A polymerizable compound, formation of polymerizable compounds, and their use in negative dispersion optical film materials

Abstract

The application discloses a polymerizable compound, a polymerizable compound formed by the same and application of the polymerizable compound in a negative dispersion optical film material, and belongs to the technical field of optical materials. The polymerizable compound is selected from compounds shown in a general formula (1). The polymerizable compound has a wide-band type ideal wavelength dispersion. The application further provides a polymerizable compound composition, which effectively modifies optical performance of the polymerizable compound, so that the polymerizable compound has a wide-band type ideal wavelength dispersion. The polymerizable compound and the polymerizable compound composition can be applied to the negative dispersion optical film material.

Description

Technical Field

[0001] This invention relates to a polymerizable compound, the formation of polymerizable compounds therefrom, and their application in negative dispersion optical film materials, belonging to the field of optical materials technology. Background Technology

[0002] Polymerizable compounds (RMs) are raw materials for preparing various optical anisotropies. Typically, an RM solution is coated onto a substrate to orient it, and after curing, an optical anisotropy polymer film with a uniform orientation is formed, which is an optical anisotropy. The orientation of the film can be planar (the liquid crystal molecules are basically parallel to the layer orientation), vertical (rectangular or perpendicular to the layer), or inclined, or it can be cholesteric phase orientation. Therefore, RM raw materials have attracted widespread attention.

[0003] Depending on the application field, optical anisotropic materials include, but are not limited to, birefringent films, optical retardation films (phase difference films), negative dispersion optical films, optical compensation films, visual magnification films, reflective films, selective reflection films, antireflective films, brightness enhancement films, liquid crystal alignment films, polarizing films (deflection plates), polarizing elements, circular polarizing elements, elliptical polarizing elements, and various other optical elements.

[0004] Negative dispersion optical films control optical anisotropy by optically compensating for the dispersion caused by different wavelengths of light propagating in a medium, thereby improving optical efficiency and increasing the viewing angle. However, because negative dispersion optical films exhibit wavelength dispersion relative to phase difference, light of different wavelengths experiences varying degrees of phase delay when passing through them.

[0005] Therefore, in order to solve the above-mentioned technical problems, it is necessary to provide a polymerizable compound, the formation of polymerizable compounds, and their application in negative dispersion optical film materials. Summary of the Invention

[0006] To address at least one problem existing in the prior art, the present invention provides a polymerizable compound having ideal wavelength dispersion with a wide bandwidth, and also provides a polymerizable compound composition that effectively modifies the optical properties of the liquid to give it ideal wavelength dispersion with a wide bandwidth. Both the polymerizable compound and the polymerizable compound composition can be applied to negative dispersion optical film materials, thus solving the above-mentioned problem.

[0007] To achieve the above objectives, the present invention adopts the following technical solution: a polymerizable compound, wherein the polymerizable compound is selected from compounds represented by general formula (1), (1) In the formula, P1 and P2 each independently represent polymerizable groups; L1 and L2 each independently represent a single bond or an alkylene group with 1 to 30 carbon atoms; R1 represents hydrogen atom, alkyl group with 1-30 carbon atoms, haloalkyl group with 1-30 carbon atoms, alkoxy group with 1-30 carbon atoms, haloalkoxy group with 1-30 carbon atoms, alkoxycarbonyl group with 1-30 carbon atoms, haloalkoxycarbonyl group with 1-30 carbon atoms, alkylcarbonyl group with 1-30 carbon atoms, haloalkylcarbonyl group with 1-30 carbon atoms, alkylacyloxy group with 1-30 carbon atoms, haloalkylacyloxy group with 1-30 carbon atoms, and group with 2-30 carbon atoms. Alkenyl, haloalkenyl with 2 to 30 carbon atoms, alkenoxy with 2 to 30 carbon atoms, haloalkenoxy with 2 to 30 carbon atoms, alkylaryl with 6 to 30 carbon atoms, arylalkyl with 6 to 30 carbon atoms, alkylaryloxy with 6 to 30 carbon atoms, arylalkyloxy with 6 to 30 carbon atoms, arylcarbonyl with 6 to 30 carbon atoms, arylcarbonyloxy with 6 to 30 carbon atoms, or aryloxycarbonyloxy with 6 to 30 carbon atoms; R2 represents hydrogen atom, halogen, cyano, hydroxyl, nitro, carboxyl, carbamoyloxy, amino, aminosulfonyl, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, thioisocyanate, alkyl with 1 to 30 carbon atoms, haloalkyl with 1 to 30 carbon atoms, alkoxy with 1 to 30 carbon atoms, haloalkoxy with 1 to 30 carbon atoms, alkoxycarbonyl with 1 to 30 carbon atoms, haloalkoxycarbonyl with 1 to 30 carbon atoms, alkylcarbonyl with 1 to 30 carbon atoms, haloalkylcarbonyl with 1 to 30 carbon atoms, alkylacyloxy with 1 to 30 carbon atoms, haloalkylacyloxy with 1 to 30 carbon atoms, alkenyl with 2 to 30 carbon atoms, haloalkenyl with 2 to 30 carbon atoms, alkenyloxy with 2 to 30 carbon atoms, or haloalkenyloxy with 2 to 30 carbon atoms.

