Negative dispersion compound containing carbonic ester group and preparation and application thereof

Abstract

The invention discloses a negative dispersion compound containing a carbonic ester group and preparation and application thereof, and belongs to the technical field of optical materials, and the negative dispersion compound containing the carbonic ester group is selected from compounds shown in a general formula (1). According to the negative dispersion compound containing the carbonic ester group, due to the existence of the carbonic ester group, the damp-heat durability life of a diaphragm is effectively prolonged, and the negative dispersion compound containing the carbonic ester group can be applied to a negative dispersion optical film material.

Description

Technical Field

[0001] The invention relates to a negative dispersion compound containing a carbonate group and a preparation method and application thereof, belonging to the technical field of optical materials. Background Art

[0002] A polymerizable compound (RM) is a raw material for preparing various optically anisotropic bodies. Usually, an RM solution is coated on a substrate to align it. After curing, an optically anisotropic polymer film with uniform orientation is formed, which is an optically anisotropic body. The orientation of the film can be planar (the liquid crystal molecules are basically parallel to the layer orientation), homeotropic (rectangular or perpendicular to the layer) or inclined, or it can be cholesteric oriented. Therefore, polymerizable compound materials have received widespread attention.

[0003] Depending on the application field, optical anisotropic bodies include, but are not limited to, birefringent films, optical retardation films (phase difference films), negative dispersion optical films, optical compensation films, vision expansion films, reflective films, selective reflective films, anti-reflective films, brightness enhancement films, liquid crystal orientation films, polarizing films (deflecting plates), polarizing elements, circular polarizing elements, elliptically polarizing elements, and various other optical elements.

[0004] The polymerizable compound material controls the optical anisotropy by optically compensating the dispersion caused by different wavelengths when light propagates in the medium, thereby improving the optical efficiency and increasing the viewing angle. However, the wet and hot durability of the film made of the existing polymerizable compound material is still unsatisfactory.

[0005] Therefore, it is required to develop the following negative dispersion compound containing carbonate group and its synthesis method and application, so as to solve the above technical problems. Summary of the invention

[0006] In order to address at least one problem existing in the above-mentioned prior art, the present invention provides a negative dispersion compound containing a carbonate group and its preparation method. The negative dispersion compound effectively improves the wet and hot durability life of the film due to the carbonate group. The negative dispersion compound containing a carbonate group can be applied to negative dispersion optical film materials.

[0007] In order to achieve the above object, the present invention adopts the following technical solution: a polymerizable compound, wherein the polymerizable compound is a negative dispersion compound containing a carbonate group.

[0008] The dispersion compound containing carbonate groups is selected from the compounds represented by general formula (1), (1); In the compound 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 -CH2- in the alkylene group may be substituted by -O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, or -COS-; and P1 represents a polymerizable group.

[0009] Preferably, the polymerizable group P1 is selected from the group represented by the 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 each independently represents a hydrogen atom, a halogen, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, a carbamoyloxy group, an amino group, a sulfamoyl group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyanate, a cyano group, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a haloalkoxy group having 1 to 30 carbon atoms, an alkoxycarbonyl group having 1 to 30 carbon atoms, a haloalkoxycarbonyl group having 1 to 30 carbon atoms, an alkylcarbonyl group having 1 to 30 carbon atoms, a haloalkylcarbonyl group having 1 to 30 carbon atoms, an alkylacyloxy group having 1 to 30 carbon atoms, a haloalkylacyloxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a haloalkenyl group having 2 to 30 carbon atoms, an alkenyloxy group having 2 to 30 carbon atoms, or a haloalkenyloxy group having 2 to 30 carbon atoms.

[0010] Preferably, the polymerizable group represented by P1 is selected from the group described in the 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 a carbonate group is selected from the general formula T-1, the general formula T-2 or the general formula T-3, and the general formula T-1, the general formula T-2 and the general formula T-3 are as follows: T-1; T-2; T-3.

