Polymerizable compounds and their applications in optically anisotropic bodies

Abstract

The present invention provides a polymerizable compound, which is selected from compounds of general formula (I). In addition, a polymerizable composition containing the polymerizable compound and their use in various optically anisotropic bodies are also disclosed. The polymerizable compound is added to the polymerizable composition, which has good solubility and high storage stability, and the polymerizable composition has excellent light resistance after being polymerized into a film.

Description

Technical Field

[0001] The invention belongs to the technical field of optical film materials and relates to a polymerizable compound and an application thereof, in particular to a polymerizable compound and an application thereof in an optically anisotropic body. Background Art

[0002] As the raw material of optical anisotropic bodies, polymerizable compounds are receiving more and more attention. In the prior art, a solution of a polymerizable compound is usually coated on a substrate to align it, and then heated or irradiated with active energy rays to cure it, thereby forming an optical anisotropic polymer film with uniform orientation, also known as an optical 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.

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

[0004] As an optical delay film (phase difference film), it is usually able to give a phase difference of λ / 4 or λ / 2 to monochromatic light of a specific wavelength, thereby controlling optical anisotropy through optical compensation, improving optical efficiency, and increasing the viewing angle. In order to increase the viewing angle, the wavelength dispersion of the birefringence of the phase difference film is required to be small, or to be reversed wavelength dispersion.

[0005] However, when a polymerizable compound used for this purpose is added to a polymerizable composition, crystals are easily precipitated and storage stability is poor. In addition, when a polymerizable composition is applied to a substrate and polymerized, the resulting film-like polymer is irradiated with ultraviolet light, which easily causes problems such as discoloration and peeling from the substrate.

[0006] Therefore, it is necessary to develop a new polymerizable compound with reverse wavelength dispersion to solve the above technical problems. Summary of the invention

[0007] The main purpose of the present invention is to provide a polymerizable compound to solve the problems of poor storage stability and poor light resistance of the polymerizable compound in the prior art.

[0008] In order to achieve the above object, according to one aspect of the present invention, there is provided a polymerizable compound, which is represented by the general formula (I):

[0009]

[0010] in,

[0011] A1 and A2 each independently represent -O-, -S-, -OCH2-, -CH2O-, -CH2CH2-, -CO-, -COO-, -OCO-, -COS-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -ONH-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH=CH -COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COOCH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, -N=N-, -CH=N-, -N=CH-, -CH=NN=CH-, -CF=CF-, -C≡C- or single bond;

[0012] When A1 and / or A2 appear in multiple forms, they may be the same or different;

[0013] B1 and B2 each independently represent 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, naphthalene-1,4-diyl, tetrahydronaphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,3-dioxane-2,5-diyl, and these groups may be unsubstituted or substituted with one or more W;

[0014] When B1 and / or B2 appear in multiple forms, they may be the same or different;

[0015] W represents a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or a linear or branched alkyl group having 1 to 20 carbon atoms, wherein one -CH2- or two or more non-adjacent -CH2- groups are optionally substituted with -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom;

[0016] When there are multiple W, they can be the same or different;

[0017] R represents a hydrogen atom, 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 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, a haloalkenyloxy group having 2 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, or an alkylacyloxy group having 1 to 30 carbon atoms , a haloalkylacyloxy group having 1 to 30 carbon atoms, an alkylaryl group having 6 to 30 carbon atoms, an arylalkyl group having 6 to 30 carbon atoms, an alkylaryloxy group having 6 to 30 carbon atoms, an arylalkyloxy group having 6 to 30 carbon atoms, an arylcarbonyl group having 6 to 30 carbon atoms, an aryloxycarbonyl group having 6 to 30 carbon atoms, an arylcarbonyloxy group having 6 to 30 carbon atoms, and an aryloxycarbonyloxy group having 6 to 30 carbon atoms; one or more -CH2- in the alkyl, alkoxy, alkenyl, and alkenyloxy groups may be replaced by -O-, -S-, -NH-, -NR- a -, -CO-, -OCO-, -COO-, -SCO-, -COS-, or R1 represents a group of -SP3-P3;

[0018] SP1, SP2, and SP3 each independently represent a single bond or an alkylene group with 1 to 30 carbon atoms; one or more -CH2- in the alkylene group may be replaced by -O-, -S-, -NH-, -NR a -, -CO-, -OCO-, -COO-, -SCO-, -COS-substituted;

[0019] R a represents an alkyl group having 1 to 30 carbon atoms;

[0020] P1, P2, and P3 each independently represent a polymerizable group;

[0021] D represents a deuterium atom;

[0022] m1 and m2 each independently represent an integer of 1 to 3.

