and D 2 Each group is independently selected from the groups represented by formulas (D-1) to (D-5) below: ; B 1 and B 2 Each can independently represent an aromatic ring with 6 or more carbon atoms that may have substituents; A 1 and A 2 Each of these can independently represent a single bond or -OCH2-, -CH2O-, -CO-, -COO-, -OCO-, -O-, -S-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH=CH-COO-, -CH=C H-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO- CH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=NN=CH-, -CF=CF-, or -C≡C-; SP 1 and SP 2 Each can independently represent a straight-chain or branched alkylene group having 1 to 20 carbon atoms, wherein any one -CH2- or multiple non-adjacent -CH2- can be independently replaced by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-; L 1 and L 2 Each of these independently represents a hydrogen atom or a polymeric group, wherein the polymeric group is selected from the groups represented by formula (J-1) or formula (J-2) above.

2. The polymerizable liquid crystal compound according to claim 1, characterized in that, V 1 V 2 and V 3 At least one of them is selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy, methoxycarbonyl, or ethoxycarbonyl or cyano; and / or, W 1 Selected from Among them, W 1 The hydrogen atom at any position on the aromatic ring may be replaced by one or more substituents U, wherein U is selected from straight-chain or branched alkyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, sulfonyl pentafluoride, nitro, cyano, isocyano, amino, hydroxyl, methoxy, ethoxy, mercapto, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, or thioisocyano, having 1 to 20 carbon atoms.

3. The polymerizable liquid crystal compound according to claim 1, characterized in that, T 1 Selected from -CH2CH2OCH2CH2OCH2CH2- or -CH2CH2OCH2CH2-; and / or, J 1 Selected from groups represented by formula (J-1) or formula (J-2).

4. The polymerizable liquid crystal compound according to claim 1, characterized in that, B 1 and B 2 It can be represented by the following formula (B-1): ; and / or, L 1 and L 2 Each group is independently selected from the groups represented by formula (J-1) or formula (J-2).

5. The polymerizable liquid crystal compound according to claim 1, characterized in that, The polymerizable liquid crystal compound is selected from the following structures: 。 6. A polymerizable composition, characterized in that, The polymeric composition includes the polymeric liquid crystal compound according to any one of claims 1-5.

7. The polymerizable composition according to claim 6, characterized in that, The polymerizable composition further comprises a polymerizable compound selected from the following structures: 。 8. The polymerizable composition according to claim 7, characterized in that, The polymeric composition comprises, by weight, 50 to 100 parts of the polymeric liquid crystal compound and 0.1 to 50 parts of the polymeric compound.

9. A phase retardation film, characterized in that, It comprises a polymeric product polymerized from any of the polymeric compositions described in claims 6-8.

10. The phase retardation film according to claim 9, characterized in that, The phase difference Re(450) at 450 nm wavelength and the phase difference Re(550) at 550 nm wavelength satisfy the condition: Re(450) / Re(550) < 1.0.

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