Polymerizable compound having good film-forming performance, and negative-dispersion optical film

Abstract

Disclosed is a polymerizable compound, which is selected from compounds of general formula (1). In addition, it is also disclosed that when the polymerizable compound is added to a polymerizable composition, the occurrence of poor film thickness uniformity and orientation non-uniformity is reduced. Therefore, the polymerizable compound can be used as a component of the polymerizable composition. Furthermore, an optically anisotropic body using the polymerizable composition containing the polymerizable compound can be used for uses such as optical films.

Description

Polymerizable compound with good film-forming performance and negative dispersion optical film Technical Field

[0001] The present invention relates to the field of light regulation technology, and specifically to a polymerizable compound with good film-forming performance and a negative dispersion optical film. Background Art

[0002] Polymerizable compounds (RMs) are gaining increasing attention as raw materials for preparing various optically anisotropic materials. Existing techniques typically involve coating a RM solution 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] The optically anisotropic body has at least one of the following characteristics, preferably all of them: low haze value, high film thickness uniformity, little orientation unevenness, high surface hardness, high adhesion, good appearance after ultraviolet irradiation, and little orientation defect.

[0004] Depending on the application field, optical anisotropic bodies include, but are not limited to, birefringent films, optical delay 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.

[0005] In the case of negative dispersion optical films, a polymerizable compound is added to a parent liquid crystal to obtain a polymerizable composition, thereby reducing the wavelength dispersion of its birefringence and effectively increasing the viewing angle of the display (Patent Documents 1 and 2). However, existing negative dispersion optical films are prone to poor film thickness uniformity and uneven orientation.

[0006] Therefore, there is a demand for the development of the following polymerizable compounds, polymerizable compositions containing the polymerizable compounds, and optically anisotropic bodies using the same, which can solve the above-mentioned technical problems.

[0007] Prior art literature:

[0008] Patent document 1: CN113861128A;

[0009] Patent document 2: CN116768822A.

[0010] Summary of the Invention

[0011] Problems to be Solved by the Invention

[0012] The present invention aims to provide a polymerizable compound that, when added to a polymerizable composition, does not cause crystal precipitation and exhibits high storage stability. Furthermore, the present invention provides a polymerizable composition that, when polymerizing a polymerizable composition containing the polymerizable compound, produces a film-like polymer with minimal poor film thickness uniformity and less uneven orientation. Furthermore, the present invention provides a polymer obtained by polymerizing the polymerizable composition and an optically anisotropic article using the same.

[0013] Solutions to Problems

[0014] The present inventors have conducted intensive studies and, as a result, have developed a polymerizable compound represented by the general formula (1), a polymerizable composition containing the polymerizable compound, and an optically anisotropic body using the same, thereby solving the above-mentioned problems and completing the present invention.

[0015] The present invention for solving the above-mentioned problems is constructed as follows:

[0016] In one aspect, the present application relates to a polymerizable compound, wherein the polymerizable compound is selected from the compounds represented by general formula (1),

[0017] Where,

[0018] P1 and P2 each independently represent a polymerizable group;

[0019] L1 and L2 each independently represent an alkylene group with 1 to 30 carbon atoms; the alkylene group may be linear or branched; one or more -CH2- in the alkylene group may be replaced by -O-, -S-, -NH-, -NR a -, -CO-, -OCO-, -COO-, -OCOO-, -SCO-, -COS-; R1-R6 and R aEach independently represents an H 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, 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 substituted by -O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, or -COS-; optionally, one or more H atoms in the alkyl, alkoxy, alkenyl, and alkenyloxy groups may be substituted by halogen, halogen, cyano, hydroxyl, nitro, carboxyl, carbamoyloxy, amino, sulfamoyl, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, thioisocyano, Substituted with 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 alkylacyloxy group having 1 to 30 carbon atoms, a haloalkylacyloxy group having 1 to 30 carbon atoms, or a polymerizable group;

[0020] m, n and r each independently represent an integer from 0 to 4;

[0021] p and q each independently represent an integer of 0-3.