[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 formula M-1, formula M-2 or formula M-3; formula M-1, formula M-2 or formula M-3 is as follows: ; ; .

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

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

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

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

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

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

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

[0023] Preferably, the additives include, but are not limited to, polymerization initiators, sensitizers, sensitizers, stabilizers, leveling agents, surfactants, inhibitors, antioxidants, colorants, dispersants, lubricants, hydrophobic agents, adhesives, flow improvers, defoamers, degassing agents, diluents, thixotropic agents, gelling agents, catalysts, metals, metal complexes, luminescent materials, and the like.

[0024] Preferably, the content of the additive is 0.01 to 10 wt %, preferably 0.02 to 8 wt %, more preferably 0.05 to 5 wt %, most preferably 0.1 to 3 wt %, based on the total weight of the polymerizable composition.

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

[0026] Preferably, the organic solvent has good solubility in the polymerizable compound composition and can be removed by drying at a temperature below 100°C. The organic solvent includes, but is not limited to, an organic solvent in which the polymerizable compound shows good solubility, preferably aromatic solvents such as toluene, xylene, isopropylbenzene, 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, etc.

[0027] The organic solvents described above and below may be used alone or in combination of two or more.

[0028] Based on the consideration of solution stability, it is preferred to use one or more of ketone solvents, ether solvents, ester solvents and aromatic solvents.

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

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

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

[0032] In still another aspect, the present invention provides an optically anisotropic body comprising a substrate and a polymer film formed by curing a solution of the polymerizable compound composition as described above and below, and, if necessary, an alignment film.

[0033] Preferably, the substrate includes, but is not limited to, a glass substrate, a metal substrate, a ceramic substrate, a polymer substrate, which is selected according to the need for the presence of an oriented film and a polymer film formed by curing a solution of a polymerizable compound composition, thereby forming an optically anisotropic body.

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

[0035] Preferably, the polymer substrate is polyester, polystyrene, polyolefin, cellulose derivative, polyarylate, polycarbonate, based on the process applicability of the optically anisotropic body, especially based on the consideration of heat resistance and chemical stability.

[0036] Preferably, the alignment film material includes, but is not limited to, polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, acrylic resin, epoxy acrylic resin, coumarin, chalcones, cinnamate, anthraquinone, azo compounds, aromatic vinyl compounds and other materials.

[0037] Preferably, the alignment treatment of the alignment film is a stretching treatment, a rubbing treatment, polarized ultraviolet visible light irradiation or an ion beam treatment.

[0038] Preferably, the alignment treatment of the alignment film is 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 applicator method, rod coating method, spin coating method, gravure printing method, flexographic printing method, inkjet method, die coating method, CAP coating method, dipping, etc., which are all methods well known in the art.

[0041] Preferably, after coating the polymerizable composition solution on the negative dispersion optical film material, the solution is dried.

[0042] When polymerizing the polymerizable compound composition of the present invention in a solution, it is desired to polymerize rapidly, and therefore it is preferably polymerized by irradiating it with active energy rays such as ultraviolet visible light or electron beams; when using ultraviolet visible light, either a polarized light source or a non-polarized light source can be used.

[0043] The optically anisotropic body of the present invention is preferably a birefringent film. The birefringent film of the present invention is produced in the same manner as the optically anisotropic body of the present invention.

[0044] The polymerizable compound provided by the present invention is a negative dispersion compound containing a carbonate group, which has good orientation. At the same time, the negative dispersion compound effectively improves the life of the film due to the presence of the carbonate group. The negative dispersion compound containing a carbonate group can be applied to negative dispersion optical film materials. DETAILED DESCRIPTION

[0045] The following is a clear and complete description of the technical solutions in the implementation of the present invention. The described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present invention. If the specific conditions are not specified in the embodiments, they are carried out according to the normal conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents, instruments, and components used, they are all conventional products that can be purchased commercially.

