Polymerizable compound and use thereof in optically anisotropic body

Abstract

Provided is a polymerizable compound. The polymerizable compound is selected from the compound of general formula (I). Moreover, further disclosed is a polymerizable composition containing the polymerizable compound, and the use thereof in various optically anisotropic bodies. By adding the polymerizable compound to the polymerizable composition, good solubility and a high storage stability are obtained; and a film formed by the polymerization of the polymerizable composition has good light resistance.

Description

Polymerizable compounds and their applications in optically anisotropic materials Technical Field

[0001] The present invention belongs to the technical field of optical thin 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] Polymeric compounds are gaining increasing attention as raw materials for optically anisotropic materials. Conventional techniques typically involve coating a solution of the polymeric compound onto a substrate, aligning it, and curing it by heating or irradiating it with active energy rays. This results in a uniformly oriented optically anisotropic polymer film, also known as an optically anisotropic material. The film's orientation can be planar (liquid crystal molecules oriented substantially parallel to the layers), homeotropic (rectangular or perpendicular to the layers), or tilted, or even cholesteric.

[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 expansion 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] Optical retardation films (phase difference films) typically impart 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. To increase the viewing angle, the phase difference film's birefringence must have a low wavelength dispersion or inverse wavelength dispersion.

[0005] However, polymerizable compounds used for this purpose, when added to polymerizable compositions, tend to cause crystal precipitation and suffer from poor storage stability. Furthermore, when the polymerizable composition is applied to a substrate and polymerized, the resulting film-like polymer is irradiated with ultraviolet light, which can lead to poor light resistance, 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.

[0007] Summary of the Invention

[0008] 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 polymerizable compounds in the prior art.

[0009] 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):

[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-, -CH 2CH2-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 multiple A1 and / or A2 appear, they can 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 Ws;

[0014] When B1 and / or B2 appear multiple times, they can 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 by -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 by 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, 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 with 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] in,

[0027] 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.

[0028] 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-.

[0029] Furthermore, in the above general formula (I), P1 and P2 both represent polymerizable groups.

[0030] Furthermore, the polymerizable compound represented by the general formula (I) is preferably a compound represented by the following formulas (I-1) to (I-3),

[0031] As the above-mentioned polymerizable compound, due to the presence of deuterated hydrogen, the yellowing of the membrane can be significantly inhibited, thereby effectively extending the service life of the membrane.

[0032] In yet another aspect, the present invention provides a polymerizable composition comprising the polymerizable compound.

[0033] In the polymerizable composition, the content of the compound of formula (I) is 10-100 wt %, based on the total weight of the polymerizable composition.

[0034] Preferably, the content of the compound of general formula (I) is 20-98 wt%, based on the total weight of the polymerizable composition; more preferably, the content of the compound of general formula (I) is 30-97 wt%, based on the total weight of the polymerizable composition; and, most preferably, the content of the compound of general formula (I) is 40-96 wt%, based on the total weight of the polymerizable composition.

[0035] Optionally, the polymerizable composition includes a monoreactive polymerizable compound.

[0036] Optionally, the polymerizable composition further includes additives.

[0037] 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, degassing agents, 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.

[0038] Advantageously, the additive is present in an amount of 0.01 to 10 wt%, preferably 0.02 to 8 wt%, more preferably 0.05 to 5 wt%, and most preferably 0.1 to 2 wt%, based on the total weight of the polymerizable composition.

[0039] In a specific embodiment, a stabilizer may be added to the polymerizable composition of the present invention in order to improve the storage stability thereof.

[0040] Examples of usable stabilizers include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, and nitroso compounds.

[0041] When a 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.

[0042] In another aspect, the present invention provides a use of the polymerizable composition in an optically anisotropic body.

[0043] 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.

[0044] 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.

[0045] The organic solvent is not particularly limited, but is preferably an organic solvent that exhibits good solubility in the polymerizable liquid crystal compound. Preferred examples include 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 tetrahydrothiophene, 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.

[0046] The organic solvents may be used alone or in combination of two or more.

[0047] 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.

[0048] In a specific embodiment, the organic solvent is cyclopentanone.

[0049] 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.

[0050] When preparing the polymerizable composition solution, heating and / or stirring are advantageously performed to promote dissolution of the polymerizable composition.