[0022] As the compound of general formula (1), wherein the polymerizable group is selected from the following groups:

[0023] Among them, R 7Each independently represents an H 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, an alkyl group having 1 to 30 carbon atoms Acyloxy, haloalkylacyloxy having 1 to 30 carbon atoms, alkylaryl having 6 to 30 carbon atoms, arylalkyl having 6 to 30 carbon atoms, alkylaryloxy having 6 to 30 carbon atoms, arylalkyloxy having 6 to 30 carbon atoms, arylcarbonyl having 6 to 30 carbon atoms, aryloxycarbonyl having 6 to 30 carbon atoms, arylcarbonyloxy having 6 to 30 carbon atoms and aryloxycarbonyloxy 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-, -CO-, -OCO-, -COO-, -SCO-, -COS-substituted; optionally, one or more H atoms in the alkyl, alkoxy, alkenyl, alkenyloxy group may be substituted by halogen, halogen, cyano, hydroxyl, nitro, carboxyl, carbamoyloxy, amino, sulfamoyl, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, thioisocyanato, alkyl having 1 to 30 carbon atoms, haloalkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, haloalkoxy having 1 to 30 carbon atoms, alkylacyloxy having 1 to 30 carbon atoms, haloalkylacyloxy having 1 to 30 carbon atoms.

[0024] As a compound of general formula (1), wherein P1 and P2 each independently represent a group (P-1) and (P-2); preferably, P1 and P2 each independently represent a group (P-1); more preferably, P1 and P2 each independently represent an acrylate group.

[0025] As a compound of the general formula (1), wherein L1 and L2 each independently represent an alkylene group having 1 to 30 carbon atoms; the alkylene group is linear; one or more -CH2- in the alkylene group may be substituted by -O-, -S-, or -NH-;

[0026] Preferably, L1 and L2 each independently represent an alkylene group having 2 to 20 carbon atoms; the alkylene group is linear; and one or more -CH2- groups in the alkylene group may be substituted by -O-.

[0027] More preferably, L1 and L2 each independently represent an alkylene group having 2 to 15 carbon atoms; one or more -CH2- groups in the alkylene group may be substituted by -O-.

[0028] As a compound of the general formula (1), wherein R1-R6 and R arepresents an alkyl group having 1 to 30 carbon atoms, an alkylaryl group having 6 to 30 carbon atoms, or an arylalkyl group having 6 to 30 carbon atoms; one or more -CH2- groups in the alkyl group may be substituted by -O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, or -COS-; optionally, one or more H atoms in the alkyl group may be substituted by 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 thioisocyanato 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 alkylacyloxy group having 1 to 30 carbon atoms, a haloalkylacyloxy group having 1 to 30 carbon atoms, or a polymerizable group.

[0029] Preferably, R1-R6 and R a represents an alkyl group having 1 to 25 carbon atoms, an alkylaryl group having 6 to 25 carbon atoms, or an arylalkyl group having 6 to 25 carbon atoms; one or more -CH2- groups in the alkyl group may be substituted by -O-, -S-, or -NH-; optionally, one or more H atoms in the alkyl group may be substituted by a halogen, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 25 carbon atoms, a haloalkyl group having 1 to 25 carbon atoms, an alkoxy group having 1 to 25 carbon atoms, a haloalkoxy group having 1 to 25 carbon atoms, an alkylacyloxy group having 1 to 25 carbon atoms, a haloalkylacyloxy group having 1 to 25 carbon atoms, or a polymerizable group.

[0030] More preferably, R1-R6 and R a represents an alkyl group having 1 to 20 carbon atoms, an alkylaryl group having 6 to 20 carbon atoms, or an arylalkyl group having 6 to 20 carbon atoms; one or more -CH2- groups in the alkyl group may be substituted by -O-, -S-, or -NH-; optionally, one or more H atoms in the alkyl group may be substituted by a halogen, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a haloalkoxy group having 1 to 20 carbon atoms, an alkylacyloxy group having 1 to 20 carbon atoms, a haloalkylacyloxy group having 1 to 20 carbon atoms, or a polymerizable group.

[0031] More preferably, R1-R6 and R a represents an alkyl group having 1 to 15 carbon atoms, an alkylaryl group having 6 to 15 carbon atoms, or an arylalkyl group having 6 to 15 carbon atoms; one or more -CH2- groups in the alkyl group may be substituted by -O-, -S-, or -NH-; optionally, one or more H atoms in the alkyl group may be substituted by a halogen, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 15 carbon atoms, a haloalkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, a haloalkoxy group having 1 to 15 carbon atoms, an alkylacyloxy group having 1 to 15 carbon atoms, a haloalkylacyloxy group having 1 to 15 carbon atoms, or a polymerizable group.

[0032] Most preferably, R1-R6 and R a represents an alkyl group having 1 to 10 carbon atoms, an alkylaryl group having 6 to 10 carbon atoms, or an arylalkyl group having 6 to 10 carbon atoms; one or more -CH2- groups in the alkyl group may be substituted by -O-; optionally, one or more H atoms in the alkyl group may be substituted by a halogen, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, or a polymerizable group.