[0046] The present invention provides a polymerizable compound represented by the general formula (1), and provides a polymerizable compound composition containing the compound, a resin, a resin additive, an oil, a color filter, an adhesive, a tackifier, a grease, an ink, a pharmaceutical product, a cosmetic, a detergent, a building material, a packaging material, a liquid crystal material, an organic EL material, an organic semiconductor material, an electronic material, a display element, an electronic device, a communication device, an automobile part, an aircraft part, a machine part, a pesticide and a food, and products using the same, a polymerizable compound composition, a polymer obtained by polymerizing the polymerizable compound composition, and an optically anisotropic body using the polymer.

[0047] (1).

[0048] In order 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-butyl catechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, and the like. When a stabilizer is used, the amount added is preferably in the range of 0.005% to 1% by mass, more preferably 0.02% to 0.8% by mass, and further preferably 0.03% to 0.5% by mass, relative to the composition.

[0049] In addition, when the polymerizable compound composition containing the compound of the present invention is used for films, optical elements, functional pigments, pharmaceuticals, cosmetics, coating agents, synthetic resins, etc., metals, metal complexes, dyes, pigments, pigments, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, metal oxides such as titanium oxide, etc. may be added according to the purpose.

[0050] The polymer obtained by polymerizing the polymerizable compound composition containing the compound of the present invention can be used for various purposes. For example, the polymer obtained by polymerizing the polymerizable compound composition containing the compound of the present invention without orientation can be used as a light scattering plate, a depolarizing plate, and an anti-moiré plate. In addition, the polymer obtained by orientation and polymerization has optical anisotropy and is useful. Such an optically anisotropic body can be manufactured, for example, by the following method: the polymerizable compound composition containing the compound of the present invention is supported on a substrate rubbed with a cloth, a substrate formed with an organic thin film, or a substrate having an oriented film with SiO2 vapor-deposited obliquely, or it is sandwiched between dry substrates, and then the polymerizable compound composition is polymerized to manufacture.

[0051] In order to support the polymerizable compound composition on the substrate, the method includes spin coating, die coating, extrusion coating, roll coating, wire rod coating, gravure coating, spray coating, dipping, printing, etc. In addition, an organic solvent can be added to the polymerizable compound composition during coating. As the organic solvent, hydrocarbon solvents, halogenated hydrocarbon solvents, ether solvents, alcohol solvents, ketone solvents, ester solvents, aprotic solvents, etc. can be used. For example, toluene or hexane can be listed as a hydrocarbon solvent, monochloromethane can be listed as a halogenated hydrocarbon solvent, tetrahydrofuran, acetoxy-2-ethylhexane or diol monomethyl ethyl ester can be listed as an ether solvent, methanol, ethyl acetate or isopropanol can be listed as an alcohol solvent. Acetone, methyl ethyl ketone, cyclohexanone, γ-butyrolactone or N-methylpyrrolidone can be listed as a ketone solvent, ethyl acetate or cellosolve can be listed as an ester solvent, and dimethylformamide or acetonitrile can be listed as an aprotic solvent. These can be used alone or in combination, and can be appropriately selected in consideration of their vapor pressure and the solubility of the polymerizable compound composition. As a method for volatilizing the added organic solvent, natural drying, heating drying, pressurized drying, and pressurized heating drying can be used. In order to further improve the coating properties of polymerized liquid crystal materials, it is also effective to provide an intermediate layer such as a polyimide film on the substrate and 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 for improving the adhesion between the polymer obtained by polymerizing the polymerizable material and the substrate.

[0052] As alignment treatments other than those mentioned above, flow alignment using liquid crystal materials, and the use of electric fields or magnetic fields can be cited. These alignment means can be used alone or in combination. Furthermore, as an alignment treatment method instead of friction, a photo-alignment method can also be used. As the shape of the substrate, in addition to a flat plate, it can also have a curved surface as a component. Organic materials and inorganic materials can be used as the material constituting the substrate without limitation. As organic materials that become substrate materials, for example, polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, triacetyl cellulose, cellulose, polyetheretherketone, etc. can be cited. In addition, as inorganic materials, for example, silicon, glass, calcite, etc. can be cited.