[0008] Preferably, the polymerizable group represented by P1 or P2 is selected from groups shown in general formulas (P-1), (P-2), (P-3), (P-4), (P-5), (P-6), (P-7), (P-8), (P-9), (P-10), (P-11), or (P-12). ' In the formula, R3 independently represents hydrogen atom, halogen, cyano, hydroxyl, nitro, carboxyl, carbamoyloxy, amino, aminosulfonyl, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, thioisocyanate, cyano, alkyl with 1 to 30 carbon atoms, haloalkyl with 1 to 30 carbon atoms, alkoxy with 1 to 30 carbon atoms, haloalkoxy with 1 to 30 carbon atoms, alkoxycarbonyl with 1 to 30 carbon atoms, haloalkoxycarbonyl with 1 to 30 carbon atoms, alkylcarbonyl with 1 to 30 carbon atoms, haloalkylcarbonyl with 1 to 30 carbon atoms, alkylacyloxy with 1 to 30 carbon atoms, haloalkylacyloxy with 1 to 30 carbon atoms, alkenyl with 2 to 30 carbon atoms, haloalkenyl with 2 to 30 carbon atoms, alkenoxy with 2 to 30 carbon atoms, or haloalkenoxy with 2 to 30 carbon atoms.

[0009] Preferably, the polymerizable group represented by P1 or P2 is selected from the groups described in general formula (P-1) and general formula (P-2).

[0010] Preferably, the polymerizable group represented by P1 or P2 is selected from the group described in general formula (P-1).

[0011] Preferably, one or more of the -CH2- in the alkylene group represented by L1 or L2 are replaced by -O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, or -COS-. Preferably, R1 represents an alkyl group having 1 to 10 carbon atoms, an alkylaryl group having 6 to 10 carbon atoms, or an arylalkyl group having 6 to 10 carbon atoms.

[0012] Preferably, R1 represents an alkyl group having 1 to 10 carbon atoms.

[0013] Preferably, one or more of the -CH2- groups among alkyl, alkoxy, alkenyl, and alkenyloxy groups represented by R1 are replaced by -O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, or -COS-.

[0014] Preferably, one or more of the -CH2- in the alkyl group represented by R1 are substituted with -O-.

[0015] Preferably, one or more H atoms in the alkyl, alkoxy, alkenyl, or alkenyloxy group represented by R1 are substituted by a halogen, cyano, hydroxyl, nitro, carboxyl, carbamoyloxy, amino, aminosulfonyl, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, thioisocyano, alkyl with 1 to 30 carbon atoms, haloalkyl with 1 to 30 carbon atoms, alkoxy with 1 to 30 carbon atoms, haloalkoxy with 1 to 30 carbon atoms, alkylacyloxy with 1 to 30 carbon atoms, or haloalkylacyloxy with 1 to 30 carbon atoms or a polymerizable group.

[0016] Preferably, one or more H atoms in the alkyl group represented by R1 are substituted with halogen, cyano, hydroxyl, nitro, carboxyl, alkyl group with 1 to 10 carbon atoms, haloalkyl group with 1 to 10 carbon atoms, alkoxy group with 1 to 10 carbon atoms, haloalkoxy group with 1 to 10 carbon atoms, alkylacyloxy group with 1 to 10 carbon atoms, or haloalkylacyloxy group with 1 to 10 carbon atoms or polymerizable groups.

[0017] Preferably, one or more H atoms in the alkyl group represented by R1 are replaced by hydroxyl groups, alkyl groups having 1 to 10 carbon atoms, or polymerizable groups.