[0023] Furthermore, in the above general formula (I), A1 and A2 are simultaneously represented by -CH2O-, -OCH2-, -COO- or -OCO-.

[0024] Furthermore, in the above general formula (I), B1 and B2 are both 1,4-phenylene or 1,4-cyclohexylene.

[0025] Furthermore, in the above general formula (I), the polymerizable group is selected from the following groups:

[0026]

[0027] in,

[0028] R b Each independently represents a hydrogen atom, a halogen, 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 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, a haloalkenyloxy group having 2 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, or a haloalkylacyloxy group having 1 to 30 carbon atoms.

[0029] Furthermore, in the above general formula (I), SP1, SP2, and SP3 each independently represent an alkylene group having 1 to 10 carbon atoms, and one or more -CH2- groups in the alkylene group may be substituted by -O-, -CO-, -OCO-, or -COO-.

[0030] Furthermore, in the above general formula (I), P1 and P2 both represent polymerizable groups.

[0031] Furthermore, the polymerizable compound represented by the general formula (I) is preferably a compound represented by the following formulas (I-1) to (I-3):

[0032]

[0033]

[0034] As the above-mentioned polymerizable compound, due to the presence of deuterated hydrogen, the yellowing of the film can be significantly inhibited, thereby effectively extending the service life of the film.

[0035] In another aspect, the present invention provides a polymerizable composition comprising the polymerizable compound.

[0036] In the above polymerizable composition, the content of the compound of the general formula (I) is 10-100 wt %, based on the total weight of the polymerizable composition.

[0037] Preferably, the content of the compound of general formula (I) is 20-98wt%, based on the total weight of the polymerizable composition; more preferably, the content of the compound of general formula (I) is 30-97wt%, based on the total weight of the polymerizable composition; and, most preferably, the content of the compound of general formula (I) is 40-96wt%, based on the total weight of the polymerizable composition.

[0038] Optionally, the polymerizable composition includes a monoreactive polymerizable compound.

[0039] Optionally, the polymerizable composition further includes an additive.

[0040] Additives include, but are not limited to, polymerization initiators, sensitizers, sensitizers, stabilizers, leveling agents, surfactants, inhibitors, antioxidants, dyes, pigments, pigments, dispersants, lubricants, hydrophobic agents, adhesives, flow improvers, defoamers, deaerators, diluents, thixotropic agents, gelling agents, catalysts, metals, metal complexes, fluorescent materials, phosphorescent materials, polysaccharides, ultraviolet absorbers, infrared absorbers, ion exchange resins, titanium oxide, and the like.

[0041] Advantageously, the additive is present in an amount of 0.01-10 wt%, preferably 0.02-8 wt%, more preferably 0.05-5 wt%, and most preferably 0.1-2 wt%, based on the total weight of the polymerizable composition.

[0042] In a specific embodiment, in order to improve the storage stability of the polymerizable composition of the present invention, a stabilizer may be added thereto.

[0043] As the stabilizer which can be used, for example, hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds and the like can be mentioned.

[0044] When the stabilizer is used, the amount added is preferably in the range of 0.005 to 1 wt %, more preferably 0.02 to 0.8 wt %, and even more preferably 0.03 to 0.5 wt % relative to the polymerizable composition.

[0045] In another aspect, the present invention provides a use of the polymerizable composition in an optically anisotropic body.

[0046] Advantageously, the polymerizable composition can be used in the form of a solution. The polymerizable composition solution comprises the polymerizable composition and an organic solvent.

[0047] As the organic solvent, one that has good solubility in the polymerizable composition and can be removed by drying at 100° C. or lower is preferred.