[0053] When polymerizing a polymerizable compound composition containing the compound of the present invention, since it is desired to polymerize rapidly, a method of polymerizing by irradiating active energy rays such as ultraviolet rays or electron rays is preferred. When ultraviolet rays are used, a polarized light source may be used, or a non-polarized light source may be used. In addition, when the liquid composition is polymerized in a state where it is sandwiched between two substrates. At least the substrate on the irradiated side must have appropriate transparency with respect to the active energy rays. Alternatively, the following means may be used: after polymerizing only a specific portion using a mask during light irradiation, the orientation state of the unpolymerized portion is changed by changing conditions such as an electric field, a magnetic field or temperature, and further irradiating with active energy rays to polymerize. In addition, the temperature during irradiation is preferably within the temperature range in which the liquid crystal state of the polymerizable compound composition of the present invention is maintained. In particular, when an optically anisotropic body is to be produced by photopolymerization, it is also preferred to polymerize at a temperature as close to room temperature as possible, typically 25°C, in order to avoid inducing undesired thermal polymerization. The intensity of the active energy ray is preferably 0.1 mW / cm 2 ~2W / cm 2 The intensity is 0.1mW / cm 2 When the intensity is below 2 W / cm, a lot of time is required to complete the photopolymerization, and the productivity will deteriorate. 2 When the amount is above 1:1, the polymerizable compound or the polymerizable compound composition may be deteriorated.

[0054] The optically anisotropic body obtained by polymerization may be subjected to heat treatment for the purpose of reducing initial property changes and expressing 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 s to 12 h.

[0055] The optically anisotropic body produced by such a method may be used as a single body after being peeled off from the substrate, or may be used without being peeled off. In addition, the obtained optically anisotropic body may be laminated or bonded to other substrates for use.

[0056] The present invention is further explained below by listing synthesis examples, embodiments and application examples, but the present invention is not limited to these embodiments. Unless otherwise specified, the percentages in raw materials and compositions are percentages by weight.

[0057] Example 1 Preparation of T-1 The preparation steps of T-1 are as follows: Step 1, preparation of intermediate S-3: Add 25g of S-1 to a 500ml reaction bottle, add 245ml of DMF, lower the temperature to below 10°C, protect with nitrogen, add 25g of potassium tert-butoxide in batches, continue stirring for 1h, then add 28g of S-2 dropwise, after the addition is complete, heat to 25°C and react for 5h; the reaction equation of step 1 is as follows: ; Post-treatment, lower the temperature, then add 350g of dichloromethane, add 400g of water, extract by separation, wash once with 400g of saturated brine, wash once with 300g, 10% brine, add sodium sulfate to dry, add 70g of alumina and stir for 1h, then pass through a 140g alumina chromatography column, elute with 150g of DCM, desolventize with the eluent, and obtain 45g of green oily substance, stir and crystallize with 40g of dichloromethane and 40g of petroleum ether at low temperature, and filter to obtain 28g of green solid S-3, with a yield of 69%; Step 2, preparation of intermediate S-5: Add 25g of S-4 to a 500ml reaction bottle, add 250ml of dichloromethane, add 9g of S-3, add 1g of camphorsulfonic acid. Protect with nitrogen, heat to 50°C and react for 5h to obtain S-5; the reaction equation of step 2 is as follows: ; It was directly used as the raw material for the next step without purification. Since it was impure, the yield of this step was converted to 100%; Step 3, preparation of intermediate S-7: In a 1L three-necked flask, add 110g S-6, 162g N,N-dimethylaniline, 500g dichloromethane, lower the temperature to 0°C, add 75g triphosgene and 250g dichloromethane dropwise thereto, after the addition is complete, heat to 25°C and react for 4h, take a sample for derivatization, send to HPLC for testing, and perform post-treatment after passing: lower the temperature, add 320g 15% hydrochloric acid dropwise thereto, wash the separated liquid with water, extract the aqueous phase once with 250g dichloromethane, combine the organic phases, add 0.12g BHT, heat and reduce pressure distillation to obtain 150g S-7 product, with a yield of 95%; the reaction equation of step 3 is as follows: ; Step 4, preparation of intermediate T-1: add 21 g of triethylamine to the reaction solution of S-5, protect with nitrogen, lower the temperature to 0°C, add a dichloromethane solution of S-7 (32.7 g of S-7 dissolved in 50 g of dichloromethane) dropwise thereto, raise the temperature to 25°C after the addition is complete, and react for 3 hours; the reaction equation of step 4 is as follows: ; After treatment, the reaction solution was directly passed through a silica gel chromatography column and then concentrated. The oil was dissolved with 30 g of dichloromethane, 300 g of methanol was added dropwise, stirred for crystallization, and filtered and dried to obtain 23 g of T-1 product with a yield of 70%.

