Negative dispersion compound containing carbonic ester group, and preparation and use thereof

Abstract

The present invention belongs to the technical field of optical materials. Disclosed are a negative dispersion compound containing a carbonic ester group, and the preparation and use thereof. The negative dispersion compound containing a carbonic ester group is selected from a compound represented by general formula (1). In the negative dispersion compound containing a carbonic ester group in the present invention, due to the presence of the carbonic ester group, the damp-heat durability life of a film is effectively prolonged. The negative dispersion compound containing a carbonic ester group can be used in a negative dispersion optical film material.

Description

A negatively dispersive compound containing carbonate groups, its preparation and application Technical Field

[0001] This invention relates to a negative dispersive compound containing carbonate groups, its preparation and application, and belongs 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 optically anisotropic polymer film with a uniform orientation is formed, which is an optical anisotropy. The orientation of the film can be planar (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, polymerizable compound 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] Polymerizable compound materials 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, the damp heat durability of films made from existing polymerizable compound materials is still unsatisfactory.

[0005] Therefore, there is a need to develop negatively dispersive compounds containing carbonate groups, their synthesis methods, and applications, in order to solve the aforementioned technical problems. Summary of the Invention

[0006] In response to at least one problem existing in the prior art, the present invention provides a negative dispersion compound containing carbonate groups and its preparation. Due to the carbonate groups, the negative dispersion compound effectively improves the damp heat durability life of the film. The negative dispersion compound containing carbonate groups can be applied to negative dispersion optical film materials.

[0007] To achieve the above objectives, the present invention adopts the following technical solution: a polymerizable compound, wherein the polymerizable compound is a negative dispersion compound containing carbonate groups.

[0008] The dispersive compound containing carbonate groups is selected from compounds represented by general formula (1). In compounds of general formula (1), L1 and L2 each independently represent a single bond or an alkylene group having 1 to 30 carbon atoms; one or more of the -CH2- groups in the alkylene group may be substituted with -O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, or -COS-; P1 represents a polymerizable group.

[0009] Preferably, the polymerizable group of P1 is selected from the group shown in general formula P-1, general formula P-2, general formula P-3, general formula P-4, general formula P-5, general formula P-6, general formula P-7, general formula P-8, general formula P-9, general formula P-10, general formula P-11 or general formula 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, alkenyloxy with 2 to 30 carbon atoms, or haloalkenyloxy with 2 to 30 carbon atoms.

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

[0011] Preferably, R3 represents a hydrogen atom.

[0012] Preferably, L1 and L2 each independently represent an alkylene group having 1 to 30 carbon atoms.

[0013] Preferably, the general formula (1) of the negative dispersion compound containing carbonate groups is selected from general formula T-1, general formula T-2 or general formula T-3, and general formulas T-1, T-2 and T-3 are as follows:

[0014] The present invention also provides a polymerizable compound composition comprising a polymerizable compound of the above general formula (1) and at least one additional polymerizable compound.

[0015] Preferably, the additional polymerizable compound is selected from one or more compounds of general formula M-1, general formula M-2, or general formula M-3; general formula M-1, general formula M-2, or general formula M-3 are as follows:

[0016] Preferably, in the polymerizable compound composition, the additional polymerizable compounds include compounds of general formulas M-1, M-2 and M-3.

[0017] Preferably, the additional polymerizable compound comprises, by weight percentage, 50% of compound formula M-1, 30% of compound formula M-2 and 20% of compound formula M-3.

[0018] Preferably, in the polymerizable compound composition, the polymerizable compound of general formula (1) is added at a concentration of not less than 30 wt%.

[0019] Preferably, in the polymerizable compound composition, the polymerizable compound of general formula (1) is added at a concentration of not less than 40 wt%.

[0020] Preferably, in the polymerizable compound composition, the polymerizable compound of general formula (1) is added at a concentration of not less than 50 wt%.

[0021] Preferably, in the polymerizable compound composition, the polymerizable compound of general formula (1) is added at a concentration of not less than 60 wt%.

[0022] Preferably, the polymerizable compound composition further includes additives.

