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

Abstract

The present invention provides a polymerizable liquid crystal compound which is used for forming a phase difference film having excellent reverse wavelength dispersibility and is not liable to precipitate in a solvent, a polymerizable composition containing the polymerizable liquid crystal compound, and a phase difference film prepared from the polymerizable composition. The polymerizable liquid crystal compound provided by the invention has excellent reverse wavelength dispersibility, improved precipitation property, improved film-forming crystallinity and improved film-forming alignment defects. The phase difference film prepared from the polymerizable composition containing the polymerizable liquid crystal compound is not prone to crystallization and alignment defects in the manufacturing process.

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 in 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 (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 R450 at 450 nm and R550 at 550 nm satisfying the condition: R450 / R550 < 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 ensure the liquid crystals achieve a specific orientation, a functional alignment layer is also 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 retardation films with reverse wavelength dispersion. Existing polymeric liquid crystal compounds with reverse wavelength dispersion are typically T-type molecular designs (see patents: CN101838264B, CN101379420B, CN107001242B, CN109952323B, CN105384723B, etc.). However, these polymeric liquid crystal compounds or compositions containing them suffer from several problems, including insufficient reverse wavelength dispersion, easy precipitation in solvents, excessive film crystallization, and numerous alignment defects.

[0005] Therefore, there is an urgent need to provide a polymerizable liquid crystal compound; as well as a polymerizable composition containing the polymerizable liquid crystal compound and a phase reversal film, wherein the polymerizable liquid crystal compound satisfies the following properties: it is not easily precipitated in a solvent; the phase reversal film made using the polymerizable liquid crystal compound has excellent reverse wavelength dispersibility; and crystallization and alignment defects are not easily generated during the manufacturing process of the phase reversal film using the polymerizable liquid crystal compound. Summary of the Invention

[0006] To address the shortcomings of existing polymeric liquid crystal compounds or compositions containing them, such as insufficient reverse wavelength dispersion, easy precipitation in solvents, excessive film crystallization, and numerous film alignment defects, according to the first aspect of this application, a polymeric liquid crystal compound that is not easily precipitated in solvents is provided for forming a phase retardation film with excellent reverse wavelength dispersion, and crystallization and alignment defects are less likely to occur during the fabrication of the phase retardation film using this polymeric liquid crystal compound.

[0007] According to a first aspect of this application, a polymerizable liquid crystal compound is provided, the structural formula of which is shown in the following formula (1): R 1 -C 1 -Ar 1 -M 1 -GM 2 -Ar 2 -C 2 -R 2 (1) In equation (1), Ar 1 and Ar 2 Each of these independently represents an aromatic ring represented by either formula (Ar-1) or formula (Ar-2), with * indicating a bonding position.

[0008] In formula (Ar-1) or formula (Ar-2), Q represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms. V 1 V 2 and V 3 Each can independently represent a hydrogen atom, a straight-chain or branched alkyl group, cyano group, methoxy group, ethoxy group, methoxycarbonyl group, or ethoxycarbonyl group having 1 to 10 carbon atoms. W 1 express W 1 The hydrogen atom 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, methoxy, or ethoxy groups having 1 to 20 carbon atoms. W2 It is represented by the following formula (W-1), J 1 -T 1 -*(W-1) In the above formula (W-1), T 1 This refers to a straight-chain or branched alkylene group having 1 to 20 carbon atoms, wherein any one -CH2- or multiple non-adjacent -CH2- groups can be independently replaced by -O-, -COO-, -OCO-, -O-CO-O-, or -C≡C-. J 1 This represents a hydrogen atom or a polymerizable group, wherein the polymerizable group is selected from the groups represented by formula (J-1) or formula (J-2) below.

[0009] C 1 C 2 M 1 and M 2 Each can be independently represented as -OCH2-, -CH2O-, -COO-, -OCO-, or -O-CO-O-. G is selected from the groups represented by the following formulas (G-1) to (G-3).

[0010] R 1 R is expressed by the following equation (2). 2 It is represented by the following formula (3), L 1 -SP 1 -(A 1 -B 1 ) y -*(2) L 2 -SP 2 -(A 2 -B 2 ) z -*(3) Among them, SP 1 With SP 2 A 1 With A 2 B 1 With B 2 At least one pair of y and z is different. In equations (2) and (3), y and z each independently represent 1 or 2. A 1 and A 2Each can independently represent a single bond, -OCH2-, -CH2O-, -COO-, -OCO-, -O-, or -O-CO-O-. When y is 2, multiple A's... 1 They can be the same or different. When z is 2, multiple A's 2 They may be the same or different. B 1 and B 2 Each group is independently selected from the groups represented by formula (G-1) or formula (G-3) above, and when y is 2, multiple B groups... 1 They can be the same or different; when z is 2, multiple Bs 2 They may be the same or different. 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- groups can be independently replaced by -O-, -COO-, -OCO-, or -O-CO-O-. L 1 and L 2 Each of the above formulas (J-1) or (J-2) represents a polymerizable group.

[0011] Optionally, J 1 Selected from the groups represented by formula (J-1) or formula (J-2).

[0012] Optionally, y is different from z.

[0013] Optionally, T 1 Selected from -CH2CH2OCH2CH2OCH2CH2- or -CH2CH2OCH2CH2-.

[0014] Optionally, the polymerizable liquid crystal compound is selected from the following structures:

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[0044] According to a second aspect of this application, a polymerizable composition is provided comprising the polymerizable liquid crystal compound according to a first aspect of this application.

[0045] Optionally, the polymerizable composition further comprises a polymerizable compound; the polymerizable compound is selected from the following structures:

[0046] .

[0047] 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.