[0033] In a preferred embodiment, R1-R5 and Rx represent H atoms; R6 represents an alkyl group having 1-30 carbon atoms, wherein one or more -CH2- in the alkyl group is substituted by -O-; optionally, one or more H atoms in the alkyl group are substituted by a polymerizable group.

[0034] As aromatic rings or non-aromatic rings not specified in the present invention, include but are not limited to cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, benzene, pentalene, perhydropentalene, Azulene, perhydroazulene, indene, perhydroindene, indane, naphthalene, dihydronaphthalene, tetrahydronaphthalene, perhydronaphthalene, heptatrienol, perhydroheptatrienol, biphenyl, unsymmetrical indacene, symmetrical indacene, acenaphthene, dihydroacenaphthene, fluorene, phenanthene, phenanthracene, anthracene, spiro[4.4]nonane, spiro[4.5]decane, spiro[5.5]undecane, bicyclo[2.2.1]heptane, bicyclo[2.2.1]heptane 2-ene, bicyclo[3.1.1]heptane, bicyclo[3.1.1]hept-2-ene, bicyclo[2.2.2]octane, bicyclo[2.2.2]oct-2-ene, adamantane or noradamantane ring; pyrrole, imidazole, triazole, tetrazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, azapine, diazepine, furan, pyran, oxapine, thiophene, thiopyran, thiapine, oxazole, isoxazole, thiazole, isoxazole, Thiazole, furazan, oxadiazole, oxazine, oxadiazine, oxazepine, oxadiazepine, thiadiazole, thiazine, thiadiazine, thiazepine, thiadiazepine, indole, isoindole, indolizine, benzofuran, isobenzofuran, benzothiophene, isobenzothiophene, dithiazine, indazole, quinoline, isoquinoline, quinolizine, purine, 2,3-diazine, pteridine, 1,5-diazine, quinoxaline, quinazoline, 1,2-naphthyridine, benzoxazole, benzothiazole, benzimidazole, benzopyran, benzoxepin, benzoxazepine, benzooxydiazepine, benzothiazepine, benzothiazepine, benzothiadiazepine, benzoazepine, benzodiazepine, benzofurazan, benzothiadiazole, benzotriazole, carbazole, β-carboline, acridine, phenazine, dibenzofuran, xanthene, dibenzothiophene, phenothiazine, phenoxazine, benzoxathiazole, thianthrene, phenanthridine, phenanthroline, perylene, pyrazolopyridine, aziridine pyridine, azetidine, pyrroline, pyrrolidine, imidazoline, imidazolidine, triazoline, triazolidine, tetrazoline, tetrazolidine, pyrazoline, pyrazolidine, dihydropyridine, tetrahydropyridine, piperidine, dihydropyrazine, tetrahydropyrazine, piperazine, dihydropyrimidine, tetrahydropyrimidine, perhydropyrimidine, dihydropyridazine, tetrahydropyridazine, perhydropyridazine, dihydroazepine, tetrahydroazepine, perhydroazepine, dihydrodiazepine, tetrahydrodiazepine, perhydrodiazepine, oxirane, oxetane, dihydrofuran, tetrahydrofuran, dihydropyran, Tetrahydropyran, dihydrooxazone, tetrahydrooxazone, perhydrooxazone, thiirane, thietane, dihydrothiophene, tetrahydrothiophene, dihydrothiopyran, tetrahydrothiopyran, dihydrothiazole, tetrahydrothiazole, perhydrothiazole, dihydrooxazole, tetrahydrooxazole (oxazolidine), dihydroisoxazole, tetrahydroisoxazole (isoxazolidine), dihydrothiazole, tetrahydrothiazole (thiazolidine), dihydroisothiazole, tetrahydroisothiazole (isothiazolidine), dihydrofurazan, Tetrahydrofurazan, dihydrooxadiazole, tetrahydrooxadiazole (oxadiazolidine), dihydrooxazine, tetrahydrooxazine, dihydrooxadiazine, tetrahydrooxadiazine, dihydrooxazepine, tetrahydrooxazepine, perhydrooxazepine, dihydrooxydiazepine, tetrahydrooxydiazepine, perhydrooxydiazepine, dihydrothiadiazole, tetrahydrothiadiazole (thiadiazolidine), dihydrothiazine, tetrahydrothiazine, dihydrothiadiazine, tetrahydrothiadiazine, dihydrothiazepine, tetrahydrothiazepine, Perhydrothiazepine, dihydrothiazepine, tetrahydrothiazepine, perhydrothiazepine, morpholine, thiomorpholine, oxathiinane, dihydroindoline, isoindoline, dihydrobenzofuran, perhydrobenzofuran, dihydroisobenzofuran, perhydroisobenzofuran, dihydrobenzothiophene, perhydrobenzothiophene, dihydroisobenzothiophene, perhydroisobenzothiophene, dihydroindazole, perhydroindazole, dihydroquinoline, tetrahydroquinoline, perhydroquinoline, dihydro Isoquinoline, tetrahydroisoquinoline, perhydroisoquinoline, dihydro2,3-diazine, tetrahydro2,3-diazine, perhydro2,3-diazine, dihydro1,5-diazine, tetrahydro1,5-diazine, perhydro1,5-diazine, dihydroquinoxaline, tetrahydroquinoxaline, perhydroquinoxaline, dihydroquinazoline, tetrahydroquinazoline, perhydroquinazoline, dihydro1,2-diazine, tetrahydro1,2-diazine, perhydro1,2-naphthyridine, benzothioxane, dihydrobenzoxazine, dihydrobenzothiazine, pyrazinomorpholine, dihydrobenzoxazole, perhydrobenzoxazole, dihydrobenzothiazole, perhydrobenzothiazole, dihydrobenzimidazole, perhydrobenzimidazole, dihydrobenzazepine, tetrahydrobenzazepine, dihydrobenzodiazepine, tetrahydrobenzodiazepine, benzodioxine, dihydrobenzoxazepine, tetrahydrobenzoxazepine, dihydrocarbazole, tetrahydrocarbazole, Perhydrocarbazole, dihydroacridine, tetrahydroacridine, perhydroacridine, dihydrodibenzofuran, dihydrodibenzothiophene, tetrahydrodibenzofuran, tetrahydrodibenzothiophene, perhydrodibenzofuran, perhydrodibenzothiophene, dioxolane, dioxane, dithiolane, dithiolane, dioxaindan, benzodioxane, chroman, benzodithiolane, benzodithiolane, azaspiro[4.4]nonane, oxazazepine Spiro[4.4]nonane, dioxaspiro[4.4]nonane, azaspiro[4.5]decane, thiaspiro[4.5]decane, dithiaspiro[4.5]decane, dioxaspiro[4.5]decane, oxazaspiro[4.5]decane, azaspiro[5.5]undecane, oxaspiro[5.5]undecane, dioxaspiro[5.5]undecane, azabicyclo[2.2.1]heptane, oxabicyclo[2.2.1]heptane , azabicyclo[3.1.1]heptane, azabicyclo[3.2.1]octane, oxabicyclo[3.2.1]octane, azabicyclo[2.2.2]octane, diazabicyclo[2.2.2]octane, tetrahydro-β-carboline, hexahydroazaindole, oxazaspiro[2.5]octane, hexahydroazaindazole, hexahydropyrazolopyridoazepine, tetrahydropyrazoloisoquinoline or tetrahydropyrazolo1,5-naphthyridine ring. ,