[0023] Preferably, the additives include, but are not limited to, polymerization initiators, 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.

[0024] Preferably, the additive content is 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%, based on the total weight of the polymerizable composition.

[0025] In another aspect, the present invention also provides a polymerizable compound composition solution comprising the polymerizable compound composition described in the context and an organic solvent.

[0026] Preferably, the organic solvent has good solubility in the polymerizable compound composition and can be removed by drying below 100°C. The organic solvent includes, but is not limited to, any organic solvent that exhibits good solubility in the polymerizable compound, 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; and solvents such as propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, γ-butyrolactone, and chlorobenzene.

[0027] The organic solvents described in the context may be used alone or in combination of two or more.

[0028] Considering solution stability, it is preferable to use one or more of the following solvents: ketones, ethers, esters, and aromatics.

[0029] Preferably, the organic solvent is selected from cyclopentanone.

[0030] Preferably, the organic solvent content in the polymerizable compound composition solution is 30-95 wt%, more preferably 40-90 wt%, more preferably 50-85 wt%, and most preferably 60-80 wt%, based on the total weight of the polymerizable compound composition solution.

[0031] In preparing a solution of a polymerizable compound composition, heating and / or stirring are advantageously performed to promote the dissolution of the polymerizable compound composition.

[0032] In another aspect, the present invention also provides an optical anisotropy comprising a substrate and a polymer film formed by curing a polymerizable compound composition solution as described in the context, and an orientation film present as needed.

[0033] Preferably, the substrate includes, but is not limited to, a glass substrate, a metal substrate, a ceramic substrate, and a polymer substrate, which are selected by sequentially stacking an orientation film as required and a polymer film formed by curing a polymerizable compound composition solution to form an optical anisotropy.

[0034] Preferably, the polymer substrate is a cellulose derivative, polyolefin, polyester, polyolefin, polycarbonate, polyacrylate, polyarylate, polyethersulfone, polyamide, polyimide, polyphenylene sulfide, polyphenylene ether, or polystyrene, etc.

[0035] Preferably, the polymer substrate is polyester, polystyrene, polyolefin, cellulose derivative, polyarylate, or polycarbonate, based on the process applicability of optical anisotropy, especially considering heat resistance and chemical stability.

[0036] Preferably, the orientation film material includes, but is not limited to, materials such as 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, and aryl vinyl compounds.

[0037] 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.

[0038] Preferably, the orientation treatment of the orientation film is a rubbing treatment or polarized ultraviolet-visible light irradiation.

[0039] Preferably, the method for preparing the negative dispersion optical film material includes a coating method.

[0040] 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.

[0041] Preferably, the negative dispersion optical film material is dried after being coated with a polymerizable composition solution.

[0042] When polymerizing the polymerizable compound composition solution of the present invention, it is desirable to polymerize rapidly. 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.

[0043] 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.

[0044] The polymerizable compound provided by this invention is a negative dispersion compound containing carbonate groups, which has good orientation. At the same time, the presence of carbonate groups in the negative dispersion compound effectively improves the lifespan of the film. This negative dispersion compound containing carbonate groups can be applied to negative dispersion optical film materials. Detailed Implementation

[0045] 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.

[0046] The present invention provides polymerizable compounds represented by general formula (1), and provides polymerizable compound 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 thereof, polymerizable compound compositions, polymers obtained by polymerizing the polymerizable compound composition, and optical anisotropies using the polymer.

[0047]

[0048] To improve the storage stability of the polymerizable compound 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 is preferably from 0.005% to 1% by mass relative to the composition, more preferably from 0.02% to 0.8% by mass, and even more preferably from 0.03% to 0.5% by mass.

[0049] In addition, when polymerizable compound 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.

[0050] Polymers obtained by polymerizing polymerizable compound 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 polymerizable compound compositions 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 them between dry substrates, and then polymerizing the polymerizable compound composition.