[0058] 1H NMR of the product T-1 in this example: δ1.30~1.32 (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 of the product T-1 in this example is as follows: .

[0060] Example 2 Preparation of T-2 The preparation steps of T-2 are as follows: Step 1, preparation of intermediate S-9: Add 25g of S-1 to a 500ml reaction bottle, add 245ml of DMF, lower the temperature to below 10°C, protect with nitrogen, add 25g of potassium tert-butoxide in batches, continue stirring for 1h, then add 28g of S-8 dropwise, after the addition is complete, heat to 25°C and react for 5h; the reaction equation of step 1 is as follows: ; Post-treatment, lower the temperature, then add 350g of dichloromethane, add 400g of water, extract by separation, wash once with 400g of saturated brine, wash once with 300g, 10% brine, add sodium sulfate to dry, add 70g of alumina and stir for 1h, then pass through a 140g alumina chromatography column, elute with 150g of DCM, desolventize with the eluent, and obtain 45g of a green oily substance, stir and crystallize with 40g of dichloromethane and 40g of petroleum ether at low temperature, and filter to obtain S-9 product with suction, and the yield is 70%; Step 2, preparation of intermediate S-10: Add 25g of S-4 to a 500ml reaction bottle, add 250ml of dichloromethane, add 9g of S-9, and add 1g of camphorsulfonic acid. Protect with nitrogen, heat to 50°C and react for 5h to obtain S-10; the reaction equation of step 2 is as follows: ; It was directly used as the raw material for the next step without purification. Since it was impure, the yield of this step was converted to 100%; Step 3, preparation of intermediate S-7: the same as the preparation step of S-7 in Example 1; Step 4, preparation of product P-2: add 20 g of triethylamine to the reaction solution of S-10, protect with nitrogen, lower the temperature to 0°C, add a dichloromethane solution of S-7 (30.5 g of S-7 dissolved in 50 g of dichloromethane) dropwise thereto, raise the temperature to 25°C after the addition is complete, and react for 3 hours; the reaction equation of step 4 is as follows: ; Post-treatment: The reaction solution was directly passed through a silica gel chromatography column and then concentrated. The oil was dissolved with 30 g of dichloromethane, 300 g of methanol was added dropwise thereto, stirred for crystallization, filtered and dried to obtain 30.2 g of P-2 product with a yield of 81%.