[0035] Preferably, the aromatic ring or non-aromatic ring includes, but is not limited to, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, benzene, naphthalene, dihydronaphthalene, tetrahydronaphthalene, biphenyl, unsymmetrical indacene, symmetrical indacene, acenaphthene, fluorene, phenanthrene, anthracene; pyrrole, imidazole, triazole, tetrazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, azepine, diazepine, furan, pyran, oxazone, thiophene, thiopyran, thiazone, oxazole, isoxazole, thiazole, isothiazole, furazan, oxadiazole, oxazine, oxadiazine, oxazepine, oxadiazepine, thiadiazole, thiazine, thiadiazine, thiazepine, thiadiazepine, indole, isoindole, indolizine, benzofuran, isobenzofuran, benzothiophene, isobenzothiophene, dithiaphthene, indazole, quinoline, isoquinoline, quinolizine, purine, 2,3-naphthyridine, pteridine, 1,5-naphthyridine, quinoxaline, quinazoline, 1,2-naphthyridine, benzoxazole, benzothiazole, benzimidazole, benzopyran, benzoxepin, benzoxazepine, benzooxydiazepine, benzothiazepine, benzothiazepine, benzothiadiazepine, benzoazepine, benzodiazepine, benzofurazan, benzothiadiazole, benzotriazole, carbazole, β-carboline, acridine, phenazine, dibenzofuran, xanthene, dibenzothiophene, phenothiazine, phenoxazine, benzoxathine, thianthrene, phenanthridine, phenanthroline, perylene, pyrazolopyridine.