[0051] Methods for loading polymerizable compound 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 compound composition during coating. As organic solvents, hydrocarbon solvents, halogenated hydrocarbon solvents, ether solvents, alcohol solvents, ketone solvents, ester solvents, and aprotic solvents can be used. 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 diol; examples of alcohol solvents include methanol, acetylene, or isopropanol; examples of ketone solvents include acetone, methyl ethyl ketone, cyclohexanone, γ-butyrolactone, or N-methylpyrrolidones; examples of ester solvents include ethyl acetate or cellosolve; 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 compound 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.

[0052] 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.

[0053] When polymerizing a polymerizable compound 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 compound 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 compound composition.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] Example 1: Preparation of T-1. The preparation method of T-1 is as follows: Step 1: Preparation of intermediate S-3: Add 25g of S-1 to a 500ml reaction flask, add 245ml of DMF, lower the temperature to below 10℃, under nitrogen protection, add 25g of potassium tert-butoxide in batches, and continue stirring for 1h after completion. Then add 28g of S-2 dropwise. After the addition is complete, raise the temperature to 25℃ and react for 5h. The reaction equation for step 1 is as follows: Post-processing: The temperature was lowered, then 350g of dichloromethane and 400g of water were added. Extraction was performed by separation, followed by washing once with 400g of saturated brine, then once with 300g of 10% brine. Sodium sulfate was added for drying, and 70g of alumina was added and stirred for 1 hour. The mixture was then passed through a 140g alumina chromatography column and eluted with 150g of DCM. The eluent was desolvated, yielding 45g of a green oily substance. Crystallization was achieved by stirring with 40g of dichloromethane and 40g of petroleum ether at low temperature. Filtration yielded 28g of green solid S-3, with a yield of 69%. Step 2: Preparation of intermediate S-5: 25g of S-4 was added to a 500ml reaction flask, along with 250ml of dichloromethane, 9g of S-3, and 1g of camphor sulfonic acid. Under nitrogen protection, the mixture was heated to 50℃ and reacted for 5 hours to obtain S-5. The reaction equation for step 2 is as follows: The sample was used directly as the raw material for the next step without purification. Due to impurity, the yield of this step was converted to 100%. Step 3, preparation of intermediate S-7: In a 1L three-necked flask, 110g of S-6, 162g of N,N-dimethylaniline, and 500g of dichloromethane were added. The temperature was lowered to 0℃, and 75g of triphosgene and 250g of dichloromethane were added dropwise. After the addition was complete, the temperature was raised to 25℃ and reacted for 4 hours. A sample was taken for derivatization and sent for HPLC analysis. After passing the analysis, post-processing was performed: The temperature was lowered, and 320g of 15% hydrochloric acid was added dropwise. The sample was washed with water and separated. The aqueous phase was extracted once with 250g of dichloromethane. The organic phases were combined, and 0.12g of BHT was added. The sample was heated and distilled under reduced pressure to obtain 150g of S-7 product, with a yield of 95%. The reaction equation for step 3 is as follows: Step 4, Preparation of intermediate T-1: Add 21g of triethylamine to the reaction solution of S-5, under nitrogen protection, lower the temperature to 0℃, and add a dichloromethane solution of S-7 dropwise (32.7g of S-7 dissolved in 50g of dichloromethane). After the addition is complete, raise the temperature to 25℃ and react for 3h. The reaction equation for step 4 is as follows: For post-processing, the reaction solution was directly passed through a silica gel chromatography column, then concentrated, and then the oily substance was dissolved in 30g of dichloromethane. 300g of methanol was added dropwise, stirred to induce crystallization, and then filtered and dried to obtain 23g of product T-1, with a yield of 70%.

[0058] The 1H NMR spectra of product T-1 in this embodiment are as follows: δ 1.30–1.32 (m, 6H), 1.45–1.47 (m, 6H), 1.51–1.54 (m, 8H), 1.58–1.61 (m, 4H), 1.78–1.82 (m, 14H), 1.88–1.90 (m, 8H), 2.44–2.45 (m, 2H), 3.92–3.94 (m, 4H), 4.00–4.02 (m). ,8H), 4.14~4.16(m,6H), 4.27~4.29(m,2H), 6.11(d,2H), 6.36(d.1H), 6.41(d,2H), 6.8 3~6.90(m,6H), 6.94~6.97(m,2H), 7.13(t,1H), 7.38(d,1H), 7.51(s,1H), 8.43(s,1H).

