CN113816854A - Polymerizable compound based on 2, 7-dihydroxyfluorene as well as preparation method and application thereof - Google Patents

Polymerizable compound based on 2, 7-dihydroxyfluorene as well as preparation method and application thereof Download PDF

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CN113816854A
CN113816854A CN202111265757.XA CN202111265757A CN113816854A CN 113816854 A CN113816854 A CN 113816854A CN 202111265757 A CN202111265757 A CN 202111265757A CN 113816854 A CN113816854 A CN 113816854A
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叶永
殷勇
谭玉东
靳灿辉
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Jiangsu Creative Electronic Chemicals Co ltd
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    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
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    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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Abstract

Disclose aPolymerizable compound based on 2, 7-dihydroxyfluorene and preparation method and application thereof, wherein the compound is selected from compounds of general formula (1), P1、P2、L1、L2And R is as described above and below. The polymerizable compound can exhibit one or more of favorable substrate high adhesion in RM optical retardation films, is highly transparent to Vis-light, exhibits reduced random yellowing, and exhibits good high temperature stability.

Description

Polymerizable compound based on 2, 7-dihydroxyfluorene as well as preparation method and application thereof
Technical Field
The invention relates to a polymerizable compound based on 2, 7-dihydroxyfluorene, a preparation method and application thereof, in particular to application of the polymerizable compound in various optical anisotropic bodies; belongs to the technical field of optical materials.
Background
Polymerizable (mesogenic) compounds (RM) are gaining increasing attention as starting materials for the preparation of various optically anisotropic bodies. The prior art generally applies a solution of a polymerizable compound onto a substrate, aligns it, and cures it by heating or irradiating an active energy ray, thereby forming an optically anisotropic polymer film, also called an optically anisotropic body, having uniform orientation. The film orientation may be planar (liquid crystal molecules oriented substantially parallel to the layer), homeotropic (rectangular or perpendicular to the layer) or tilted, as well as cholesteric.
The optically anisotropic body includes, but is not limited to, an optical retardation film (phase difference film), an optical compensation film, a vision expanding film, a reflective film, a selective reflective film, an antireflection film, a brightness enhancement film, a liquid crystal alignment film, a polarizing element, a circular polarizing element, an elliptical polarizing element, and other various optical elements according to the application field.
Polymerizable compounds, while stable at room temperature, degrade at elevated temperatures. For example, when heated for a period of time, the optical properties of the dispersion or retardation degrade, resulting in a degradation of the properties of the optically anisotropic body over time. According to different studies, this can be attributed to a low degree of polymerization, a correspondingly high residual radical content of the polymer, shrinkage or thermo-oxidative degradation of the polymer, etc.
The optically anisotropic body is required to have various properties such as optical properties, polymerization rate, solubility, melting point or glass transition temperature, transparency, mechanical strength, surface hardness, heat resistance and light resistance, which are required. The characteristics of the optically anisotropic body depend not only on the kind of the polymerizable compound used but also on the ratio of the polymerizable compounds.
RM optical retardation films with low diacrylate content are well suited for applications where good adhesion of the RM optical retardation film to the substrate is important. However, in RM optical retardation films with low diacrylate content, the optical retardation usually drops significantly, especially due to polymer shrinkage.
On the other hand, in the case of the optical retardation film, it is necessary to add a polymerizable compound to a mother liquid crystal to obtain a polymerizable composition, thereby making the wavelength dispersion of birefringence thereof small while effectively improving the viewing angle of the display. In this case, a high addition concentration of the polymerizable compound is advantageous. However, the conventional polymerizable compound is not easily stored stably in such a case and is easily precipitated. In the case where the maximum stable concentration is insufficient, there is brought about an adverse effect that the nonuniformity of the film becomes poor.
Therefore, it is required to develop a polymerizable compound, the use of which can solve the above-mentioned technical problems.
Disclosure of Invention
It is an object of the present invention to provide a polymerizable compound capable of exhibiting one or more of favorable high substrate adhesion in an RM optical retardation film, high transparency to Vis-light, exhibiting reduced random yellowing, and exhibiting good high temperature stability and the like. Further, the compound can exhibit not only favorable substrate adhesion in RM optical retardation films, but also good high temperature stability. Meanwhile, high addition concentration in the mother liquid crystal can be realized, sufficient maximum stable concentration is obtained, and further, the nonuniformity of the film is improved.
It is a second object of the present invention to further provide a process for the preparation of a polymerizable compound comprising the above and below.
It is a further object of the present invention to provide the use of the polymerizable compounds described above and below in various optically anisotropic bodies.
To achieve the above object, in one aspect, the present invention provides a polymerizable compound selected from compounds of the general formula (1),
Figure BDA0003326934100000031
in the formula (I), the compound is shown in the specification,
P1and P2Each independently represents a polymerizable group;
L1and L2Each independently represents a single bond, -O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, -COS-, -OCOO-, -NHCO-, -CONH-, -OCH2-、-CH2O-、-SCH2-、-CH2S-、-OCF2-、-CF2O-、-SCF2-、-CF2S-、-CH＝CHOCO-、-CH＝CHCOO-、-OCOCH＝CH-、-COOCH＝CH-、-CH2CH2OCO-、-CH2CH2COO-、-OCOCH2CH2-、-COOCH2CH2-、-CH2OCO-、-CH2COO-、-OCOCH2-、-COOCH2-, -CH ═ CH-, -N ═ CH-, -CH ═ N-, -N ═ N-, -CH ═ CF-, -CF ═ CH-, -N ═ CF-, -CF ═ N-, -C ≡ C-, or alkylene having a carbon number of 1 to 30; one or more-CH's in said alkylene group2May be substituted by-O-, -S-, -NH-, -NRa-, -CO-, -OCO-, -COO-, -SCO-, -COS-substitution;