[0036] More preferably, the aromatic ring or non-aromatic ring includes, but is not limited to, cyclohexene, cyclohexadiene, benzene, naphthalene, dihydronaphthalene, biphenyl, fluorene, phenanthrene, and anthracene.

[0037] More preferably, the aromatic ring or non-aromatic ring includes, but is not limited to, cyclohexene, benzene, and naphthalene.

[0038] In another aspect, the present invention provides a polymerizable composition comprising a polymerizable compound as described above and below.

[0039] The polymerizable composition as described above and below further comprises a matrix liquid crystal.

[0040] Advantageously, the parent liquid crystals as described above and below are commercially available.

[0041] In a specific embodiment, as the context described polymerizable composition, wherein the mother liquid crystal 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.

[0042] Preferably, the compound of formula (1) is added to the polymerizable composition at a concentration of not less than 10 wt %.

[0043] More preferably, the compound of formula (1) is added to the polymerizable composition at a concentration of not less than 20 wt %.

[0044] More preferably, the compound of formula (1) is added to the polymerizable composition at a concentration of not less than 30 wt%.

[0045] The polymerizable composition as described above and below optionally further comprises additives.

[0046] 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.

[0047] Advantageously, the additive is present in an amount of 0-10 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.

[0048] The polymerizable composition as described above and below further comprises an organic solvent.

[0049] As the organic solvent mentioned above and below, it is preferred that the organic solvent has good solubility in the polymerizable composition and can be removed by drying at 100° C. or below.

[0050] The organic solvent is not particularly limited, but is preferably an organic solvent in which the polymerizable composition shows good solubility, preferably aromatic solvents such as toluene, xylene, isopropyl benzene, 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, etc.

[0051] The organic solvents described above and below may be used alone or in combination of two or more.

[0052] Considering the stability of the solution, it is preferred to use one or more of ketone solvents, ether solvents, ester solvents and aromatic solvents.

[0053] As the polymerizable composition described above and below, the organic solvent content is 25-95 wt%, preferably 30-90 wt%, more preferably 35-85 wt%, and most preferably 40-80 wt%, based on the total weight of the polymerizable composition.

[0054] When preparing a solution of the polymerizable composition, heating and / or stirring are advantageously performed in order to promote dissolution of the polymerizable composition.

[0055] Furthermore, the polymerizable composition described above and below is coated on a substrate and cured to form a cured product.

[0056] Coating methods include, but are not limited to, coater coating, rod coating, spin coating, gravure printing, flexographic printing, inkjet coating, die coating, CAP coating, dipping, and other methods known in the art. After coating the polymerizable composition, it is cured (dried).

[0057] Advantageously, curing is performed by polymerization. When polymerizing the polymerizable composition, it is desirable to rapidly polymerize it, and therefore, polymerization is preferably performed by irradiation with active energy rays such as ultraviolet-visible light or electron beams. When ultraviolet-visible light is used, either a polarized or non-polarized light source may be used.

[0058] The substrate of the cured product includes, but is not limited to, a glass substrate, a metal substrate, a ceramic substrate, and a polymer substrate. 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, among others.

[0059] Based on process suitability, especially heat resistance and chemical stability, polyester, polystyrene, polyolefin, cellulose derivative, polyarylate, and polycarbonate are preferred.

[0060] In yet another aspect, the present invention provides an optically anisotropic body comprising a substrate, a polymer film formed from a cured product of the polymerizable composition as described above and below, and, if necessary, an alignment film.

[0061] Advantageously, the optically anisotropic body is formed by laminating a substrate, an alignment film if necessary, and a polymer film formed of a cured product of the polymerizable composition in this order.

[0062] Materials for the alignment film include, but are not limited to, polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene oxide, polyarylate, polyethylene terephthalate, polyethersulfone, epoxy resin, acrylic resin, epoxy acrylic resin, coumarin, chalcone, cinnamate, anthraquinone, azo compounds, and aromatic vinyl compounds. Polyimide is preferred based on process applicability, especially heat resistance and chemical stability.

[0063] Advantageously, the oriented film is obtained by an orientation treatment, which may be a stretching treatment, a rubbing treatment, polarized ultraviolet-visible light irradiation, an ion beam treatment, etc. Preferably, the orientation treatment is a rubbing treatment or polarized ultraviolet-visible light irradiation.

[0064] In yet another aspect, the present invention provides an optically anisotropic body formed from the cured product described above and below and / or use of the optically anisotropic body in optical, optoelectronic, electronic, or semiconductor components or devices.

[0065] The applications described in the context include, but are not limited to, birefringent films, optical delay films (phase difference films), negative dispersion optical films, optical compensation films, vision enlargement 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, and elliptically polarizing elements.