[0059] The general formula for product T-1 in this embodiment is as follows:

[0060] Example 2 Preparation of T-2 The preparation method of T-2 is as follows: Step 1, Preparation of intermediate S-9: Add 25g of S-1 to a 500ml reaction flask, add 245ml of DMF, lower the temperature to below 10℃, under nitrogen protection, add 25g of potassium tert-butoxide in batches, and after completion, continue stirring for 1h, then add 28g of S-8 dropwise. After the addition is complete, raise the temperature to 25℃ and react for 5h; The reaction equation of step 1 is as follows: Post-processing: The temperature was lowered, then 350g of dichloromethane and 400g of water were added. Extraction was performed by separation, followed by washing once with 400g of saturated brine, then once with 300g of 10% brine. Sodium sulfate was added for drying, and 70g of alumina was added and stirred for 1 hour. The mixture was then passed through a 140g alumina chromatography column and eluted with 150g of DCM. The eluent was desolvated, yielding 45g of a green oily substance. Crystallization was achieved by stirring with 40g of dichloromethane and 40g of petroleum ether at low temperature. The crystals were then filtered to obtain product S-9, with a yield of 70%. Step 2: Preparation of intermediate S-10: 25g of S-4 was added to a 500ml reaction flask, along with 250ml of dichloromethane, 9g of S-9, and 1g of camphor sulfonic acid. Under nitrogen protection, the temperature was raised to 50℃ and reacted for 5 hours to obtain S-10. The reaction equation for step 2 is as follows: Without purification, it is directly used as the raw material for the next step. Due to impurity, the yield of this step is converted to 100%. Step 3, Preparation of intermediate S-7: The preparation steps of S-7 in Example 1 are the same. Step 4, Preparation of product P-2: Add 20g of triethylamine to the reaction solution of S-10, under nitrogen protection, lower the temperature to 0°C, and add a dichloromethane solution of S-7 dropwise (30.5g of S-7 dissolved in 50g of dichloromethane). After the addition is complete, raise the temperature to 25°C and react for 3h. The reaction equation for step 4 is as follows: Post-processing: The reaction solution was directly passed through a silica gel chromatography column, then concentrated, and the oily substance was dissolved in 30g of dichloromethane. 300g of methanol was added dropwise, and the mixture was stirred to induce crystallization. After filtration and drying, 30.2g of P-2 product was obtained, with a yield of 81%.

[0061] The 1H NMR spectra of product T-2 in this embodiment are as follows: δ 1.44–1.47 (m, 8H), 1.49–1.52 (m, 8H), 1.61–1.63 (m, 2H), 1.79–1.83 (m, 14H), 1.87–1.91 (m, 6H), 2.43–2.45 (m, 2H), 3.66–3.68 (m, 2H), 3.75–3.79 (m, 6H), 3.90–3.93 (m, 4H), 4.0 0~4.03(m,8H), 4.14~4.16(m,6H), 4.27~4.29(m,2H), 6.12(d,2H), 6.35(d.1H), 6.40(d,2H) ), 6.82~6.89(m,6), 6.94~6.96(m,2H), 7.14(t,1H), 7.37(d,1H), 7.50(s,1H), 8.42(s,1H).

[0062] The general formula for product T-2 in this embodiment is as follows:

[0063] Example 3: Preparation of T-3. The preparation method of T-3 is as follows: Step 1: Preparation of intermediate S-12: Add 25g of S-1 to a 500ml reaction flask, add 245ml of DMF, lower the temperature to below 10℃, under nitrogen protection, add 25g of potassium tert-butoxide in batches, and continue stirring for 1h after completion. Then add 28g of S-11 dropwise. After the addition is complete, raise the temperature to 25℃ and react for 5h. The reaction equation for step 1 is as follows: Post-processing: The temperature was lowered, then 350g of dichloromethane and 400g of water were added. Extraction was performed by separation, followed by washing once with 400g of saturated brine, then once with 300g of 10% brine. Sodium sulfate was added for drying, and 70g of alumina was added and stirred for 1 hour. The mixture was then passed through a 140g alumina chromatography column and eluted with 150g of DCM. The eluent was desolvated, yielding 45g of a green oily substance. Crystallization was achieved by stirring with 40g of dichloromethane and 40g of petroleum ether at low temperature. The crystals were then filtered to obtain product S-12, with a yield of 70%. Step 2: Preparation of intermediate S-13: 25g of S-4 was added to a 500ml reaction flask, along with 250ml of dichloromethane, 9g of S-12, and 1g of camphor sulfonic acid. Under nitrogen protection, the temperature was raised to 50℃ and reacted for 5 hours to obtain S-13. The reaction equation for step 2 is as follows: Without purification, it is directly used as the raw material for the next step. Due to impurity, the yield of this step is converted to 100%. Step 3, Preparation of intermediate S-7: The preparation steps of S-7 in Example 1 are the same. Step 4, Preparation of product P-2: Add 20g of triethylamine to the reaction solution of S-13, under nitrogen protection, lower the temperature to 0°C, and add a dichloromethane solution of S-7 dropwise (30.5g of S-7 dissolved in 50g of dichloromethane). After the addition is complete, raise the temperature to 25°C and react for 3h. The reaction equation for step 4 is as follows: Post-processing: The reaction solution was directly passed through a silica gel chromatography column, then concentrated, and the oily substance was dissolved in 30g of dichloromethane. 300g of methanol was added dropwise, and the mixture was stirred to induce crystallization. After filtration and drying, 26.4g of P-3 product was obtained, with a yield of 73%.

[0064] The 1H NMR spectra of product T-2 in this embodiment are as follows: δ 1.43–1.47 (m, 8H), 1.48–1.52 (m, 8H), 1.60–1.62 (m, 2H), 1.78–1.82 (m, 14H), 1.86–1.90 (m, 6H), 2.42–2.44 (m, 2H), 3.65–3.67 (m, 2H), 3.76–3.78 (m, 6H), 3.911–3.94 (m, 8H). ,4H), 4.01~4.04(m,8H), 4.15~4.17(m,4H), 6.14(d,2H), 6.36(d.1H), 6.43(d,2H), 6.8 4~6.89(m,6H), 6.95~6.97(m,2H), 7.16(t,1H), 7.39(d,1H), 7.52(s,1H), 8.44(s,1H).

[0065] The general formula for product T-3 in this embodiment is as follows:

[0066] To evaluate its good reliability, we will compare it with three products, compounds B-1, B-2, and B-3, as comparative examples: Comparative Example 1: Using compound B-1 as a comparison, the general formula of compound B-1 is as follows:

[0067] Comparative Example 2 uses compound B-2 as a comparison. The general formula of compound B-2 is as follows:

[0068] Comparative Example 3 uses compound B-3 as a comparison. The general formula of compound B-3 is as follows:

[0069] In addition, a liquid crystal composition is provided as a parent liquid crystal (M), the liquid crystal composition comprising 50% of the compound (M-1) described in JP-A-2005-015473, 30% of the compound (M-2) described in JP-A-10-87565, and 20% of the compound (M-3) described in JP-T-2002-537280.

[0070] The general formula of compound M-1 is as follows: The general formula of compound M-2 is as follows: The general formula of compound M-3 is as follows:

[0071] An alignment film was coated onto a glass substrate with a thickness of 0.7 mm using a polyimide solution, dried at 100°C, and then fired at 200°C for 60 minutes to obtain a coating. The resulting coating was then subjected to a friction treatment using a commercially available friction device to obtain a rubbed glass substrate.