[0048] According to a third aspect of this application, a phase retardation film is provided, the phase retardation film comprising a polymeric product polymerized from the polymeric composition according to a second aspect of this application.

[0049] Optionally, the phase difference R450 at a wavelength of 450 nm and the phase difference R550 at a wavelength of 550 nm satisfy the following condition: R450 / R550 < 1.0.

[0050] The technical solution adopted in this invention can achieve the following beneficial effects: This application provides a polymerizable liquid crystal compound that is not easily precipitated in a solvent for forming a retardation film with excellent reverse wavelength dispersibility. Furthermore, using a polymerizable composition containing the polymerizable liquid crystal compound of this application can suppress the generation of crystallization and alignment defects during the manufacturing process of the retardation film, and can significantly improve film crystallinity and film alignment defects. Detailed Implementation

[0051] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention 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 invention, and not all of them. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0052] The inventors have discovered through research that: 1. The disclosed compound structures typically have only one chromophore side chain, resulting in fewer chromophores and higher R450 / R550 values, indicating insufficient reverse wavelength dispersion; 2. The disclosed compound structures have strong main chain rigidity and high symmetry, making them prone to precipitation in solvents and easily leading to crystallization and alignment defects during film formation.

[0053] Therefore, the object of the present invention is to provide a non-depositional polymeric liquid crystal compound for forming a retardation film with excellent reverse wavelength dispersion, a polymeric composition containing the compound, and a retardation film.

[0054] To achieve the above objectives, the inventors conducted in-depth research and discovered that when a polymeric liquid crystal compound has multiple chromophore side chains spaced at a certain distance, the compound exhibits excellent reverse wavelength dispersion after film formation. Furthermore, when the structures at both ends of the polymeric liquid crystal compound's main chain are different, the compound exhibits excellent precipitation suppression capabilities. Crystallization and alignment defects are less likely to occur during the fabrication of phase retardation films using polymeric compositions containing the above-mentioned polymeric liquid crystal compounds. This invention thus completes the present invention.

[0055] In one embodiment, this application provides a polymerizable liquid crystal compound.

[0056] [Polymerizable liquid crystal compounds] The polymeric liquid crystal compound of the present invention has the structure shown in formula (1).

[0057] R 1 -C 1 -Ar 1 -M 1 -GM 2 -Ar 2 -C 2 -R 2 (1) In the above formula (1), Ar 1 and Ar 2 Each of the aromatic rings is represented independently by the following formula (Ar-1) or formula (Ar-2), and * indicates the bonding position.

[0058]

[0059] In the formula (Ar-1) or formula (Ar-2), Q represents a hydrogen atom, a straight-chain or branched alkyl group with 1 to 20 carbon atoms, or a cycloalkyl group with 3 to 8 carbon atoms.

[0060] V 1 V 2 and V 3 Each can independently represent a hydrogen atom, a straight-chain or branched alkyl group, a cyano group, a methoxy group, an ethoxy group, a methoxycarbonyl group, or an ethoxycarbonyl group with 1 to 10 carbon atoms.

[0061] W 1 express W 1 The hydrogen atom 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, methoxy, or ethoxy groups having 1 to 20 carbon atoms.

[0062] W 2 It can be represented by the following formula (W-1): J1 -T 1 -*(W-1) In the above formula (W-1), T 1 This refers to a straight-chain or branched alkylene group having 1 to 20 carbon atoms, wherein any one -CH2- or multiple non-adjacent -CH2- groups can be independently replaced by -O-, -COO-, -OCO-, -O-CO-O-, or -C≡C-. From the perspective of suppressing the precipitation of the compound from the solvent, T is preferred. 1 It represents -CH2CH2OCH2CH2OCH2CH2- or -CH2CH2OCH2CH2-.

[0063] J 1 This represents a hydrogen atom or a polymeric group, which is selected from groups of formula (J-1) or formula (J-2) below.

[0064] As a preferred implementation, J 1 The group is selected from the group shown in formula (J-1) or formula (J-2).

[0065] C 1 C 2 M 1 and M 2 Each can be independently represented as -OCH2-, -CH2O-, -COO-, -OCO-, or -O-CO-O-.

[0066] G is selected from the groups represented by the following formulas (G-1) to (G-3).

[0067]

[0068] From the perspective of ease of obtaining raw materials and ease of synthesis, G is preferred. .

[0069] R 1 R is expressed by the following equation (2). 2 It is represented by the following formula (3).

[0070] L 1 -SP 1 -(A 1 -B 1 ) y -*(2) L 2 -SP 2 -(A 2 -B 2 ) z -*(3) Among them, SP1 With SP 2 A 1 With A 2 B 1 With B 2 At least one pair of y and z is different, where SP 1 With SP 2 Forming the first group, A 1 With A 2 Forming the second group, B 1 With B 2 The third group is formed by y and z, and the fourth group is formed by y and z. In these four groups, at least two members in one group are different from each other (i.e., SP). 1 With SP 2 Different; or / and A 1 With A 2 Different; or / and B 1 With B 2 (Different; or / and y is different from z). From the perspective of suppressing crystallization and alignment defects, it is preferable that y and z are different.

[0071] In equations (2) and (3), y and z each independently represent 1 or 2.

[0072] A 1 and A 2 Each can independently represent a single bond, -OCH2-, -CH2O-, -COO-, -OCO-, -O-, or -O-CO-O-. When y is 2, multiple A's... 1 They can be the same or different. When z is 2, multiple A's 2 They can be the same or different.

[0073] B 1 and B 2 Each group is independently selected from the groups represented by formula (G-1) or formula (G-3) above, and when y is 2, multiple B groups... 1 They can be the same or different. When z is 2, multiple Bs 2 They can be the same or different.