[0066] Preferably, the application is a negative dispersion optical film.

[0067] The negative dispersion optical films described above and below exhibit minimal poor thickness uniformity and orientational inhomogeneity. Therefore, each of the compounds described above and below can be used as a component of a polymerizable composition. Furthermore, optically anisotropic polymers produced using polymerizable compositions containing the compounds of the present invention can be used in applications such as optical films. DETAILED DESCRIPTION

[0068] In the present invention, technical terms are further explained and defined in detail.

[0069] The term "liquid crystal" or "mesogenic compound" refers to a compound that forms a mesomorphic phase or a liquid crystal phase under certain conditions.

[0070] The term "polymerizable mesogen" or "polymerizable compound", abbreviated as RM, denotes a polymerizable liquid crystal or mesogenic compound, in particular a monomeric compound.

[0071] The term "monoreactive" or "direactive" means that the polymerizable mesogen or polymerizable compound has one or two polymerizable groups.

[0072] The term "polymerizable group" refers to a group that is polymerized by light, heat, a catalyst, or the like to form a polymer of higher molecular weight.

[0073] The term "film" refers to a mechanically stable rigid or flexible coating or layer; optionally, the film can be alone; on a supporting substrate; or sandwiched between two substrates.

[0074] The term "negative dispersion" or "reverse wavelength dispersion" means that in a graph plotted with the wavelength λ of the incident light on the retardation film as the horizontal axis and the birefringence Δn as the vertical axis, the birefringence Δn decreases as the wavelength λ is shorter.

[0075] The present invention is further described below in conjunction with synthesis examples and embodiments, but the application of the present invention is not limited thereto. Unless otherwise specified, the percentages in the embodiments are all by mass.

[0076] Synthesis example:

[0077] The specific polymerizable compound is the following structural formula:

[0078] The preparation method of P-1 is as follows:

[0079] Preparation of intermediate S-3

[0080] 30g of S-1 was added to a 250ml reaction flask, followed by 240g of DMF and 10.2g of S-2 under nitrogen. The temperature was raised to 90°C and the reaction was allowed to proceed for 24 hours. Post-treatment: The reaction solution was added to 720g of water. Solids precipitated after standing. The crude product was filtered and passed through a silica gel chromatography column with dichloromethane to obtain 19.4g of intermediate S-3, a 66% yield.

[0081] Preparation of intermediate S-4

[0082] Add 16g of S-3 to a 100ml reaction flask, along with 100g of methanol, 10g of water, and 10g of sodium hydroxide. Heat to 60°C and react for 8h. Post-treatment: Remove the solvent under reduced pressure, then dissolve in 200g of water. Adjust the pH to approximately 5 with hydrochloric acid. Filter, wash, and dry to obtain S-4: 13g of solid, 86% yield.

[0083] Preparation of intermediate S-6

[0084] 10g of S-4 and 23.3g of S-5 were added to a 250ml reaction flask. 100g of dichloromethane and 1.3g of DMAP were added. The temperature was then lowered to 0°C and a dichloromethane solution of DCC (12g dissolved in 60g of dichloromethane) was added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction was allowed to proceed for 12 hours. Post-treatment: First, the filter cake was filtered with suction and washed with dichloromethane. The liquid phase was retained and washed with 100g of 5% hydrochloric acid and then twice with 100g of water. After drying, the organic phase was passed through a silica gel column. 0.07g of p-methoxyphenol was added to the eluate, and the solvent was removed under reduced pressure. The product was recrystallized from 200g of methanol and 20g of dichloromethane. S-6 (16g) was obtained, with a yield of 80%.

[0085] Preparation of intermediate S-8

[0086] Add 15g of S-6 to a 250ml reaction flask, along with 100ml of dichloromethane, 6.9g of S-7, and 3g of camphorsulfonic acid. Heat to 50°C under nitrogen for 5h. Use this as raw material for the next step without purification. The yield in this step is calculated as 100%.

[0087] Preparation of product P-1

[0088] To the reaction mixture of S-8, add 6 g of DIPEA. Under nitrogen, lower the temperature to 0°C and dropwise add 2.7 g of acryloyl chloride. After complete addition, raise the temperature to 25°C and react for 3 h. Post-processing: Pass the reaction mixture directly through a silica gel chromatography column and concentrate. Dissolve the oil in 30 g of dichloromethane, add 300 g of methanol dropwise, stir to crystallize, and filter and dry to obtain 17 g of the product (85% yield).