[0061] 1H NMR of the product T-2 in this example: δ1.44~1.47 (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), 4.00~4.03(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 of the product T-2 in this example is as follows:

[0063] Example 3 Preparation of T-3 The preparation steps of T-3 are as follows: Step 1, preparation of intermediate S-12: Add 25g of S-1 to a 500ml reaction bottle, add 245ml of DMF, lower the temperature to below 10°C, protect with nitrogen, add 25g of potassium tert-butoxide in batches, continue stirring for 1h, then add 28g of S-11 dropwise, after the addition is complete, heat to 25°C and react for 5h; the reaction equation of step 1 is as follows: ; Post-treatment, lower the temperature, then add 350g of dichloromethane, add 400g of water, extract by separation, wash once with 400g of saturated brine, wash once with 300g, 10% brine, add sodium sulfate to dry, add 70g of alumina and stir for 1h, then pass through a 140g alumina chromatography column, elute with 150g of DCM, desolventize with the eluent, and obtain 45g of a green oily substance, stir and crystallize with 40g of dichloromethane and 40g of petroleum ether at low temperature, and filter to obtain S-12 product with a yield of 70%; Step 2, preparation of intermediate S-13: Add 25g of S-4 to a 500ml reaction bottle, add 250ml of dichloromethane, add 9g of S-12, and add 1g of camphorsulfonic acid. Protect with nitrogen, heat to 50°C and react for 5h to obtain S-13; the reaction equation of step 2 is as follows: ; It was directly used as the raw material for the next step without purification. Since it was impure, the yield of this step was converted to 100%; Step 3, preparation of intermediate S-7: the same as the preparation step of S-7 in Example 1; Step 4, preparation of product P-2: add 20 g of triethylamine to the reaction solution of S-13, protect with nitrogen, lower the temperature to 0°C, add a dichloromethane solution of S-7 (30.5 g of S-7 dissolved in 50 g of dichloromethane) dropwise thereto, raise the temperature to 25°C after the addition is complete, and react for 3 hours; the reaction equation of step 4 is as follows: ; Post-treatment: the reaction solution was directly passed through a silica gel chromatography column and then concentrated. The oil was dissolved with 30 g of dichloromethane, 300 g of methanol was added dropwise thereto, stirred for crystallization, filtered and dried to obtain 26.4 g of P-3 product with a yield of 73%.

[0064] 1H NMR of the product T-2 in this example: δ1.43-1.47 (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, 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), 6.84~6.89(m,6 H), 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 of the product T-3 in this example is as follows: .

[0066] In order to evaluate its good reliability, we will compare it with the following three products: Compound B-1, B-2, and B-3 as comparative examples: Comparative Example 1 Taking compound B-1 as a comparison, the general formula of compound B-1 is as follows: .

[0067] Comparative Example 2 Taking compound B-2 as a comparison, the general formula of compound B-2 is as follows: .

[0068] Comparative Example 3 Taking compound B-3 as a comparison, the general formula of compound B-3 is as follows: .

[0069] application Furthermore, a liquid crystal composition is provided as a mother liquid crystal (M), the liquid crystal composition comprising 50% of a compound (M-1) described in JP-A-2005-015473, 30% of a compound (M-2) described in JP-A-10-87565, and 20% of a 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] The oriented film was coated with a polyimide solution on a glass substrate with a thickness of 0.7 mm, dried at 100°C, and then sintered at 200°C for 60 minutes to obtain a coating film. The obtained coating film was subjected to a friction treatment using a commercially available friction device to obtain a rubbed glass substrate.

[0072] The product compounds of Examples 1 to 3 and Comparative Examples 1 to 3 shown in Table 1 were added to the matrix liquid crystal M in an amount of 40% by weight of the matrix liquid crystal M as the compounds to be evaluated, a polymerizable compound composition was prepared, 1% of a photopolymerization initiator Irgacure 907 (manufactured by BASF), 0.1% of a polymerization inhibitor 4-methoxyphenol and 80% of chloroform were added to prepare a coating solution; the coating solution was applied to the 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 a high-pressure mercury lamp was used to heat the glass substrate at 40 mW / cm 2 The film to be evaluated was prepared by irradiating ultraviolet rays for 25 seconds at an intensity of 1000 nm. The film to be evaluated was as shown in Application Examples 1 to 6 in Table 1.