[0074] SP 1 and SP 2 Each independently represents a straight-chain or branched alkylene group having 1 to 20 carbon atoms, wherein any one of -CH2- or multiple non-adjacent -CH2- groups can be independently replaced by -O-, -COO-, -OCO-, or -O-CO-O-.

[0075] L 1 and L 2Each of these groups independently represents a polymerizable group, which is selected from the groups represented by formula (J-1) or formula (J-2) above.

[0076] Specifically, as the specific compound represented by general formula (1), compounds represented by the following formulas (R-1) to (R-32) are preferred:

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[0106] There are no particular limitations on the method of manufacturing the compound shown in 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.

[0107] According to another embodiment of this application, a polymeric composition comprising the above-described polymeric liquid crystal compound is also provided, and the "polymeric composition" will be described in detail below.

[0108] [Polymerizable Composition] The polymerizable composition of the present invention is a polymerizable composition containing the polymerizable liquid crystal compound of the present invention described above. In addition to the polymerizable liquid crystal compound of the present invention, it may also contain other polymerizable compounds, photopolymerization initiators, stabilizers, other additives and solvents, etc., as described below.

[0109] [Other polymeric compounds] In addition to the polymerizable liquid crystal compounds of the present invention described above, 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.

[0110]

[0111] .

[0112] In one embodiment, 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 polymeric liquid crystal compound is present in weight parts of 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 parts or any value between these numbers; and the polymeric compound is present in weight parts of 0.1, 0.5, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 parts or any value between these numbers.

[0113] [Photopolymerization initiator] 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 in combination. 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.

[0114] [Stabilizer] To improve its storage stability, a stabilizer is generally required in the polymeric composition. Suitable stabilizers for this invention include, for example, hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, 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 in combination. 2,6-Di-tert-butyl-p-cresol (BHT) is preferably used as a stabilizer.

[0115] [Other adjuvants] 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.

[0116] [solvent] 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 of them alone, or you can use two or more at the same time.

[0117] [Phase difference film] The phase retardation film of the present invention is formed by coating the polymeric composition solution described in the present invention onto a glass substrate having an alignment layer, followed by drying and photocuring. Therefore, the phase retardation film of the present invention comprises a polymer product formed by polymerizing the above-described polymeric composition. The phase difference R450 at a wavelength of 450 nm and the phase difference R550 at a wavelength of 550 nm satisfy the following condition: R450 / R550 < 1.0.

[0118] Example The present invention will be further described below with reference to specific embodiments, but the present invention is not limited to the following embodiments.

[0119] Example 1 The preparation of the compound represented by formula (R-1)

[0120] 2,5-Dihydroxybenzaldehyde (5 g, 36.2 mmol), trans-4-[4-(6-acryloyloxyhexyloxy)phenoxycarbonyl]cyclohexanecarboxylic acid (15.14 g, 36.2 mmol), and 4-dimethylaminopyridine (0.44 g, 3.62 mmol) were dissolved in 100 mL of dichloromethane. N,N'-diisopropylcarbodiimide (5.03 g, 39.82 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 16.6 g of a white solid compound R-1a, in 85% yield.

[0121] Compound R-1a (16.6 g, 30.77 mmol), trans-1,4-cyclohexyldicarboxylate monotert-butyl ester (7.02 g, 30.77 mmol), and 4-dimethylaminopyridine (0.38 g, 3.08 mmol) were dissolved in 100 mL of dichloromethane. N,N'-diisopropylcarbodiimide (4.26 g, 33.85 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 20.25 g of white solid compound R-1b, in 88% yield.

[0122] Compound R-1b (20.25 g, 27.08 mmol) was dissolved in 50 mL of trifluoroacetic acid and 100 mL of dichloromethane, and reacted at room temperature for 2 hours. Dichloromethane was added, followed by washing with water and then saturated brine. The mixture was separated and the organic phase was concentrated. The resulting mixture was subjected to column chromatography and crystallization to give 11.99 g of a white solid, compound R-1c, in 64% yield.

[0123] Compound R-1c (10 g, 14.44 mmol), compound R-1d (7.37 g, 14.44 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (2.77 g, 14.44 mmol), and 4-dimethylaminopyridine (0.18 g, 1.44 mmol) were dissolved in 100 mL of dichloromethane and reacted at room temperature for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 15.4 g of white solid compound R-1e, in 90% yield.

[0124] Compound R-1e (15.4 g, 13 mmol), compound R-1f (8.11 g, 27.3 mmol), and racemic camphorsulfonic acid (6.33 g, 27.3 mmol) were dissolved in 100 mL of chloroform and reacted at 50 °C for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to give 5.89 g of white solid compound R-1g, in 26% yield.

[0125] Compound R-1 g (5.89 g, 3.38 mmol) and N,N-diisopropylethylamine (1.74 g, 13.52 mmol) were dissolved in 50 mL of dichloromethane. Acryloyl chloride (1.22 g, 13.52 mmol) was added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 3.69 g of white solid compound R-1, in 59% yield. 1 H NMR (400 MHz, CDCl3) δ 8.00 (s, 2H), 7.76-7.72 (m, 2H), 7.71-7.64 (m, 4H), 7.37-7.31 (m,2H), 7.20-7.15 (m, 2H), 7.14-7.08 (m, 4H), 6.99 (d, J = 8.6, 4H), 6.88 (d, J =8.5 Hz, 4H), 6.44-6.32 (m, 4H), 6.16-6.04 (m, 4H), 5.85-5.73 (m, 4H), 4.48(t, J = 5.4 Hz, 4H), 4.26-4.15 (m, 8H), 4.02-3.87 (m, 4H), 3.88 (t, J = 5.5 Hz,4H), 3.66-3.56 (m, 12H), 2.79-2.71 (m,2H), 2.70-2.57 (m, 4H), 2.44-2.26 (m,12H), 1.88-1.70 (m, 20H), 1.53-1.44 (m, 4H). Example 2 The preparation of the compound represented by formula (R-5)

[0126] Compound R-1c (2.5 g, 3.61 mmol), compound R-5a (1.51 g, 3.61 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (0.69 g, 3.61 mmol), and 4-dimethylaminopyridine (43 mg, 0.36 mmol) were dissolved in 20 mL of dichloromethane and reacted at room temperature for 12 hours. The resulting mixture was subjected to column chromatography and crystallization to give 1.5 g of white solid compound R-5b, in 38% yield.