[0018] Preferably, R2 represents a hydrogen atom, halogen, cyano, hydroxyl, nitro, carboxyl, carbamoyloxy, amino, alkyl with 1 to 10 carbon atoms, haloalkyl with 1 to 10 carbon atoms, alkoxy with 1 to 10 carbon atoms, or haloalkoxy with 1 to 10 carbon atoms.

[0019] Preferably, R2 represents a hydrogen atom.

[0020] In addition, the present invention provides a polymerizable compound comprising the polymerizable compound of the above general formula (1) and at least one additional polymerizable compound.

[0021] Preferably, the additional polymerizable compound is selected from compounds of general formula (B-1) or general formula (B-2).

[0022] .

[0023] Preferably, in the polymerizable compound composition, the polymerizable compound of general formula (1) is added in an amount of not less than 30 wt%.

[0024] Preferably, in the polymerizable compound composition, the polymerizable compound of general formula (1) is added in an amount of not less than 40 wt%.

[0025] Preferably, in the polymerizable compound composition, the polymerizable compound of general formula (1) is added in an amount of not less than 50 wt%.

[0026] Preferably, in the polymerizable compound composition, the polymerizable compound of general formula (1) is added in an amount of not less than 60 wt%.

[0027] Preferably, the polymerizable compound composition also includes additives.

[0028] Preferably, the additive is added to the polymerizable compound composition in an amount of 0.01 to 10 wt%; more preferably 0.02 to 8 wt%; more preferably 0.05 to 5 wt%; and most preferably 0.1 to 3 wt%.

[0029] Preferably, the additives include, but are not limited to, one or more of the following: polymerization initiators, sensitizers, sensitizers, stabilizers, leveling agents, surfactants, polymerization inhibitors, antioxidants, colorants, dispersants, lubricants, hydrophobic agents, adhesives, flow improvers, defoamers, degassing agents, diluents, thixotropic agents, gelling agents, catalysts, metals, metal complexes, luminescent materials, etc.

[0030] In another aspect, the present invention also provides a polymerizable composition solution comprising the polymerizable composition described in the context and an organic solvent.

[0031] Preferably, the organic solvent has good solubility in the polymerizable composition and can be removed by drying below 100°C.

[0032] Preferably, the organic solvent includes, but is not limited to, and is not particularly limited to, organic solvents that exhibit good solubility for polymerizable compounds, preferably aromatic solvents such as toluene, xylene, cumene, and mesitylene; ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone; ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane, and anisole; amide solvents such as N,N-dimethylformamide and N-methyl-2-pyrrolidone; propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, γ-butyrolactone, and chlorobenzene; the organic solvent can be used alone or in combination of two or more.

[0033] Preferably, the organic solvent is one or more of ketone solvents, ether solvents, ester solvents, and aromatic solvents.

[0034] Preferably, the organic solvent is cyclopentanone.

[0035] Preferably, the organic solvent content in the polymerizable composition solution is 30-95 wt%; more preferably 40-90 wt%; more preferably 50-85 wt%; and most preferably 60-80 wt%.

[0036] In preparing a polymerizable composition solution, heating and / or stirring are advantageously performed to promote the dissolution of the polymerizable composition.

[0037] In another aspect, the present invention also provides a negative dispersion optical film material, comprising a substrate and a polymer film formed by curing a polymerizable composition solution as described in the context, and an orientation film present as needed.

[0038] Preferably, the substrate includes, but is not limited to, a glass substrate, a metal substrate, a ceramic substrate, or a polymer substrate, which is selected by sequentially stacking an orientation film as required and a polymer film formed by curing a polymerizable composition solution to form an optical anisotropy.

[0039] Preferably, the polymer substrate is a cellulose derivative, polyolefin, polyester, polyolefin, polycarbonate, polyacrylate, polyarylate, polyethersulfone, polyamide, polyimide, polyphenylene sulfide, polyphenylene ether, or polystyrene, etc.

[0040] Preferably, the polymer substrate is a polyester, polystyrene, polyolefin, cellulose derivative, polyarylate, or polycarbonate substrate, based on the process applicability of optical anisotropy, especially considering heat resistance and chemical stability.

[0041] Preferably, the orientation film includes, but is not limited to, orientation films made of polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyethersulfone, epoxy resin, acrylic resin, epoxy acrylic resin, coumarin, chalcone, cinnamate, anthraquinone, azo compounds, aryl vinyl compounds, etc.

[0042] Preferably, the orientation treatment of the orientation film is a stretching treatment, a friction treatment, polarized ultraviolet-visible light irradiation, or an ion beam treatment.