[0073] Orientation uniformity For the obtained polymer, the degree of unevenness is evaluated by polarizing microscope observation. Ten films of the compound to be evaluated are prepared, and the number of unevenness is counted. The number of unevenness observed in the 10 films is totaled, and if the number of unevenness is 0, it is recorded as excellent, if the number of unevenness is 1, it is recorded as good, if the number of unevenness is 1 to 10, it is recorded as medium, and if the number of unevenness is more than ten, it is recorded as poor.

[0074] Wet heat durability The wet heat durability test conditions were 85°C and 85% relative humidity for 500 hours. Re (550) of the optical film before and after the test was measured, and the wet heat durability was evaluated according to the following criteria.

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

[0076] B. The change between Re (550) before the test and Re (550) after the test is not less than 10% and not more than 30% of Re (550) before the test.

[0077] C. The change between Re (550) before the test and Re (550) after the test is more than 30% of Re (550) before the test.

[0078] Table 1

[0079] It can be seen from Table 1 that the three compounds of Examples 1 to 3 and the three compounds of Comparative Examples 1 to 3 have good orientation when subjected to temperature and humidity durability tests, and the optical properties of Examples 1 to 3 and Comparative Examples 1 to 3 are all qualified; when testing the Re (550) change value, the three compounds of Examples 1 to 3 have higher temperature and humidity durability than the compounds of Comparative Examples 1 to 3, because the three compounds of Examples 1 to 3 have carbonate groups, and when preparing films, the polymerization degree is higher and the stability is better, which can effectively improve the 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 present invention can be implemented in other specific forms without departing from the spirit and essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0081] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes 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 a carbonate group.

2. A polymerizable compound according to claim 1, characterized in that The dispersion compound containing carbonate groups is selected from the compounds represented by general formula (1), (1); In the compound 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 -CH2- in the alkylene group may be substituted by -O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, or -COS-; and P1 represents a polymerizable group.

3. A polymerizable compound according to claim 2, characterized in that L1 and L2 each independently represent an alkylene group having 1 to 30 carbon atoms.

4. A polymerizable compound according to claim 2, characterized in that: The polymerizable group P1 is selected from the group represented by the 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 each independently represents a hydrogen atom, a halogen, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, a carbamoyloxy group, an amino group, a sulfamoyl group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyanate, a cyano group, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a haloalkoxy group having 1 to 30 carbon atoms, an alkoxycarbonyl group having 1 to 30 carbon atoms, a haloalkoxycarbonyl group having 1 to 30 carbon atoms, an alkylcarbonyl group having 1 to 30 carbon atoms, a haloalkylcarbonyl group having 1 to 30 carbon atoms, an alkylacyloxy group having 1 to 30 carbon atoms, a haloalkylacyloxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a haloalkenyl group having 2 to 30 carbon atoms, an alkenyloxy group having 2 to 30 carbon atoms, or a haloalkenyloxy group having 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 the general formula P-1.

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

7. A polymerizable compound according to claim 2, characterized in that: The general formula (1) of the negative dispersion compound containing carbonate groups is selected from the general formula T-1, the general formula T-2 or the general formula T-3. The general formula T-1, the general formula T-2 and the general formula T-3 are as follows: T-1； T-2； T-3。 8. A polymerizable compound composition, characterized in that A polymerizable compound comprising the polymerizable compound of the general formula (1) according to any one of claims 1 to 7 and at least one additional polymerizable compound.

9. A polymerizable compound composition according to claim 8, characterized in that: The additional polymerizable compound is selected from one or more compounds described in Formula M-1, Formula M-2 or Formula M-3; Formula M-1, Formula M-2 or Formula M-3 is as follows: ； ； 。 10. An application of a polymerizable compound, characterized in that: The dispersion compound containing carbonate groups as described in any one of claims 1 to 7 is used in negative dispersion optical film materials.

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