[0127] Compounds R-5b (1.5 g, 1.37 mmol), R-1f (0.85 g, 2.88 mmol), and racemic camphorsulfonic acid (0.67 g, 2.88 mmol) were dissolved in 10 mL of chloroform and reacted at 50 °C for 3 hours. The resulting mixture was subjected to column chromatography and crystallization to give 1.49 g of white solid compound R-5c, in 66% yield.

[0128] Compound R-5c (1.49 g, 0.9 mmol) and N,N-diisopropylethylamine (0.46 g, 3.6 mmol) were dissolved in 10 mL of dichloromethane. Acryloyl chloride (0.33 g, 3.6 mmol) was added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 1.06 g of white solid compound R-5, in 67% yield. 1 H NMR (400 MHz, CDCl3) δ8.02-7.99 (m, 2H), 7.75-7.72 (m, 2H), 7.71.7.64 (m, 4H), 7.37-7.31 (m, 2H),7.20-7.15 (m, 2H), 7.13-7.08 (m, 4H), 6.99 (d, J = 9.0 Hz, 2H), 6.88 (d, J =9.0 Hz, 2H), 6.45-6.32 (m, 4H), 6.18-6.03 (m, 4H), 5.87-5.72 (m, 4H), 4.48(t, J = 5.1 Hz, 4H), 4.25-4.10 (m, 10H), 3.95 (t, J = 6.4 Hz, 2H), 3.88 (t, J=5.4 Hz, 4H), 3.66-3.54 (m, 12H), 2.85-2.56 (m, 5H), 2.46-2.12 (m, 13H), 1.87-1.70 (m, 18H), 1.54-1.44 (m, 6H). Example 3 The preparation of the compound represented by formula (R-14)

[0129] Trans-1,4-cyclohexanedicarboxylic acid (156 g, 0.91 mol), 2,5-dihydroxybenzaldehyde (263 g, 1.91 mol), and 4-dimethylaminopyridine (11 g, 0.09 mol) were dissolved in 1.5 L of dichloromethane. N,N'-diisopropylcarbodiimide (252 g, 2 mol) was added dropwise under an ice-water bath, and the reaction was carried out at 30 °C for 48 hours. The resulting mixture was crystallized to give 315 g of a white solid compound R-14a, in 84% yield.

[0130] Compound R-14a (20 g, 48.54 mmol), trans-4-[4-(6-acryloyloxyhexyloxy)phenoxycarbonyl]cyclohexanecarboxylic acid (10.14 g, 24.27 mmol), and 4-dimethylaminopyridine (0.3 g, 2.43 mmol) were dissolved in 200 mL of dichloromethane. N,N'-diisopropylcarbodiimide (3.36 g, 26.7 mmol) was 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 15 g of white solid compound R-14b, in 76% yield.

[0131] Compound R-14b (8 g, 9.85 mmol), trans-4-[4-(4-acryloyloxybutoxy)phenoxycarbonyl]cyclohexanecarboxylic acid (3.84 g, 9.85 mmol), and 4-dimethylaminopyridine (0.12 g, 0.99 mmol) were dissolved in 100 mL of dichloromethane. N,N'-diisopropylcarbodiimide (1.37 g, 10.84 mmol) was 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 10.5 g of white solid compound R-14c, in 90% yield.

[0132] Compounds R-14c (10.5 g, 8.86 mmol), R-1f (5.53 g, 18.61 mmol), and racemic camphorsulfonic acid (4.11 g, 17.72 mmol) were dissolved in 150 mL of chloroform and reacted at 50 °C for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 10 g of white solid compound R-14d, in 65% yield.

[0133] Compound R-14d (10 g, 5.73 mmol) and N,N-diisopropylethylamine (2.96 g, 22.92 mmol) were dissolved in 100 mL of dichloromethane. Acryloyl chloride (2.07 g, 22.92 mmol) was added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 8.85 g of white solid compound R-14, in 83% yield. 1 H NMR (400 MHz, CDCl3) δ 8.00 (s, 2H), 7.76 (d, J = 2.2 Hz, 2H), 7.71-7.65 (m, 4H), 7.37-7.31(m, 2H), 7.20-7.08 (m, 6H), 6.98 (d, J = 8.9, 4H), 6.88 (d, J = 8.8 Hz, 4H),6.45-6.33 (m, 4H), 6.17-6.04 (m, 4H), 5.86-5.73 (m, 4H), 4.48 (t, J = 5.5 Hz,4H), 4.27-4.22 (m, 2H), 4.22-4.15 (m, 6H), 4.01-3.92 (m, 4H), 3.89 (t, J = 5.6Hz, 4H), 3.67-3.56 (m, 12H), 2.77-2.66 (m,4H), 2.65-2.56 (m, 2H), 2.43-2.27(m, 12H), 1.91-1.86 (m, 4H), 1.84-1.65 (m, 16H), 1.55-1.42 (m, 4H). Example 4 Preparation of the compound represented by formula (R-15)

[0134] Compound R-14b (7 g, 8.62 mmol), 4-(6-(acryloyloxy)hexyloxy)benzoic acid (3.78 g, 12.93 mmol), and 4-dimethylaminopyridine (0.21 g, 1.72 mmol) were dissolved in 100 mL of dichloromethane. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (2.46 g, 12.93 mmol) was added in portions, and the mixture was reacted at room temperature for 12 hours. The resulting mixture was crystallized to give 4.7 g of a white solid, compound R-15a, in 50% yield.