[0043] Preferably, the orientation treatment of the orientation film is a rubbing treatment or polarized ultraviolet-visible light irradiation.

[0044] Preferably, the method for preparing the negative dispersion optical film material includes a coating method.

[0045] Preferably, the coating method includes coating applicator method, bar coating method, spin coating method, gravure printing method, flexographic printing method, inkjet printing method, die coating method, CAP coating method, impregnation, etc., all of which are methods known in the art.

[0046] Preferably, the negative dispersion optical film material is dried after being coated with a polymerizable composition solution.

[0047] When polymerizing the polymerizable composition solution of the present invention, it is desirable to polymerize rapidly, and therefore it is preferable to polymerize by irradiating it with active energy rays such as ultraviolet-visible light or electron beams; when using ultraviolet-visible light, a polarized light source or a non-polarized light source can be used.

[0048] Advantageously, the optical anisotropy body of the present invention is a birefringent film; the birefringent film of the present invention is manufactured in the same manner as the optical anisotropy body of the present invention. Detailed Implementation

[0049] The following is a clear and complete description of the technical solutions in the implementation of this invention. 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. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents, instruments, or components used that do not specify the manufacturer are all conventional products that can be purchased commercially.

[0050] The present invention provides polymerizable compounds represented by general formula (1), and provides polymerizable compositions containing the compound, resins, resin additives, oils, color filters, adhesives, greases, inks, pharmaceuticals, cosmetics, detergents, building materials, packaging materials, liquid crystal materials, organic EL materials, organic semiconductor materials, electronic materials, display elements, electronic devices, communication equipment, automotive parts, aircraft parts, mechanical parts, pesticides and food, and articles using the same, polymerizable compositions, polymers obtained by polymerizing the polymerizable compositions, and optical anisotropies using the polymers.

[0051] To improve the storage stability of the polymerizable composition of the present invention, a stabilizer may be added thereto. Examples of usable stabilizers include 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 composition is preferably 0.005 to 1 wt%, more preferably 0.02 wt% to 0.8 wt%, and even more preferably 0.03 wt% to 0.5 wt%.

[0052] In addition, when polymerizable compositions containing the compounds of the present invention are used in applications such as films, optical components, functional pigments, pharmaceuticals, cosmetics, coating agents, and synthetic resins, metals, metal complexes, dyes, pigments, colorants, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, and metal oxides such as titanium dioxide may be added according to their purpose.

[0053] Polymers obtained by polymerizing polymerizable compositions containing compounds of the present invention can be used for various applications. For example, polymers obtained by polymerizing polymerizable compositions containing compounds of the present invention without orientation can be used as light scattering plates, anti-polarization plates, and anti-moiré stripe plates. Furthermore, polymers obtained by polymerizing after orientation exhibit optical anisotropy, which is useful. Such optically anisotropic materials can be manufactured, for example, by loading a polymerizable composition containing compounds of the present invention onto a substrate that has been rubbed with cloth or the like, a substrate with an organic thin film formed, or a substrate having an orthorhombic SiO2 oriented film, or by sandwiching it between dry substrates, and then polymerizing the polymerizable composition.

[0054] Methods for loading polymerizable compositions onto a substrate include spin coating, die coating, extrusion coating, roller coating, wire rod coating, gravure coating, spray coating, dip coating, and printing. Furthermore, an organic solvent can be added to the polymerizable composition during coating. Organic solvents that can be used include hydrocarbon solvents, halogenated hydrocarbon solvents, ether solvents, alcohol solvents, ketone solvents, ester solvents, and aprotic solvents. Examples of hydrocarbon solvents include toluene or hexane; examples of halogenated hydrocarbon solvents include chloromethane; examples of ether solvents include tetrahydrofuran, acetoxy-2-ethylhexyl, or monomethyl ethyl esters of glycol; examples of alcohol solvents include methanol, acetylene, or isopropanol; examples of ketone solvents include acetone, methyl ethyl ketone, cyclohexanone, γ-butyrolactone, or N-methylpyrrolidone; examples of ester solvents include ethyl acetate or cellosol; and examples of aprotic solvents include dimethylformamide or acetonitrile. These can be used individually or in combination, depending on their vapor pressure and the solubility of the polymerizable composition. Methods for evaporating the added organic solvent include natural drying, heat drying, pressure drying, and pressure-heat drying. To further improve the coatability of the polymerizable liquid crystal material, it is also effective to provide an intermediate layer such as a polyimide film on the substrate or to add a leveling agent to the polymerizable liquid crystal material. The method of providing an intermediate layer such as a polyimide film on the substrate is effective in improving the adhesion between the polymer obtained from the polymerization of the polymerizable material and the substrate.