[0051] In yet another aspect, the present invention provides an optically anisotropic body comprising a substrate, a polymer film formed by curing the polymerizable composition solution as described above and below, and, if necessary, an alignment film.

[0052] In one embodiment, an optically anisotropic body is formed by sequentially laminating a substrate, an alignment film (if necessary), and a polymer film formed by curing a polymerizable composition solution.

[0053] 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.

[0054] Furthermore, the polymer substrate may be, for example, a cellulose derivative, polyolefin, polyester, polyolefin, polycarbonate, polyacrylate, polyarylate, polyethersulfone, polyamide, polyimide, polyphenylene sulfide, polyphenylene ether, or polystyrene, and the like.

[0055] Based on the process applicability 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, or polycarbonate.

[0056] The materials for the alignment films of optical anisotropes include, but are not limited to, 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, aromatic vinyl compounds, and the like.

[0057] The alignment treatment may be stretching treatment, rubbing treatment, polarized ultraviolet-visible light irradiation, ion beam treatment, etc. Preferably, the alignment treatment is rubbing treatment or polarized ultraviolet-visible light irradiation.

[0058] As coating methods 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, and dipping method can be used. After coating the polymerizable composition solution, it is dried.

[0059] When solution polymerization is performed using the polymerizable composition of the present invention, it is desirable that polymerization proceeds rapidly. Therefore, polymerization is preferably performed by irradiation with active energy rays such as ultraviolet, visible light, or electron beams.

[0060] When using ultraviolet-visible light, either a polarized light source or a non-polarized light source can be used.

[0061] In a specific embodiment, polymerization is performed while the liquid polymerizable composition is sandwiched between two substrates, and at least the substrate on the irradiated side must have appropriate transparency to the active energy rays.

[0062] 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 further irradiated with active energy rays to polymerize the portion.

[0063] Furthermore, the temperature during irradiation is preferably within the temperature range in which the liquid crystal state of the polymerizable composition of the present invention is maintained. In particular, when producing an optically anisotropic body by photopolymerization, it is also preferable to polymerize at a temperature as close to room temperature as possible, typically 25°C, in order to avoid inducing undesirable 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 Below 2W / 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.

[0064] The optically anisotropic body obtained by polymerization may be subjected to heat treatment for the purpose of reducing initial property changes and developing 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.

[0065] The optically anisotropic body produced by such a method can be used as a single body after being peeled off from the substrate, or can be used without being peeled off. In addition, the obtained optically anisotropic body can be laminated or laminated with other substrates.

[0066] The present invention provides a polymerizable compound represented by general formula (I), and also provides a polymerizable composition containing the compound, resins, resin additives, oils, color filters, adhesives, tackifiers, greases, inks, pharmaceuticals, cosmetics, detergents, building materials, packaging materials, liquid crystal materials, organic EL materials, organic semiconductor materials, electronic materials, display elements, electronic equipment, communication equipment, automobile parts, aircraft parts, machine parts, pesticides, and foods using the polymerizable composition, as well as products using the same, a polymerizable composition, a polymer obtained by polymerizing the polymerizable composition, and an optically anisotropic body using the polymer.

[0067] The optically anisotropic body of the present invention is advantageously a retardation film. The retardation film of the present invention is produced 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 planarly oriented state, a retardation film having in-plane birefringence relative to the substrate can be obtained.

[0068] 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.

[0069] 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.

[0070] In addition, when the substrate also has a phase difference, the phase difference film of the present invention is superimposed with the birefringence possessed by the substrate to obtain a birefringent phase difference film. The birefringence possessed by the two substrates can be in the same direction or in different directions within the plane of the substrate. DETAILED DESCRIPTION

[0071] The present invention is further illustrated below with reference to synthesis examples and embodiments, but the scope of protection of the present invention is not limited thereto.

[0072] 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.

[0073] Unless otherwise stated, all percentages in the synthesis examples and embodiments are by mass.

[0074] Synthesis example

[0075] 1. Synthesis of Compound (I-1)

[0076] The reaction scheme of compound (I-1) is as follows:

[0077] Preparation of intermediate S-2

[0078] 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%.