[0135] Compounds R-15a (4.7 g, 4.32 mmol), R-1f (2.82 g, 9.5 mmol), and racemic camphorsulfonic acid (2 g, 8.64 mmol) were dissolved in 50 mL of chloroform and reacted at 55 °C for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 3.3 g of white solid compound R-15b, in 46% yield.

[0136] Compound R-15b (3.3 g, 2.01 mmol) was dissolved in 40 mL of dichloromethane with N,N-diisopropylethylamine (1.04 g, 8.04 mmol). Acryloyl chloride (0.73 g, 8.04 mmol) was added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 2.7 g of white solid compound R-15, in 78% yield. 1 H NMR (400 MHz, CDCl3) δ 8.19 (d, J = 8.8 Hz, 2H), 8.12 (s, 1H), 8.01 (s, 1H), 7.78 (dd, J =8.5, 2.2 Hz, 2H), 7.72-7.62 (m, 4H), 7.37-7.30 (m, 2H), 7.26-7.25 (m, 1H), 7.20-7.09 (m, 5H), 7.04-6.96 (m, 4H), 6.90-6.86 (m, 2H), 6.45-6.33 (m, 4H), 6.18-6.04 (m, 4H), 5.85-5.74 (m, 4H), 4.49 (t, J = 5.5 Hz, 2H), 4.42 (t, J =5.5 Hz, 2H), 4.23-4.12 (m, 8H), 4.07 (t, J = 6.4 Hz, 2H), 3.95 (t, J= 6.4 Hz, 2H), 3.89 (t, J = 5.5 Hz, 2H), 3.78 (t, J = 5.5 Hz, 2H), 3.66-3.52 (m, 8H), 3.45-3.40 (m, 4H), 2.75-2.57 (m, 4H), 2.45-2.27 (m, 8H), 1.91-1.65 (m, 16H), 1.54-1.42 (m, 8H). Example 5 Preparation of the compound represented by formula (R-17)

[0137] R-14b (4 g, 4.93 mmol), trans-4-[4-(acryloyloxy)butoxycarbonyl]cyclohexanecarboxylic acid (1.47 g, 4.93 mmol), and 4-dimethylaminopyridine (60 mg, 0.49 mmol) were dissolved in 100 mL of dichloromethane. N,N'-diisopropylcarbodiimide (0.68 g, 5.42 mmol) was added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to give 1.89 g of a white solid, R-17a, in 35% yield.

[0138] Compounds R-17a (1.89 g, 1.72 mmol), R-1f (1.07 g, 3.61 mmol), and racemic camphorsulfonic acid (0.8 g, 3.44 mmol) were dissolved in 60 mL of chloroform and reacted at 70 °C for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to give 2.48 g of white solid compound R-17b, in 87% yield.

[0139] Compound R-17b (2.48 g, 1.5 mmol) was dissolved in 40 mL of dichloromethane with N,N-diisopropylethylamine (0.77 g, 6 mmol). Acryloyl chloride (0.54 g, 6 mmol) was added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 1 hour. The resulting mixture was subjected to column chromatography and crystallization to give 2 g of white solid compound R-17, in 76% yield. 1H NMR (400 MHz, CDCl3) δ8.01 (s, 1H), 7.99 (s, 1H) 7.77-7.74 (m, 2H), 7.72-7.65 (m, 4H), 7.39-7.31(m, 2H), 7.20-7.15 (m, 2H), 7.15-7.07 (m, 4H), 7.00-6.96 (m, 2H), 6.90-6.86(m, 2H), 6.45-6.34 (m, 4H), 6.17-6.05 (m, 4H), 5.87-5.74 (m, 4H), 4.51-4.45(m, 4H), 4.24-4.11 (m, 10H), 3.97-3.93 (m, 2H), 3.91-3.86 (m, 4H), 3.66-3.55(m, 12H), 2.72-2.65 (m, 5H), 2.40-2.27 (m, 11H), 2.20-2.12 (m, 2H), 1.82-1.64(m, 18H), 1.56-1.40(m, 6H). Example 6 Preparation of the compound represented by formula (R-19)

[0140] Compound R-14a (20 g, 48.54 mmol), trans-4-[4-(acryloyloxy)butoxycarbonyl]cyclohexanecarboxylic acid (7.24 g, 24.27 mmol), and 4-dimethylaminopyridine (0.3 g, 2.43 mmol) were dissolved in 200 mL of dichloromethane. N,N'-diisopropylcarbodiimide (3.06 g, 24.27 mmol) was 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 12.4 g of white solid compound R-19a, in 74% yield.

[0141] Compound R-19a (12.4 g, 17.92 mmol), trans-4-[6-(acryloyloxy)hexyloxycarbonyl]cyclohexanecarboxylic acid (5.84 g, 17.92 mmol), and 4-dimethylaminopyridine (0.22 g, 1.79 mmol) were dissolved in 100 mL of dichloromethane. N,N'-diisopropylcarbodiimide (2.48 g, 19.71 mmol) was 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 13.6 g of white solid compound R-19b, in 76% yield.