[0089] The NMR data are as follows, 1 H NMR(CDCl3)δ: 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, 4H), 7.14(t, 2H), 7.32(t, 2H), 7.53(d, 2H), 7.65(d, 1H), 7.69 (d,1H).

[0090] Preparation of P-2

[0091] Preparation of intermediate S-6

[0092] Prepared as per P-1.

[0093] Preparation of product P-2

[0094] Add 15g of S-9 to a 250ml reaction flask, add 100ml of dichloromethane, add 5.0g of S-9, and add 3g of camphorsulfonic acid. Under nitrogen, heat to 50°C and react for 5h. Post-processing: The reaction solution was directly passed through a silica gel chromatography column and then concentrated. The oil was dissolved in 30g of dichloromethane, to which 300g of methanol was added dropwise. The mixture was stirred to crystallize, and filtered and dried to obtain 17.2g of the product, with a yield of 92%.

[0095] The NMR data are as follows, 1 H NMR(CDCl3)δ: 1.22-1.28(m, 4H), 1.44-1.47(m, 8H), 1.60-1.82(m, 12H), 1.90(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), 3.85-3.89( 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, 4H), 7.14(t, 2H), 7.32(t, 2H), 7.52(t, 2H), 7.67(t, 2H).

[0096] Preparation of product P-3

[0097] Preparation of intermediate S-6

[0098] Prepared as per P-1.

[0099] Preparation of product P-3

[0100] Add 15g of S-6 to a 250ml reaction flask, followed by 100ml of dichloromethane, 4.6g of S-10, and 3g of camphorsulfonic acid. Under nitrogen, heat to 50°C and react for 5h. For post-treatment, pass the reaction solution directly through a silica gel chromatography column and concentrate. Dissolve the oil in 30g of dichloromethane, then add 300g of methanol dropwise. Stir and crystallize. Filter and dry to obtain 17g of the product, with a yield of 93%.

[0101] The NMR data are as follows, 1 H NMR (CDCl3) δ: 1.17 (m, 3H), 1.24 (m, 4H), 1.48-1.93 (m, 28H), 2.08 (t, 4H), 2.23(m, 4H), 2.54(m, 2H), 3.86(d, 4H), 3.94(t, 4H), 4.17(t, 4H), 4.53(t, 2H), 4.65(t, 2H), 5.82(d, 2H), 6.12(d, 2H), 6.40(d, 2H), 6.88(m, 6H), 6.9 7(d, 4H), 7.16(t, 2H), 7.34(t, 2H), 7.54(d, 2H), 7.66(d, 1H), 7.70(d, 1H).

[0102] Example

[0103] A polyimide solution for an alignment film was applied to a glass substrate having a thickness of 0.7 mm, dried at 100° C. for 10 minutes, and then fired at 200° C. for 60 minutes to obtain a coating film. The obtained coating film was subjected to a rubbing treatment using a commercially available rubbing device.

[0104] 40% of the compound to be evaluated was added to the mother liquid crystal M to prepare a polymerizable composition. 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. This coating solution was applied to the rubbed glass substrate by spin coating. After drying at 80°C for 1 minute and then at 120°C for 1 minute, the solution was heated at 40 mW / cm using a high-pressure mercury lamp. 2 The film to be evaluated was prepared by irradiating the film with ultraviolet rays at an intensity of 1000 nm for 25 seconds.

[0105] Table 1

[0106] Comparative Examples 1-3 used compounds B-1 to B-3 known in the prior art.

[0107] For the polymer obtained, the degree of unevenness is evaluated by polarizing microscope observation. Make 10 films each with the compound of evaluation object added, count out uneven number. The uneven number observed in 10 films is added up, and if the uneven number is 0, it is recorded as excellent, if it is not 1, it is recorded as good, if it is not 1-10, it is recorded as medium, and if it is not more than ten, it is recorded as poor.

[0108] See Table 1 for the results.

[0109] Table 1

[0110] To evaluate its film-forming properties, the film thickness is measured at the four corners and five points in the middle of a film. The average value is then calculated and the difference between each test point and the average value is compared.

[0111] Table 2

[0112] As shown in Table 1-2, the compound of the present invention has high storage stability when constituting a polymerizable composition, and the optical anisotropy of the composition containing the compound of the present invention is preferably oriented, and the film formed is relatively thin (i.e., less uneven orientation occurs); the thickness of the formed film is relatively uniform, and the error range is small (i.e., less occurrence of poor film thickness uniformity). Compared with Comparative Examples 1-3, the optical properties of the film material are effectively improved. Therefore, the compound of the present invention is useful as a constituent component of a polymerizable composition. In addition, the optical anisotropy of the polymerizable liquid crystal composition containing the compound of the present invention is useful in applications such as optical films.