[0072] In the parent liquid crystal M, 40% of the product compounds of Examples 1-3 and Comparative Examples 1-3 shown in Table 1, which were the evaluation objects, were added to the parent liquid crystal M. A polymerizable compound composition was prepared by adding 1% of the photopolymerization initiator Irgacure 907 (manufactured by BASF), 0.1% of the polymerization inhibitor 4-methoxyphenol, and 80% of chloroform to prepare a coating solution. This coating solution was then applied to a rubbed glass substrate by spin coating. After drying at 80°C for 1 min, it was further dried at 120°C for 1 min, and then subjected to a high-pressure mercury lamp at 40 mW / cm². 2 The membrane of the evaluation object was prepared by irradiating it with ultraviolet light at an intensity of 25s. The membranes of the evaluation objects are shown in Table 1 as application examples 1 to 6.

[0073] Orientation uniformity of the obtained polymer was evaluated by observing the degree of non-uniformity using a polarizing microscope. Ten films containing the compound to be evaluated were prepared, and the number of non-uniformities was counted. The number of non-uniformities observed in the ten films was totaled. If the number of non-uniformities was 0, it was recorded as excellent; if there was 1 non-uniformity, it was recorded as good; if there were 1 to 10 non-uniformities, it was recorded as fair; and if there were more than 10 non-uniformities, it was recorded as poor.

[0074] For damp heat durability testing, a 500-hour test was conducted at 85°C and 85% relative humidity. The Re(550) of the optical film before and after the test was measured, and the damp heat durability was evaluated based on the following criteria.

[0075] A. The change in Re(550) before the experiment and Re(550) after the experiment is less than 10% of the change in Re(550) before the experiment.

[0076] B. The change in Re(550) before the experiment and Re(550) after the experiment is more than 10% but less than 30% of the Re(550) before the experiment.

[0077] C. The change in Re(550) before the experiment and the change in Re(550) after the experiment are more than 30% of the change in Re(550) before the experiment.

[0078] Table 1

[0079] As can be seen from Table 1, the three compounds in Examples 1-3 and the three compounds in Comparative Examples 1-3 all showed good orientation when subjected to temperature and humidity durability tests, and the optical properties of Examples 1-3 and Comparative Examples 1-3 were all qualified. When testing their Re(550) change values, the three compounds in Examples 1-3 showed higher temperature and humidity durability compared to the compounds in Comparative Examples 1-3. This is because the three compounds in Examples 1-3 have carbonate groups, which result in higher polymerization degree and better stability when making films, thus effectively improving temperature and humidity durability.

[0080] 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.

[0081] 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 a negative dispersion compound containing carbonate groups.

2. The polymerizable compound according to claim 1, characterized in that, The dispersive compound containing carbonate groups is selected from compounds represented by general formula (1). In compounds of general formula (1), L1 and L2 each independently represent a single bond or an alkylene group having 1 to 30 carbon atoms; one or more of the -CH2- groups in the alkylene group may be substituted with -O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, or -COS-; P1 represents a polymerizable group.

3. The polymerizable compound according to claim 2, characterized in that, L1 and L2 each independently represent alkylene groups with 1 to 30 carbon atoms.

4. The polymerizable compound according to claim 2, characterized in that, P1 can be polymerizable by groups represented by 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, alkenyloxy with 2 to 30 carbon atoms, or haloalkenyloxy with 2 to 30 carbon atoms.

5. A polymerizable compound according to claim 4, characterized in that, The polymerizable group represented by P1 is selected from the group described in general formula P-1.

6. The polymerizable compound according to claim 4, characterized in that, R3 represents a hydrogen atom.

7. The polymerizable compound according to claim 2, characterized in that, The general formula (1) of the negative dispersive compound containing carbonate groups is selected from general formula T-1, general formula T-2 or general formula T-3, and general formulas T-1, T-2 and T-3 are as follows:

8. A polymerizable compound composition, characterized in that, It includes a polymerizable compound of general formula (1) according to any one of claims 1 to 7 and at least one additional polymerizable compound.

9. The polymerizable compound composition according to claim 8, characterized in that, The additional polymerizable compound is selected from one or more compounds of general formula M-1, general formula M-2 or general formula M-3; general formula M-1, general formula M-2 or general formula M-3 are as follows:

10. An application of a polymerizable compound, characterized in that, The dispersive compound containing carbonate groups as described in any one of claims 1 to 7 is used in negative dispersive optical film materials.

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