[0142] Compounds R-19b (13.6 g, 13.59 mmol), R-1f (8.48 g, 28.54 mmol), and racemic camphorsulfonic acid (6.31 g, 27.18 mmol) were dissolved in 150 mL of chloroform and reacted at 50 °C for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 19 g of white solid compound R-19c, in 90% yield.

[0143] Compound R-19c (19 g, 12.18 mmol) and N,N-diisopropylethylamine (6.28 g, 48.72 mmol) were dissolved in 100 mL of dichloromethane. Acryloyl chloride (4.41 g, 48.72 mmol) was added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 17.2 g of white solid compound R-19, in 85% yield. 1 H NMR (600MHz, CDCl3) δ 8.03 (s, 2H), 7.79 (d, J = 2.5 Hz, 2H), 7.80-7.70 (m, 4H), 7.41-7.36 (m, 2H), 7.24-7.16 (m, 2H), 7.17-7.11 (m, 4H), 6.48-6.38 (m, 4H), 6.20-6.09 (m, 4H), 5.90-5.79 (m, 4H), 4.52 (t, J = 5.3 Hz, 4H), 4.27-4.21 (m, 8H), 4.20-4.16 (m, 4H), 3.92 (t, J = 5.5 Hz, 4H), 3.68-3.64 (m, 8H), 3.63-3.59 (m,4H), 2.76-2.66 (m, 4H), 2.44-2.37 (m, 6H), 2.36-2.30 (m, 4H), 2.23-2.16 (m,4H), 1.83-1.50 (m, 20H), 1.38-1.32 (m, 4H). Example 7 Preparation of the compound represented by formula (R-20)

[0144] Compounds R-17a (7 g, 6.4 mmol), R-20a (3.94 g, 13.45 mmol), and racemic camphorsulfonic acid (2.97 g, 12.8 mmol) were dissolved in 50 mL of chloroform and reacted at 50 °C for 2 hours. The resulting mixture was subjected to column chromatography to give 5 g of brown colloidal compound R-20b, in 48% yield.

[0145] Compound R-20b (5 g, 3.04 mmol) was dissolved in 40 mL of dichloromethane with N,N-diisopropylethylamine (1.57 g, 12.16 mmol). Acryloyl chloride (1.10 g, 12.16 mmol) was added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 1 hour. The resulting mixture was subjected to column chromatography to give 3.4 g of a yellow oily compound R-20, in 64% yield. 1 H NMR (400 MHz, CDCl3) δ 7.77-7.74 (m, 2H), 7.71-7.64 (m, 6H), 7.36-7.32 (m, 2H), 7.19-7.14 (m, 2H), 7.14-7.09 (m, 4H), 7.00-6.95 (m, 2H), 6.90-6.86 (m, 2H), 6.44-6.35 (m, 4H), 6.17-6.05 (m, 4H), 5.86-5.77 (m, 4H), 4.35-4.27 (m, 4H), 4.23-4.09 (m, 10H), 3.94(t, J = 6.4 Hz, 2H), 2.72-2.58 (m, 5H), 2.40-2.24 (m, 11H), 2.19-2.13 (m, 2H), 1.78-1.25 (m, 48H). Example 8 The preparation of the compound represented by formula (R-21)

[0146] Compounds R-17a (7 g, 6.4 mmol), R-21a (3.4 g, 13.45 mmol), and racemic camphorsulfonic acid (2.97 g, 12.8 mmol) were dissolved in 50 mL of chloroform and reacted at 50 °C for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 5.3 g of white solid compound R-21b, in 53% yield.

[0147] Compound R-21b (5.3 g, 3.39 mmol) was dissolved in 40 mL of dichloromethane with N,N-diisopropylethylamine (1.75 g, 13.56 mmol). Acryloyl chloride (1.23 g, 13.56 mmol) was added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 4.5 g of white solid compound R-21, in 79% yield. 1 H NMR (400 MHz, CDCl3) δ 8.04 (m, 1H), 8.03 (m, 1H), 7.77-7.73 (m, 2H), 7.72-7.66 (m, 4H), 7.38-7.32 (m, 2H), 7.21-7.16 (m, 2H), 7.13-7.07 (m, 4H), 6.98 (d, J = 9.0 Hz, 2H), 6.88 (d, J = 9.1 Hz, 2H), 6.45-6.38 (m, 2H), 6.31-6.24 (m, 2H), 6.18-6.09(m, 2H), 5.98-5.90 (m, 2H), 5.86-5.80 (m, 2H), 5.72-5.66 (m, 2H), 4.51-4.46(m, 4H), 4.27-4.12 (m, 10H), 3.97-3.89 (m, 6H), 3.74-3.68 (m, 4H), 2.74-2.58(m, 5H), 2.42-2.26 (m, 11H), 2.19-2.12 (m, 2H), 1.82-1.64 (m, 18H), 1.62–1.46 (m, 6H). Example 9 The preparation of the compound represented by formula (R-23)

[0148] (trans,trans)-[1,1'-bicyclohexane]-4,4'-dicarboxylic acid (13.7 g, 53.94 mmol), 2,5-dihydroxybenzaldehyde (15.63 g, 113.27 mmol), and 4-dimethylaminopyridine (1.32 g, 10.79 mmol) were dissolved in 150 mL of dichloromethane. N,N'-diisopropylcarbodiimide (14.28 g, 113.27 mmol) was added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 6 hours. The resulting mixture was crystallized to give 24.4 g of a white solid compound R-23a, in 92% yield.

[0149] Compound R-23a (24.4 g, 49.39 mmol), trans-4-[4-(6-acryloyloxyhexyloxy)phenoxycarbonyl]cyclohexanecarboxylic acid (10.32 g, 24.70 mmol), and 4-dimethylaminopyridine (0.3 g, 2.47 mmol) were dissolved in 200 mL of dichloromethane. N,N'-diisopropylcarbodiimide (3.42 g, 27.17 mmol) was 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 16.1 g of white solid compound R-23b, in 73% yield.