[0048] The organic solvent is not particularly limited, but is preferably an organic solvent that shows good solubility in the polymerizable liquid crystal compound. Preferred are aromatic solvents such as toluene, xylene, isopropylbenzene, mesitylene, etc.; ester solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc.; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, etc.; ether solvents such as tetrahydrothiophene, 1,2-dimethoxyethane, anisole, etc.; amide solvents such as N,N-dimethylformamide, N-methyl-2-pyrrolidone, etc.; propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, γ-butyrolactone, chlorobenzene, etc.

[0049] The organic solvents may be used alone or in combination of two or more.

[0050] Considering the stability of the solution, the organic solvent is preferably one or more of a ketone solvent, an ether solvent, an ester solvent and an aromatic solvent.

[0051] In a specific embodiment, the organic solvent is cyclopentanone.

[0052] The polymerizable composition solution contains an organic solvent in an amount of 30-95 wt %, preferably 40-90 wt %, more preferably 50-85 wt %, and most preferably 60-80 wt %, based on the total weight of the polymerizable composition solution.

[0053] When preparing the polymerizable composition solution, heating and / or stirring are advantageously performed in order to promote dissolution of the polymerizable composition.

[0054] In yet another aspect, the present invention provides an optically anisotropic body comprising a substrate and a polymer film formed by curing the polymerizable composition solution as described above and below, and, if necessary, an alignment film.

[0055] In one embodiment, an optically anisotropic body is formed by laminating a substrate, an alignment film if necessary, and a polymer film formed by curing a polymerizable composition solution in this order.

[0056] The substrate of the optically anisotropic body includes, but is not limited to, a glass substrate, a metal substrate, a ceramic substrate, and a polymer substrate.

[0057] Furthermore, the polymer substrate may be, for example, a cellulose derivative, polyolefin, polyester, polyolefin, polycarbonate, polyacrylate, polyarylate, polyethersulfone, polyamide, polyimide, polyphenylene sulfide, polyphenylene oxide or polystyrene, and the like.

[0058] Based on the process suitability of the optically anisotropic body, in particular, based on the considerations of heat resistance and chemical stability, the polymer substrate is preferably polyester, polystyrene, polyolefin, cellulose derivative, polyarylate, polycarbonate.

[0059] The materials for the oriented films of optical anisotropies include, but are 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, chalcone, cinnamate, anthraquinone, azo compounds, aromatic vinyl compounds, and the like.

[0060] The alignment treatment may be a stretching treatment, a rubbing treatment, polarized ultraviolet visible light irradiation, an ion beam treatment, etc. Preferably, the alignment treatment is a rubbing treatment or polarized ultraviolet visible light irradiation.

[0061] As the coating method for obtaining the optically anisotropic body of the present invention, methods known in the art such as applicator method, bar coating method, spin coating method, gravure printing method, flexographic printing method, inkjet method, die coating method, CAP coating method, dipping, etc. can be used. After coating the polymerizable composition solution, it is dried.

[0062] When the polymerizable composition of the present invention is used for solution polymerization, it is desirable that the polymerization proceeds rapidly, and therefore, it is preferred to polymerize by irradiation with active energy rays such as ultraviolet visible light or electron beams.

[0063] When using ultraviolet and visible light, either a polarized light source or a non-polarized light source can be used.

[0064] In a specific embodiment, the liquid polymerizable composition is polymerized while being sandwiched between two substrates, and at least the substrate on the irradiated side must have appropriate transparency with respect to the active energy rays.

[0065] Alternatively, the following method may be used: a mask is used during light irradiation to polymerize only a specific portion, and then the orientation state of the unpolymerized portion is changed by changing conditions such as the electric field, magnetic field or temperature, and then active energy rays are further irradiated to polymerize the portion.

[0066] In addition, the temperature during irradiation is preferably within a temperature range in which the liquid crystal state of the polymerizable 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, i.e., 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, it takes a lot of time to complete the photopolymerization, and the productivity will decrease. 2 If the concentration is above 50%, the polymerizable compound or the polymerizable composition may be degraded.

[0067] 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 seconds to 12 hours.

[0068] 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.

[0069] The present invention provides a polymerizable compound represented by general formula (I), and provides a polymerizable 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 composition, a polymer obtained by polymerizing the polymerizable composition, and an optically anisotropic body using the polymer.