[0079] Preparation of intermediate S-4

[0080] Add 26g of S-2 to a 1000ml reaction flask, add 800g of DMF, add 100g of S-3, add 160g of potassium phosphate, protect with nitrogen, heat to 90℃ and react for 24 hours.

[0081] Post-treatment: The reaction solution was added to 1600 g of water and allowed to stand to obtain a solid precipitated. The crude product was filtered and passed through a silica gel chromatography column with dichloromethane solvent to obtain 64 g of intermediate S-3 with a yield of 72%.

[0082] Preparation of intermediate S-5

[0083] Add 60g of S-4 to a 250ml reaction flask, add 600g of methanol and 60g of water, add 44g of sodium hydroxide, and heat to 60°C for 8h.

[0084] After treatment, the solvent was removed under reduced pressure, 400 g of water was added for dissolution, and the pH was adjusted to below 2 with hydrochloric acid. S-5 was filtered, washed with water, and dried to obtain 53 g of solid S-5 with a yield of 95%.

[0085] Preparation of intermediate S-7

[0086] Add 50 g of S-5 and 66.2 g of S-6 to a 1000 ml reaction flask, add 350 g of dichloromethane, add 7.3 g of DMAP, then lower the temperature to 0°C, add a dichloromethane solution of DCC (54 g dissolved in 150 g of dichloromethane) dropwise, raise the temperature to 25°C, and react for 12 hours.

[0087] After treatment, first filter and wash the filter cake with dichloromethane, retaining the liquid phase. The liquid phase was washed with 200g of 5% hydrochloric acid, and then washed twice with 200g of water. Dry, the organic phase was passed through a silica gel column, 0.07g of p-methoxyphenol was added to the eluate, and then desolventized and recrystallized with 500g of methanol and 100g of dichloromethane. S-7: 76.2g, yield 70%

[0088] Preparation of intermediate S-9

[0089] Add 30g of S-7 to a 500ml reaction flask, along with 250ml of dichloromethane, 11.8g of S-8, and 1g of camphorsulfonic acid. Heat to 50°C under nitrogen for 5 hours. Use this as raw material for the next step without purification. The yield in this step is calculated as 100%.

[0090] Preparation of product (I-1)

[0091] 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 complete, the temperature was raised to 25°C and the reaction was carried out for 3 h.

[0092] 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%.

[0093] The structural characterization results of the product compound (I-1) are as follows:

[0094] 1 H NMR (300MHz, CDCl3), 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).

[0095] 2. Synthesis of Compound (I-2)

[0096] The reaction scheme of compound (I-2) is as follows:

[0097] The synthesis of intermediate S-7 was carried out according to the method of (I-1).

[0098] Add 30 g of S-7 to a 500 ml reaction flask, add 250 ml of dichloromethane, add 10.6 g of S-10, and add 1 g of camphorsulfonic acid. Under nitrogen protection, heat to 50°C and react for 5 h.

[0099] 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%.

[0100] The structural characterization results of the product compound (I-2) are as follows:

[0101] 1 H NMR (300MHz, CDCl3), 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).

[0102] 3. Synthesis of Compound (I-3)

[0103] The reaction scheme of compound (I-3) is as follows:

[0104] The synthesis of intermediate S-7 was carried out according to the method of (I-1).

[0105] Add 30 g of S-7 to a 500 ml reaction flask, add 250 ml of dichloromethane, add 10.6 g of S-10, and add 1 g of camphorsulfonic acid. Under nitrogen protection, heat to 50°C and react for 5 h.

[0106] 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%.

[0107] The structural characterization results of the product compound (I-3) are as follows:

[0108] 1H NMR (300MHz, CDCl3), 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).

[0109] Example

[0110] In order to evaluate the performance of the polymerizable compound of the present invention, it was compared with the following three products:

[0111] 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.

[0112] Example 1

[0113] The polyimide solution for the alignment film was coated on a 0.7 mm thick glass substrate, 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.

[0114] 40% of the polymerizable compound (I-1) was added to the mother liquid crystal M to prepare a polymerizable composition, and 1% of the 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 a 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. 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 100 nm for 25 seconds.