[0113] It should be understood that the specific embodiments of the present invention are intended only to illustrate the spirit and principles of the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the present invention, those skilled in the art may make various changes, substitutions, deletions, corrections, or adjustments to the technical solutions of the present invention, and such equivalent technical solutions also fall within the scope defined by the claims of the present invention.

Claims

1. A polymerizable compound, characterized in that The polymerizable compound is selected from the compounds represented by general formula (1), In the formula, P1 and P2 each independently represent a polymerizable group; L1 and L2 each independently represent an alkylene group having 1 to 30 carbon atoms; the alkylene group may be linear or branched; one or more -CH2- in the alkylene group may be replaced by -O-, -S-, -NH-, -NR a -, -CO-, -OCO-, -COO-, -OCOO-, -SCO-, -COS-substituted; R1-R6 and R a Each independently represents an H 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, an alkyl group having 1 to 30 carbon atoms The alkyl, alkoxy, alkenyl, and alkenyloxy groups may be substituted with -O-, -S-, -NH-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C-, -C- -CO-, -OCO-, -COO-, -SCO-, -COS-substituted; optionally, one or more H atoms in the alkyl, alkoxy, alkenyl, alkenyloxy group may be substituted by halogen, halogen, cyano, hydroxyl, nitro, carboxyl, carbamoyloxy, amino, sulfamoyl, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, thioisocyano, alkyl having 1 to 30 carbon atoms, haloalkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, haloalkoxy having 1 to 30 carbon atoms, alkylacyloxy having 1 to 30 carbon atoms, haloalkylacyloxy having 1 to 30 carbon atoms, or a polymerizable group; m, n and r each independently represent an integer from 0 to 4; p and q each independently represent an integer of 0-3.

2. The polymerizable compound according to claim 1, wherein The polymerizable group is selected from the following groups: Among them, R 7 Each independently represents an H 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, The present invention relates to a halogenated alkylcarbonyl group having 1-30 carbon atoms, an alkylacyloxy group having 1-30 carbon atoms, a halogenated alkylacyloxy group having 1-30 carbon atoms, an alkylaryl group having 6-30 carbon atoms, an arylalkyl group having 6-30 carbon atoms, an alkylaryloxy group having 6-30 carbon atoms, an arylalkyloxy group having 6-30 carbon atoms, an arylcarbonyl group having 6-30 carbon atoms, an aryloxycarbonyl group having 6-30 carbon atoms, an arylcarbonyloxy group having 6-30 carbon atoms, and an aryloxycarbonyloxy group having 6-30 carbon atoms; one or more -CH2- in the alkyl, alkoxy, alkenyl, and alkenyloxy groups may be substituted by -O-, -S-, -NH-, -CO-, -OCO-, -COO- -, -SCO-, -COS-; optionally, one or more H atoms in the alkyl, alkoxy, alkenyl, alkenyloxy group may be substituted by halogen, halogen, cyano, hydroxyl, nitro, carboxyl, carbamoyloxy, amino, sulfamoyl, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, thioisocyano, alkyl having 1 to 30 carbon atoms, haloalkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, haloalkoxy having 1 to 30 carbon atoms, alkylacyloxy having 1 to 30 carbon atoms, and haloalkylacyloxy having 1 to 30 carbon atoms.

3. The polymerizable compound according to claim 2, wherein P1 and P2 each independently represent a group of (P-1) and (P-2).

4. The chiral photosensitive compound according to claim 3, wherein P1 and P2 each independently represent an acrylate group.

5. The chiral photosensitive compound according to claim 1, wherein L1 and L2 each independently represent an alkylene group having 1 to 16 carbon atoms.

6. The chiral photosensitive compound according to claim 1, wherein R1-R5 and R a Each independently represents a hydrogen atom; R6 represents an alkyl group having 1 to 30 carbon atoms, one or more -CH2- in the alkyl group is substituted by -O-; optionally, one or more H atoms in the alkyl group are substituted by a polymerizable group.

7. A polymerizable composition, characterized in that The method comprises the polymerizable compound according to claim 1 and a mother liquid crystal.

8. The polymerizable composition according to claim 7, wherein The mother liquid crystal contains 50% of compound (M-1), 30% of compound (M-2) and 20% of compound (M-3), 9. An optically anisotropic body, characterized in that: The polymerizable composition according to claim 7 or 8 is used.

10. The optically anisotropic body according to claim 9, wherein The optical anisotropic body is selected from negative dispersion optical films.

Images