[0070] The optically anisotropic body of the present invention is advantageously a phase difference film. The phase difference film of the present invention is prepared in the same manner as the optically anisotropic body of the present invention. When the polymerizable compound in the polymerizable composition solution is polymerized in a planar orientation state, a phase difference film having birefringence in the plane relative to the substrate can be obtained.

[0071] When the polymerizable compound and the polymerizable chiral compound in the polymerizable composition solution are polymerized in a planarly oriented state, a retardation film having birefringence out-of-plane with respect to the substrate can be obtained.

[0072] When the polymerizable compound and the polymerizable discotic compound in the polymerizable composition solution are polymerized in a planarly oriented state, a retardation film having birefringence both in-plane and out-of-plane with respect to the substrate can be obtained.

[0073] In addition, when the substrate also has a phase difference, the phase difference film of the present invention is superimposed with the birefringence it has to obtain a birefringence phase difference film. The birefringence of the two can be in the same direction or in different directions within the plane of the substrate. DETAILED DESCRIPTION

[0074] The present invention is further described below in conjunction with synthesis examples and embodiments, but the protection scope of the present invention is not limited thereto.

[0075] The materials and reagents used in the present invention are all purchased from commercial sources or prepared according to synthetic methods known in the art.

[0076] Unless otherwise stated, all percentages in the synthesis examples and embodiments are by mass.

[0077] Synthesis example

[0078] 1. Synthesis of Compound (I-1)

[0079] The reaction scheme of compound (I-1) is as follows:

[0080]

[0081] Preparation of intermediate S-2

[0082] Weigh 100 g of S-1 and add it to a 500 ml three-necked flask, add 300 g of deuterated heavy water, heat and reflux for 24 h, then cool, filter and dry to obtain 96.5 g of product with a yield of 96%.

[0083] Preparation of intermediate S-4

[0084] Add 26g of S-2 to a 1000ml reaction bottle, add 800g of DMF, add 100g of S-3, add 160g of potassium phosphate, protect with nitrogen, raise the temperature to 90°C and react for 24 hours.

[0085] Post-treatment: the reaction solution was added to 1600 g of water, and solid was precipitated after standing. The crude product was filtered and passed through a silica gel chromatography column with dichloromethane solvent to obtain intermediate S-3: 64 g, with a yield of 72%.

[0086] Preparation of intermediate S-5

[0087] Add 60g of S-4 into a 250ml reaction bottle, add 600g of methanol and 60g of water, add 44g of sodium hydroxide, and heat to 60°C for 8h.

[0088] Post-treatment: desolventize under reduced pressure, then add 400 g of water to dissolve, and adjust the pH to below 2 with hydrochloric acid. Filter by suction, wash with water, and dry to obtain S-5: 53 g solid, with a yield of 95%.

[0089] Preparation of intermediate S-7

[0090] Add 50g of S-5 and 66.2g of S-6 to a 1000ml reaction bottle, add 350g of dichloromethane, add 7.3g of DMAP, then lower the temperature to 0°C, add a dichloromethane solution of DCC (54g dissolved in 150g of dichloromethane) dropwise, raise the temperature to 25°C, and react for 12 hours.

[0091] Post-treatment: first filter, wash the filter cake with dichloromethane, retain the liquid phase, wash the reaction liquid with 200g of 5% hydrochloric acid, and then wash twice with 200g of water. Dry, pass the organic phase through a silica gel column, add 0.07g of p-methoxyphenol to the eluent, then desolventize under reduced pressure, and recrystallize with 500g of methanol and 100g of dichloromethane. Obtain S-7: 76.2g, yield 70%

[0092] Preparation of intermediate S-9

[0093] Add 30g of S-7 to a 500ml reaction bottle, add 250ml of dichloromethane, add 11.8g of S-8, and add 1g of camphorsulfonic acid. Protect with nitrogen, heat to 50℃ and react for 5h. Directly use it as raw material for the next step without purification. The yield of this step is converted to 100%.

[0094] Preparation of product (I-1)

[0095] 17.5 g of DIPEA was added to the reaction solution of S-9. Under nitrogen protection, the temperature was lowered to 0°C, and 11.9 g of acryloyl chloride was added dropwise. After the addition was completed, the temperature was raised to 25°C and the reaction was carried out for 3 hours.