[0055] Other alignment methods besides those mentioned above include alignment using liquid crystal material flow, and alignment using electric or magnetic fields. These alignment methods can be used individually or in combination. Furthermore, photoalignment can be used as an alternative to friction alignment. As for the shape of the substrate, in addition to flat plates, curved surfaces can also be used as constituent parts. The materials constituting the substrate can be organic or inorganic materials without limitation. Examples of organic materials used as substrate materials include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, triacetyl cellulose, cellulose, polyetheretherketone, etc. Examples of inorganic materials include silicon, glass, calcite, etc.

[0056] When polymerizing a polymerizable composition containing the compounds of the present invention, rapid polymerization is desired, therefore, polymerization by irradiation with active energy rays such as ultraviolet light or electron beams is preferred. When using ultraviolet light, either polarized or unpolarized light sources can be used. Furthermore, when polymerization is performed while the liquid composition is sandwiched between two substrates, at least the substrate on the irradiated side must have appropriate transparency relative to the active energy rays. Alternatively, a method can be used where, after polymerization of specific portions using a mask during light irradiation, the orientation state of the unpolymerized portions is changed by altering conditions such as electric field, magnetic field, or temperature, and then further polymerization is achieved by irradiation with active energy rays. Additionally, the irradiation temperature is preferably within the temperature range where the liquid crystal state of the polymerizable composition of the present invention is maintained. In particular, when manufacturing optical anisotropies by photopolymerization, polymerization is preferably performed at a temperature as close to room temperature as possible, typically 25°C, to avoid inducing undesirable thermal polymerization. The intensity of the active energy rays is preferably 0.1 mW / cm². 2 ~2W / cm 2 The strength is 0.1 mW / cm. 2 At the following times, a significant amount of time is required to complete photopolymerization, productivity deteriorates, and the intensity is 2W / cm². 2 At the above levels, there is a risk of degradation of the polymerizable compound or polymerizable composition.

[0057] Regarding the optical anisotropy obtained by polymerization, heat treatment can also be performed to reduce initial property changes and exhibit stable properties. The heat treatment temperature is preferably in the range of 50 to 250°C, and the heat treatment time is preferably in the range of 30 seconds to 12 hours.

[0058] The optical anisotropy manufactured in this way can be used as a single unit by peeling it off from the substrate, or it can be used without peeling. In addition, the resulting optical anisotropy can be laminated or bonded to other substrates for use.

[0059] The invention is further illustrated below with examples of synthesis, embodiments, and applications, but the invention is not limited to these embodiments. Unless otherwise specified, the percentages of raw materials and compositions are weight percentages.