[0150] Compound R-23b (16.1 g, 17.99 mmol), trans-4-[4-(acryloyloxy)butoxycarbonyl]cyclohexanecarboxylic acid (5.36 g, 17.99 mmol), and 4-dimethylaminopyridine (0.22 g, 1.8 mmol) were dissolved in 100 mL of dichloromethane. N,N'-diisopropylcarbodiimide (2.49 g, 19.79 mmol) was 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 11.4 g of white solid compound R-23c, in 54% yield.

[0151] Compounds R-23c (11.4 g, 9.7 mmol), R-1f (6.05 g, 20.37 mmol), and racemic camphorsulfonic acid (4.5 g, 19.4 mmol) were dissolved in 150 mL of chloroform and reacted at 50 °C for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 12.7 g of white solid compound R-23d, in 75% yield.

[0152] Compound R-23d (12.7 g, 7.32 mmol) and N,N-diisopropylethylamine (3.78 g, 29.28 mmol) were dissolved in 100 mL of dichloromethane. Acryloyl chloride (2.65 g, 22.92 mmol) was added dropwise under an ice-water bath, and the reaction was carried out at room temperature for 2 hours. The resulting mixture was subjected to column chromatography and crystallization to give 9.9 g of white solid compound R-23, in 73% yield. 1H NMR (400 MHz, CDCl3) δ 8.00 (s, 1H), 7.99 (s, 1H) 7.78-7.74 (m, 2H), 7.72-7.65 (m, 4H), 7.39-7.30 (m, 2H), 7.20-7.16 (m, 2H), 7.14-7.07 (m, 4H), 7.00-6.96 (m, 2H),6.90-6.86 (m, 2H), 6.45-6.34 (m, 4H), 6.17-6.05 (m, 4H), 5.87-5.73 (m, 4H),4.52-4.45 (m, 4H), 4.23-4.10 (m, 10H), 3.98-3.93 (m, 2H), 3.91-3.85 (m, 4H), 3.66-3.53 (m, 12H), 2.72-2.55 (m, 5H), 2.39-2.27 (m, 11H), 2.20-2.12 (m, 2H),1.97-1.60 (m, 22H), 1.56-1.40 (m, 6H), 1.29-1.11 (m, 6H). Example 10 The preparation of the compound represented by formula (R-31)

[0153] Compounds R-17a (7 g, 6.4 mmol), R-31a (3.59 g, 13.45 mmol), and racemic camphorsulfonic acid (2.97 g, 12.8 mmol) were dissolved in 50 mL of chloroform and reacted 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-31, in 59% yield. 1 H NMR (400 MHz, CDCl3) δ 8.08-8.05 (m,2H), 7.77-7.69 (m, 6H), 7.37-7.32 (m, 2H), 7.21-7.16 (m, 2H), 7.14-7.11 (m,4H), 6.98 (d, J = 9.0 Hz, 2H), 6.88 (d, J= 9.0 Hz, 2H), 6.45-6.37 (m, 2H), 6.18-6.08 (m, 2H), 5.87-5.80 (m, 2H), 4.55-4.48 (m, 4H), 4.22-4.14 (m, 4H), 3.98-3.86 (m, 6H), 3.65-3.60 (m, 4H), 3.53-3.45 (m, 4H), 3.35-3.27 (m, 8H), 2.75-2.60 (m, 5H), 2.45-2.30 (m, 11H), 2.21-2.12 (m, 2H), 1.83-1.70 (m, 18H),1.60-1.41 (m, 6H). Comparative Example 1 The compound represented by formula (X-1)

[0154] Comparative Example 2 The compound represented by formula (X-2)

[0155] Comparative Example 3 The compound represented by formula (X-3)

[0156] Comparative Example 4 The compound represented by formula (X-4)

[0157] [Precipitation] The precipitation properties of the compounds represented in Examples 1 to 10 and Comparative Examples 1 to 4 (i.e., the test compounds) were determined using the methods shown below. The results are shown in Table 1 below.

[0158] Specifically, weigh 1 g of the test compound and 4 g of cyclohexanone into a 30 mL sample vial. Heat and sonicate thoroughly until the solution is clear and transparent. Let stand at room temperature and observe for precipitation.

[0159] A: No precipitation after 168 hours B: Precipitation within 168 hours C: Precipitation within 72 hours D: Precipitation within 24 hours Table 1

[0160] Note: In Table 1, "-" indicates that R cannot be defined because the X-4 compound does not conform to the general structural formula (1) in this application. 1 With R 2 . [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, to obtain a phase difference film.

[0161] Table 2

[0162] For the fabricated retardation film, the phase difference at various wavelengths was measured using an Axoscan polarimeter. The phase difference R450 at 450 nm and R550 at 550 nm were recorded. The ratio R450 / R550 was calculated and evaluated according to the following criteria. The results are shown in Table 3 below, where a smaller R450 / R550 ratio indicates better inverse wavelength dispersion.

[0163] A: R450 / R550 is less than or equal to 0.8 B: R450 / R550 is greater than 0.8 and less than or equal to 0.85 C: R450 / R550 is greater than 0.85 and less than or equal to 0.9 D: R450 / R550 is greater than 0.9 [Alignment Defect] 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.

[0164] A: No defects B: 1 to 10 C: 11-100 D: The entire surface has alignment defects (>100). [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.