[0096] After treatment, the reaction solution was directly passed through a silica gel chromatography column and then concentrated. The oil was dissolved with 40 g of dichloromethane, 400 g of methanol was added dropwise thereto, stirred for crystallization, filtered and dried to obtain 37.6 g of the product with a yield of 88%.

[0097] The structural characterization results of the product compound (I-1) are as follows:

[0098] 1 H NMR (300MHz, CDC13), δ (ppm): 1.19-1.29 (m, 4H), 1.41-1.82 (m, 22H), 1.91 (m, 2H), 2.08 (m, 4H), 2. 24(m,4H),2.53(m,2H),3.62(m,3H),3.67(m,2H),3.84-3.90(m,5H),3.94(t,4H),4.15-4.19(m,6H ),4.53(t,2H),5.76(d,1H),5.82(d,2H),6.08(d,1H),6.12(d,2H),6.37(d,1H),6.40(d,2H),6.84 -6.90(m,6H),6.95-6.98(m,2H),7.14(t,1H),7.53(d,1H),7.65(d,1H),7.69(d,1H),8.34(s,1H).

[0099] 2. Synthesis of compound (I-2)

[0100] The reaction scheme of compound (I-2) is as follows:

[0101]

[0102] The synthesis of intermediate S-7 was based on (I-1).

[0103] Add 30g of S-7 to a 500ml reaction bottle, add 250ml of dichloromethane, add 10.6g of S-10, add 1g of camphorsulfonic acid, protect with nitrogen, heat to 50℃ and react for 5h.

[0104] After treatment, the reaction solution was directly passed through a silica gel chromatography column and then concentrated. The oil was dissolved with 40 g of dichloromethane, 400 g of methanol was added dropwise thereto, stirred for crystallization, filtered and dried to obtain 35.9 g of the product with a yield of 90%.

[0105] The structural characterization results of the product compound (I-2) are as follows:

[0106] 1 H NMR (300MHz, CDC13), δ (ppm): 1.22-1.28 (m, 4H), 1.44-1.47 (m, 8H), 1.60-1.82 (m, 12H), 1.9 0(m,2H),2.07(t,4H),2.24(d,4H),2.53(m,2H),3.30(s,3H),3.50(t,2H),3.66(t,2H),3.8 5-3.89(m,6H),3.93(t,4H),4.17(t,4H),4.53(t,2H),5.82(d,2H),6.13(q,2H),6.40(d,2H ),6.83-6.90(m,6H),6.95-6.98(m,2H),7.14(t,1H),7.52(t,1H),7.67(t,2H),8.33(s,1H).

[0107] 3. Synthesis of Compound (I-3)

[0108] The reaction scheme of compound (I-3) is as follows:

[0109]

[0110] The synthesis of intermediate S-7 was based on (I-1).

[0111] Add 30g of S-7 to a 500ml reaction bottle, add 250ml of dichloromethane, add 10.6g of S-10, add 1g of camphorsulfonic acid, protect with nitrogen, heat to 50℃ and react for 5h.

[0112] After treatment, the reaction solution was directly passed through a silica gel chromatography column and then concentrated. The oil was dissolved with 40 g of dichloromethane, 400 g of methanol was added dropwise thereto, stirred for crystallization, filtered and dried to obtain 32.64 g of the product with a yield of 89%.

[0113] The structural characterization results of the product compound (I-3) are as follows:

[0114] 1 H NMR (300MHz, CDC13), δ (ppm): 0.89 (t, 3H), 1.20-1.35 (m, 10H), 1.61-1.69 (m, 6H) ,1.78(m,2H),1.90(m,2H),2.07(t,4H),2.23(d,4H),2.50(m,2H),3.69-3.76(m, 10H),3.83-3.87(m,8H),4.11(t,4H),4.32(t,6H),5.82(d,2H),6.15(q,2H),6.4 2(d,2H),6.83-6.98(m,8H),7.13(t,1H),7.53(t,1H),7.66(t,2H),8.13(s,1H).

[0115] Example

[0116] In order to evaluate the performance of the polymerizable compound of the present invention, it was compared with the following three products:

[0117]

[0118] In addition, a liquid crystal composition is provided as a mother liquid crystal (M), which contains 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.