[0060] Preparation of Example 1T-1 The preparation steps of T-1 are as follows: Step 1, Preparation of intermediate S-3: 50g of S-1 was added to a 1000ml reaction flask, along with 500g of DMF and 21.6g of S-2, under nitrogen protection. 50g of potassium phosphate was added, and the mixture was heated to 120℃ and reacted for 24 hours. Post-treatment: The reaction solution was added to 1000g of water, and a solid precipitated upon standing. The crude product was obtained by filtration and chromatography with dichloromethane solvent through a silica gel column to obtain intermediate S-3: 61.4g, with a yield of 56%. Step 2, Preparation of intermediate S-4: 61.4 g of S-3 was added to a 500 ml reaction flask, along with 300 g of methanol, 30 g of water, and 10 g of sodium hydroxide. The mixture was heated to 60 °C and reacted for 8 h. Post-treatment involved desolvation under reduced pressure, followed by dissolution with 600 g of water. The pH was adjusted to approximately 5 with hydrochloric acid, and the mixture was filtered, washed with water, and dried to obtain 54 g of solid S-4, with a yield of 85%. Step 3, Preparation of intermediate S-6: 54g of S-4 and 60g of S-5 were added to a 500ml reaction flask, along with 300g of dichloromethane and 4.7g of DMAP. The temperature was then lowered to 0℃, and a dichloromethane solution of DCC (47g dissolved in 150g of dichloromethane) was added dropwise. After the addition was complete, the temperature was raised to 25℃, and the reaction was carried out for 12 hours. Post-treatment: The mixture was first filtered, and the filter cake was washed with dichloromethane. The liquid phase was then washed with 300g of 5% hydrochloric acid, followed by two washes with 300g of water. After drying, the organic phase was passed through a silica gel column. 0.2g of p-methoxyphenol was added to the eluent, and the solution was removed under reduced pressure. The solution was recrystallized from 600g of methanol and 60g of dichloromethane to obtain S-8: 78.9g, with a yield of 75%. Step 4, Preparation of intermediate S-8: Add 20g of S-6 to a 250ml reaction flask, add 100ml of dichloromethane, add 12.9g of S-7, and add 3.2g of camphor sulfonic acid. Under nitrogen protection, heat to 50℃ and react for 5 hours. This is used directly as the starting material for the next step without purification; due to impurities, the yield of this step is calculated as 100%. Step 5, Preparation of Product T-1: Add 21g of DIPEA to the reaction solution of S-8, under nitrogen protection, lower the temperature to 0℃, and add 14.3g of acryloyl chloride dropwise. After the addition is complete, raise the temperature to 25℃ and react for 3 hours. For post-processing, directly pass the reaction solution through a silica gel chromatography column, then concentrate it, dissolve the oily substance with 30g of dichloromethane, add 300g of methanol dropwise, stir to precipitate crystals, filter and dry to obtain product T-1: 25.2g, yield 76%. 1H NMR of product T-1 in this embodiment: δ, 1.31-1.33 (m, 4H), 1.45-1.47 (m, 4H), 1.51-1.54 (m, 8H), 1.61-1.63 (m, 2H), 1.78-1.82 (m, 16H), 2.44-2.46 (m, 2H), 3.67-3.67 (m, 4H), 3.75-3.79 (m, 12H), 3.94-3.96 (m, 4H), 3.98-4.00 (m, 4H), 4.14-4.16 (m, 4H), 4.23-4.26 (m, 8H), 5.82 (d, 4H), 6.13 (q, 4H), 6.40 (d, 4H), 6.84-6.86 (m, 8H), 6.91 (d, 2H)), 6.94 (d, 2H, 7.31 (d, 2H), 7.48 (d, 2H), 7.51 (t, 2H), 7.86 (d, 2H), 7.95 (d, 2H).

[0061] The reaction equation for the preparation of product T-1 in this embodiment is as follows: .

[0062] The general formula for product T-1 in this embodiment is as follows: .

[0063] Preparation of Example 2T-2 The preparation steps of T-2 are as follows: Using intermediate S-6 as raw material, the preparation of intermediate S-6 is described in Example 1; Add 20g of S-6 to a 500ml reaction flask, add 200ml of dichloromethane, add 11.9g of S-9, and add 3g of camphor sulfonic acid; under nitrogen protection, heat to 50℃ and react for 5h; for post-treatment, directly pass the reaction solution through a silica gel chromatography column, then concentrate, then dissolve the oily substance with 30g of dichloromethane, add 300g of methanol dropwise, stir to precipitate crystals, filter and dry to obtain product T-2: 28.5g, yield 93%.

[0064] 1H NMR of product T-2 in this embodiment: δ, 1.30-1.32 (m, 4H), 1.44-1.45 (m, 4H), 1.49-51 (m, 8H), 1.60-1.62 (m, 2H), 1.78-1.82 (m, 16H), 2.44-2.45 (m, 2H), 3.35 (s, 6H), 3.60-3.62 (m, 4H), 3.67-3.69 (m, 4H), 3.75-3.77 (m, 4H), 3.94-3.96 (m, 4H), 3.98 -4.01 (m, 6H), 4.14-4.16 (m, 4H), 4.23-4.25 (m, 4H), 5.82 (d, 2H)), 6.13 (q, 2H), 6.40 (d, 2H), 6.83-6.86 (m, 8H), 6.91 (d, 2H), 6.93 (d, 2H), 7.30 (d, 2H), 7.47 (d, 2H), 7.50 (t, 2H), 7.85 (d, 2H), 7.94 (d, 2H).

[0065] The reaction equation for the preparation of product T-2 in this embodiment is as follows: .

[0066] The general formula for product T-2 in this embodiment is as follows: .

[0067] Preparation of Example 3T-3 The preparation steps of T-3 are as follows: Using intermediate S-6 as raw material, the preparation of intermediate S-6 is described in Example 1; Add 20g of S-6 to a 500ml reaction flask, add 200ml of dichloromethane, add 10.8g of S-10, add 3g of camphor sulfonic acid, and under nitrogen protection, heat to 50℃ and react for 5h. For post-treatment, directly pass the reaction solution through a silica gel chromatography column, then concentrate it, dissolve the oily substance with 30g of dichloromethane, add 300g of methanol dropwise, stir to precipitate crystals, filter and dry to obtain product T-3: 29.8g, with a yield of 96%.