[0165] A: No crystallization B: Localized small-scale crystallization C: Extensive crystallization D: Dense crystallization across the entire surface Table 3

[0166] Note: In Table 3, "-" indicates that R cannot be defined because the X-4 compound does not conform to the general structural formula (1) in this application. 1 With R 2 . As shown in Table 1, the precipitation properties of the polymeric liquid crystal compounds provided by this invention are generally superior to those of the comparative examples. In particular, Examples 12 (R-5), 15 (R-17), 18 (R-21), and 19 (R-23) achieved the optimal Grade A, indicating a significant improvement in the precipitation properties of the polymeric liquid crystal compounds in solvents provided by this invention. Furthermore, as shown in Table 3, the phase retardation film formed by the polymeric liquid crystal compounds provided by this invention exhibits excellent reverse wavelength dispersion, while alignment defects and crystallinity are significantly improved. Among these, R... 1 With R 2 The more significant the structural differences between molecules, i.e., the lower the molecular symmetry (e.g., R-5, R-17, R-21, R-23), the more pronounced the improvement in precipitation properties, alignment defects, and crystallinity.

[0167] As can be seen from the data in Tables 1 and 3, the polymerizable liquid crystal compound provided in this application simultaneously possesses excellent reverse wavelength dispersibility, improved precipitation properties, improved film crystallinity, and improved film alignment defects. In contrast, the compounds in the comparative examples cannot simultaneously possess the above properties. For example, although compound X-4 has acceptable precipitation properties, it has poor reverse wavelength dispersibility and many alignment defects.

[0168] In summary, the present invention provides a non-precipitating polymeric liquid crystal compound for forming a retardation film with excellent reverse wavelength dispersion. The retardation film prepared from a polymeric composition containing the polymeric liquid crystal compound of the present invention is less prone to alignment defects and crystallization during manufacturing, and exhibits excellent reverse wavelength dispersion.

[0169] The embodiments of this application have been described above, but this application is not limited to the specific embodiments described above. The specific embodiments described above are merely illustrative and not restrictive. Those skilled in the art can make many other forms under the guidance of this application without departing from the spirit and scope of the claims, and all of these forms are within the protection scope of this application.

Claims

1. A polymerizable liquid crystal compound, characterized in that, The structural formula of the polymeric liquid crystal compound is shown in the following formula (1): R 1 -C 1 -Ar 1 -M 1 -G-M 2 -Ar 2 -C 2 -R 2 (1) In equation (1), Ar 1 and Ar 2 Each of these independently represents an aromatic ring represented by either formula (Ar-1) or formula (Ar-2), with * indicating a bonding position. In formula (Ar-1) or formula (Ar-2), Q represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms. V 1 V 2 and V 3 Each can independently represent a hydrogen atom, a straight-chain or branched alkyl group, cyano group, methoxy group, ethoxy group, methoxycarbonyl group, or ethoxycarbonyl group having 1 to 10 carbon atoms. W 1 express W 1 The hydrogen atom 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, methoxy, or ethoxy groups having 1 to 20 carbon atoms. W 2 Represented by the following formula (W-1), J 1 -T 1 -*(W-1) In the above formula (W-1), T 1 This refers to a straight-chain or branched alkylene group having 1 to 20 carbon atoms, wherein any one -CH2- or multiple non-adjacent -CH2- groups can be independently replaced by -O-, -COO-, -OCO-, -O-CO-O-, or -C≡C-. J 1 This 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) below. C 1 C 2 M 1 and M 2 Each can be independently represented as -OCH2-, -CH2O-, -COO-, -OCO-, or -O-CO-O-. G is selected from the groups represented by the following formulas (G-1) to (G-3). R 1 R is expressed by the following equation (2). 2 It is represented by the following formula (3), L 1 -SP 1 -(A 1 -B 1 ) y -*(2) L 2 -SP 2 -(A 2 -B 2 ) z -*(3) Among them, SP 1 With SP 2 A 1 With A 2 B 1 With B 2 At least one pair of y and z is different. In equations (2) and (3), y and z each independently represent 1 or 2. A 1 and A 2 Each can independently represent a single bond, -OCH2-, -CH2O-, -COO-, -OCO-, -O-, or -O-CO-O-. When y is 2, multiple A's... 1 They can be the same or different. When z is 2, multiple A's 2 They may be the same or different. B 1 and B 2 Each group is independently selected from the groups represented by formula (G-1) or formula (G-3) above, and when y is 2, multiple B groups... 1 They can be the same or different; when z is 2, multiple Bs 2 They may be the same or different. 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- groups can be independently replaced by -O-, -COO-, -OCO-, or -O-CO-O-. L 1 and L 2 Each of the above formulas (J-1) or (J-2) represents a polymerizable group.

2. The polymerizable liquid crystal compound according to claim 1, characterized in that, J 1 Selected from the groups represented by formula (J-1) or formula (J-2).

3. The polymerizable liquid crystal compound according to claim 1, characterized in that, y is different from z.

4. The polymerizable liquid crystal compound according to claim 1, characterized in that, T 1 Selected from -CH2CH2OCH2CH2OCH2CH2- or -CH2CH2OCH2CH2-.

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 liquid crystal compound comprising any one of claims 1 to 5.

7. The polymerizable composition according to claim 6, characterized in that, The polymerizable composition further comprises a polymerizable compound; The polymerizable compound is selected from the following structures: 。 8. The polymerizable composition according to claim 6, 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, The phase difference film comprises a polymer product formed by polymerizing the polymeric composition according to any one of claims 6 to 8.

10. The phase retardation film according to claim 9, characterized in that, The phase difference R450 of the phase retardation film at a wavelength of 450 nm and the phase difference R550 at a wavelength of 550 nm satisfy the following: R450 / R550 < 1.0.

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