[0115] The obtained polymer was observed under a polarizing microscope to evaluate the degree of unevenness. -3Ten films were prepared and the number of unevenness was counted. The number of unevenness observed in the ten films was totaled and recorded as excellent if the number of unevenness was 0, good if the number of unevenness was 1, fair if the number of unevenness was 1-10, and poor if the number of unevenness was more than 10.

[0116] Example 2

[0117] Ten films were prepared by replacing the polymerizable compound in Example 1 with the polymerizable compound (I-2) and maintaining the other procedures unchanged.

[0118] Example 3

[0119] Ten films were prepared by replacing the polymerizable compound in Example 1 with the polymerizable compound (I-3) and maintaining the other procedures unchanged.

[0120] Comparative Example 1

[0121] Ten films were prepared by replacing the polymerizable compound in Example 1 with the polymerizable compound (B-1) and maintaining the other procedures unchanged.

[0122] Comparative Example 2

[0123] Ten films were prepared by replacing the polymerizable compound in Example 1 with the polymerizable compound (B-2) and maintaining the other procedures unchanged.

[0124] Comparative Example 3

[0125] Ten films were prepared by replacing the polymerizable compound in Example 1 with the polymerizable compound (B-3) and maintaining the other procedures unchanged.

[0126] The prepared membranes are shown in Table 1.

[0127] Table 1

[0128] Performance evaluation

[0129] 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, 120 J, and 30°C. Discoloration and uneven orientation of the film were evaluated. The results are shown in Table 2.

[0130] The yellowness index (YI) of each film was measured, and the difference (ΔYI) between the YI value before and after the sunlight test was calculated. The YI was measured using a JASCO UV / VIS V-560 spectrophotometer and calculated using the included color diagnosis program. The calculation formula is: YI = 100 (1.28X - 1.06Z) / Y (JIS K7373) (X, Y, and Z represent the tristimulus values ​​in the XYZ color system. A smaller ΔYI value indicates less discoloration.

[0131] Table 2

[0132] The results shown in Table 2 indicate that both the Example and Comparative Example compounds exhibited good orientation under high-intensity UV irradiation. Both the deuterated and non-deuterated compounds performed satisfactorily. Yellowing tests revealed that the presence of deuterated hydrogen in the Example compounds suppressed yellowing, slowed degradation, and effectively extended the film's lifespan.

[0133] The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and the specific implementation of the present invention cannot be considered to be limited to these detailed descriptions. For those skilled in the art of the present invention, various changes and modifications can be made to the present invention 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 scope of protection of the present invention.

Claims

1. A polymerizable compound, characterized in that The compound is represented by the general formula (I), in, 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 triple C- or single bond; When multiple A1 and / or A2 appear, they can be the same or different; 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 Ws; When B1 and / or B2 appear multiple times, they can be the same or different; 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-, wherein any hydrogen atom in the alkyl group may be substituted with a fluorine atom; When there are multiple W, they can be the same or different; 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-, -O-, -S-, -NH-, -NR- a -, -CO-, -OCO-, -COO-, -SCO-, -COS-, or R represents a group of -SP3-P3; SP1, SP2, 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; R a represents an alkyl group with 1 to 30 carbon atoms; P1, P2, and P3 each independently represent a polymerizable group; D represents a deuterium atom; m1 and m2 each independently represent an integer of 1 to 3.

2. The polymerizable compound according to claim 1, wherein Said A1 and A2 are simultaneously represented by -CH2O-, -OCH2-, -COO- or -OCO-.

3. The polymerizable compound according to claim 1, wherein Said B1 and B2 are both 1,4-phenylene or 1,4-cyclohexylene.

4. The polymerizable compound according to claim 1, wherein The polymerizable group is selected from the following groups: Among them, 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.

5. The polymerizable compound according to claim 1, wherein The 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-.

6. The polymerizable compound according to claim 1, wherein The P1 and P2 both represent polymerizable groups 7. The polymerizable compound according to claim 1, wherein The polymerizable compound is a compound represented by the following formulas (I-1) to (I-3), 8. A polymerizable composition comprising the polymerizable compound according to any one of claims 1 to 7.

9. Use of the polymerizable composition according to claim 8 in an optically anisotropic body.

10. The use according to claim 9, characterized in that The optically anisotropic body is an optical retardation film.

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