[0068] 1H NMR of product T-3 in this embodiment: δ, 0.89-0.91 (m, 6H), 1.27-1.31 (m, 16H), 1.45-1.47 (m, 4H), 1.51-1.53 ​​(m, 8H), 1.58-1.61 (m, 6H), 1.78-1.83 (m, 16H), 2.44-2.46 (m, 2H), 3.75-3.77 (m, 4H), 3.94-3.97 (m, 4H), 3.9 8-4.01 (m, 4H), 4.14-4.16 (m, 4H) 5.83 (d, 2H), 6.15 (q, 2H), 6.41 (d, 2H), 6.85-6.888 (m, 8H) , 6.93 (d, 2H), 6.95 (d, 2H), 7.32 (d, 2H), 7.49 (d, 2H), 7.52 (t, 2H), 7.87 (d, 2H), 7.96 (d, 2H).

[0069] The reaction equation for the preparation of product T-3 in this embodiment is as follows: .

[0070] The general formula for product T-3 in this embodiment is as follows: .

[0071] To evaluate the wavelength dispersion of compounds T-1, T-2, and T-3 obtained in the examples, and compound B-1 (manufactured by Zeon Corporation, K35) used in Comparative Example 1 and compound B-2 (manufactured by BASF Corporation, LC242) used in Comparative Example 2, the phase differences were measured.

[0072] Comparative Example 1 Compound B-1, with the following general formula: .

[0073] Comparative Example 2 Compound B-1, with the following general formula: .

[0074] Application Examples In addition, 1g of compound T-1 from Example 1, compound T-2 from Example 2, compound T-3 from Example 2, compound B-1 from Comparative Example 1, compound B-2 from Comparative Example 1, 30mg of photopolymerization initiator N-1919 (manufactured by ADEKA, Adekaoptomer N-1919, hereinafter the same), and 100mg of surfactant KH-40 (manufactured by AGC Seimi Chemical Co., Ltd., hereinafter the same) in a 1% cyclopentanone solution were dissolved in 2.3g of cyclopentanone. The solution was filtered through a disposable filter with a micropore size of 0.45μm to obtain polymerizable compositions, namely T-1~T3, B-1~B-2, and H1~H6, wherein H1~H6 are as follows: Application Example 1 0.5 g of compound T-1 obtained in Example 1, 0.5 g of compound B-1 in Comparative Example 1, 30 mg of photopolymerization initiator N-1919, and 100 mg of surfactant KH-40 in a 1% cyclopentanone solution were dissolved in 2.3 g of cyclopentanone. The solution was filtered through a disposable filter with a micropore size of 0.45 μm to obtain polymerizable composition H-1.

[0075] Application Example 2 0.5 g of compound T-1 obtained in Example 1, 0.5 g of compound B-2 from Comparative Example 1, 30 mg of photopolymerization initiator N-1919, and 100 mg of surfactant KH-40 in a 1% cyclopentanone solution were dissolved in 2.3 g of cyclopentanone. The solution was filtered through a disposable filter with a micropore size of 0.45 μm to obtain polymerizable composition H-2.

[0076] Application Example 3 0.5g of compound T-2 obtained in Example 2, 0.5g of compound B-1 in Comparative Example 1, 30mg of photopolymerization initiator N-1919, and 100mg of surfactant KH-40 in a 1% cyclopentanone solution were dissolved in 2.3g of cyclopentanone. The solution was filtered through a disposable filter with a micropore size of 0.45μm to obtain polymerizable composition H-3.

[0077] Application Example 4 0.5 g of compound T-2 obtained in Example 2, 0.5 g of compound B-2 from Comparative Example 2, 30 mg of photopolymerization initiator N-1919, and 100 mg of surfactant KH-40 in a 1% cyclopentanone solution were dissolved in 2.3 g of cyclopentanone. The solution was filtered through a disposable filter with a micropore size of 0.45 μm to obtain polymerizable composition H-4.

[0078] Application Example 5 0.5g of compound T-3 obtained in Example 3, 0.5g of compound B-1 in Comparative Example 1, 30mg of photopolymerization initiator N-1919, and 100mg of surfactant KH-40 in a 1% cyclopentanone solution were dissolved in 2.3g of cyclopentanone. The solution was filtered through a disposable filter with a micropore size of 0.45μm to obtain polymerizable composition H-5.