[0119]

[0120] Example 1

[0121] The polyimide solution for the alignment film was coated on a glass substrate with a thickness of 0.7 mm, dried at 100° C. for ten minutes, and then heated to 200° C. and fired for 60 minutes to obtain a coating film. The obtained coating film was subjected to a rubbing treatment using a commercially available rubbing device.

[0122] 40% of polymerizable compound (I-1) was added to the mother liquid crystal M to prepare a polymerizable composition, and 1% of photopolymerization initiator Irgacure 907 (manufactured by BASF), 0.1% of 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 minute, the temperature was further raised to 120°C and dried for 1 minute, and then a high-pressure mercury lamp was used to heat the glass substrate at 40 mW / cm 2 The film was formed by irradiating ultraviolet rays at an intensity of 1000 nm for 25 seconds.

[0123] The obtained polymer was observed under a polarizing microscope to evaluate the degree of unevenness. -3 The number of unevenness observed in 10 films was totaled, and if the number of unevenness was 0, it was recorded as excellent, if the number of unevenness was 1, it was recorded as good, if the number of unevenness was 1-10, it was recorded as medium, and if the number of unevenness was more than 10, it was recorded as poor.

[0124] Example 2

[0125] The polymerizable compound in Example 1 was replaced with the polymerizable compound (I-2) and the other operations were kept unchanged to prepare 10 films.

[0126] Example 3

[0127] The polymerizable compound in Example 1 was replaced with the polymerizable compound (I-3) and the other operations were kept unchanged to prepare 10 films.

[0128] Comparative Example 1

[0129] The polymerizable compound in Example 1 was replaced with the polymerizable compound (B-1) and the other operations were kept unchanged to prepare 10 films.

[0130] Comparative Example 2

[0131] The polymerizable compound in Example 1 was replaced with the polymerizable compound (B-2) and the other operations were kept unchanged to prepare 10 films.

[0132] Comparative Example 3

[0133] The polymerizable compound in Example 1 was replaced with the polymerizable compound (B-3) and the other operations were kept unchanged to prepare 10 films.

[0134] The prepared membranes are shown in Table 1.

[0135] Table 1

[0136] membrane Polymeric compounds Example 1 I-1 Example 2 I-2 Example 3 I-3 Comparative Example 1 B-1 Comparative Example 2 B-2 Comparative Example 3 B-3

[0137] Performance Evaluation

[0138] Light resistance: Xenon irradiation tester (SuntestXLS, manufactured by ATLAS) was used at 60 mW / cm 2 Each film was subjected to a sunlight test at 26°C and 120 J. The discoloration and orientation unevenness of the film were evaluated. The results are shown in Table 2.

[0139] The yellowness index (YI) of each film was measured, and the difference (△YI) between the YI value before the sunlight test and the YI value after the sunlight test was calculated. The yellowness index (YI) was measured using a JASCO UV / VIS spectrophotometer V-560 and calculated using the attached color diagnosis program. The calculation formula is: YI = 100 (1.28X-1.06Z) / Y (JISK7373) (X, Y, Z represent the three stimulus values ​​in the XYZ color system. The smaller the △YI value, the less discoloration.

[0140] Table 2

[0141]

[0142]

[0143] As shown in Table 2, the compounds of the embodiments and the comparative examples have good orientation when subjected to high-intensity ultraviolet irradiation. The functions of the deuterated compounds and the non-deuterated compounds are both qualified. When testing the yellowing degree, it is found that due to the presence of deuterated hydrogen, the compounds of the embodiments have the ability to inhibit yellowing and delay decay, which can effectively extend the life of the film.

[0144] The above content is a further detailed description of the present invention in combination with specific preferred embodiments, and it cannot be determined that the specific implementation of the present invention is limited to these detailed descriptions. For ordinary technicians in the technical field to which the present invention belongs, the present invention can have various changes and variations without departing from the technical concept of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A polymerizable compound, characterized in that The polymerizable compound is a compound represented by the following formula (I-1) to (I-3), 2. A polymerizable composition comprising the polymerizable compound according to claim 1.

3. Use of the polymerizable composition according to claim 2 in an optically anisotropic body.

4. The use according to claim 3, characterized in that: The optically anisotropic body is an optical retardation film.

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