[0079] Application Example 6 0.5 g of compound T-3 obtained in Example 3, 0.5 g of compound B-2 from Comparative Example 2, 30 mg of photopolymerization initiator N-1919, and 100 mg of surfactant KH-40 in a 1% cyclopentanone solution were dissolved in 2.3 g of cyclopentanone. The solution was filtered through a disposable filter with a micropore size of 0.45 μm to obtain polymerizable composition H-6.

[0080] Effect Examples: Measurement of Phase Difference and Evaluation of Wavelength Dispersion 1) Formation of a liquid crystal layer using a polymeric composition On a transparent glass substrate (manufactured by EHC Co, Ltd., trade name: alignment-treated glass substrate, hereinafter the same) with a polyimide alignment film provided after grinding, T-1 to T-3 of Examples 1 to 3, B-1 to B-2 of Comparative Examples 1 and 2, and H-1 to H-6 of Application Examples 1 to 6 of the polymerizable compositions were coated using #4 wire rods. After drying the coatings for 1 minute at the temperatures shown in Table 1, they were aligned for 1 minute at the temperatures shown in Table 1 to form a liquid crystal layer. Then, the liquid crystal layer was polymerized by irradiating 2000 mJ / cm2 ultraviolet light from the coated side at the temperatures shown in Table 1 to prepare a sample for wavelength dispersion measurement.

[0081] 2) Measurement of phase difference For the obtained samples, the phase difference Re between 400 nm and 800 nm was measured using an ellipticity meter (JAWoollam M2000U).

[0082] 3) Evaluation of wavelength dispersion The measured phase difference is used to calculate the α and β values ​​as follows, and wavelength dispersion is evaluated accordingly: Number 1: α = (phase difference of 449.9 nm) / (phase difference of 548.5 nm); Number 2: β = (phase difference of 650.2nm) / (phase difference of 548.5nm); In the case of ideal wavelength dispersion exhibiting broadband characteristics, i.e., inverse wavelength dispersion, α is less than 1 and β is greater than 1. In the case of flat wavelength dispersion, α and β are values ​​of the same level. In the case of general dispersion, α is greater than 1 and β is less than 1; that is, flat wavelength dispersion in which α and β are values ​​of the same level is preferred, and inverse wavelength dispersion in which α is less than 1 and β is greater than 1 is particularly preferred.

[0083] The thickness (μm), phase difference (Re) at 548.5nm wavelength, α, and β values ​​of the negative dispersion optical film material obtained by polymerization are shown in Table 1.

[0084] Table 1

[0085] As shown in Table 1, the polymer optical isomeric types obtained using compounds T-1 to T-3 involved in this invention exhibit α less than 1 and β greater than 1, showing ideal wavelength dispersion with a wide bandwidth.

[0086] By mixing and adding B-1 and B-2, the mixed polymer can effectively exhibit ideal wavelength dispersion with a wide bandwidth.

[0087] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit and essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0088] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A polymerizable compound, characterized in that, The polymerizable compound is selected from formula (T-1), formula (T-2) or formula (T-3). （T-1）， （T-2）， （T-3）。 2. A polymerizable compound composition, characterized in that, The polymerizable compound composition comprises the polymerizable compound of any one of claims 1 and at least one additional polymerizable compound.

3. The polymerizable compound composition according to claim 2, characterized in that, Additional polymerizable compounds are selected from compounds shown in formula (B-1) or formula (B-2). 。 4. The polymerizable compound composition according to claim 2, characterized in that, The polymerizable compound is added to the polymerizable compound composition at a content of not less than 30 wt%.

5. The polymerizable compound composition according to claim 2, characterized in that, The polymerizable compound also includes additives.

6. The polymerizable compound composition according to claim 5, characterized in that, The additive is added to the polymerizable compound composition in an amount of 0.01~10 wt%.

7. An application of a polymerizable compound, characterized in that, The polymerizable compound of claim 1 is used in negative dispersion optical film materials.

8. The application of a polymerizable compound composition, characterized in that, The polymerizable compound composition according to any one of claims 2 to 5 forms a polymerizable composition with an organic solvent, a photopolymerization initiator, and a surfactant.

9. The application of the polymerizable compound composition according to claim 8, characterized in that, The polymeric composition is used in negative dispersion optical film materials.

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