C1and C2Each independently represents-CO-, -OCO-, -COO-, -SCO-, -COS-, -NHCO-, -CONH-, -CH2-、-CF2-；
R independently represents H, C1-30 alkyl, C1-30 haloalkyl, C1-30 alkoxy, C1-30 haloalkoxy, C2-30 alkenyl, C2-30 haloalkenyl, C2-30 alkenyloxy, C2-30 haloalkenyloxy, C1-30 alkoxycarbonyl, C1-30 haloalkoxycarbonyl, C1-30 alkylcarbonyl, C1-30 haloalkylcarbonyl, C1-30 alkylacyloxy or C1-30 haloalkoyloxy; raEach independently represents an alkyl group having 1 to 30 carbon atoms.
As the compound of the general formula (1), wherein the polymerizable group is selected from the following groups:
Figure BDA0003326934100000041
in the formula, R3Each 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 alkanoyloxy group having 1 to 30 carbon atoms or a haloalkoyloxy group having 1 to 30 carbon atoms.
As the compound of the general formula (1), wherein, P1And P2Each independently represents a group of (P-1) and (P-2); preferably, P1And P2Each independently represents a group of (P-1).
As the compound of the general formula (1), wherein L1And L2Each independently represents an alkylene group having 1 to 30 carbon atoms; one or more-CH's in said alkylene group2-may be substituted by-O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, -COS-.
Preferably, L1And L2Each independently represents an alkylene group having 1 to 30 carbon atoms.
Further preferably, L1And L2Each independently represents an alkylene group having 2 to 20 carbon atoms.
More preferably, L1And L2Each independently represents an alkylene group having 2 to 15 carbon atoms.
Most preferably, L1And L2Each independently represents an alkylene group having 2 to 10 carbon atoms.
As the compound of the general formula (1), wherein C1And C2Each independently represents-OCO-, -COO-, -SCO-, -COS-.
Preferably, C1And C2Each independently represents-OCO-, -COO-.
The compound of the general formula (1) is represented by R, each independently represents H or an alkyl group having 1 to 30 carbon atoms.
Preferably, each R independently represents H or an alkyl group having 1 to 10 carbon atoms.
More preferably, each R independently represents H or an alkyl group having 1 to 6 carbon atoms.
Most preferably, each R independently represents H or an alkyl group having 1 to 4 carbon atoms.
In another aspect, the present invention also provides a process for the preparation of the polymerizable compound described above and below, which comprises: reacting a compound of formula (2) with a compound of formula (3) and a compound of formula (4) to give a compound of formula (1) as described above and below;
Figure BDA0003326934100000061
P1-L1-C1-X (3)；
P2-L2-C2-X (4)；
wherein, P1、P2、L1、L2And R is as described above and below; x represents a halogen.
In a further aspect, the present invention provides the use of the polymerizable compounds described above and below in various optically anisotropic bodies.
Advantageously, the polymerizable compound is included in a polymerizable composition for use in various optically anisotropic bodies.
The polymerizable compositions described above and below optionally include a mono-reactive polymerizable compound.
The polymerizable composition as described above and below, wherein the compound of the general formula (1) is contained in an amount of 80 to 99% by weight based on the total weight of the polymerizable composition.
Preferably, the compound of formula (1) is present in an amount of 85 to 98 wt%, based on the total weight of the polymerizable composition; more preferably, the compound of formula (1) is present in an amount of 90 to 97 weight percent, based on the total weight of the polymerizable composition; and, most preferably, the compound of formula (1) is present in an amount of 92 to 96.5 wt%, based on the total weight of the polymerizable composition.
The polymerizable composition as described above and below further comprising an additive.
As the additives, there are included, but not limited to, polymerization initiators, sensitizers, stabilizers, leveling agents, surfactants, polymerization inhibitors, antioxidants, colorants, dispersants, lubricants, hydrophobing agents, adhesives, flow improvers, antifoaming agents, deaerators, diluents, thixotropic agents, gelling agents, catalysts, metals, metal complexes, luminescent materials, and the like.
Advantageously, the additive is present in an amount of from 0.01 to 10 weight percent, preferably from 0.02 to 8 weight percent, more preferably from 0.05 to 5 weight percent, and most preferably from 0.1 to 2 weight percent, based on the total weight of the polymerizable composition.
In yet another aspect, the present invention also provides a polymerizable composition solution comprising the polymerizable composition described above and below and an organic solvent.
As the organic solvent, it is preferable that the polymerizable composition has good solubility and can be removed by drying at 100 ℃. Organic solvents, including, but not limited to,
although not particularly limited, the polymerizable liquid crystal compound is preferably an organic solvent exhibiting good solubility, and is preferably an aromatic solvent such as toluene, xylene, cumene, mesitylene, or the like; ester solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and the like; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone; ether solvents such as tetrahydrofuran, 1, 2-dimethoxyethane and anisole, and amide solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone; propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, gamma-butyrolactone, chlorobenzene, and the like.
The organic solvents mentioned above and below may be used alone or in combination of two or more.
From the viewpoint of solution stability, it is preferable to use one or more of a ketone-based solvent, an ether-based solvent, an ester-based solvent and an aromatic solvent.
As the polymerizable composition solution, the organic solvent is contained in an amount of 30 to 95% by weight, preferably 40 to 90% by weight, more preferably 50 to 85% by weight, and, most preferably, 60 to 80% by weight, based on the total weight of the polymerizable composition solution.
In preparing the polymerizable composition solution, heating and/or stirring is advantageously performed in order to promote dissolution of the polymerizable composition.
In still another aspect, the present invention provides an optically anisotropic body comprising a substrate and a polymer film formed by solution-curing the above and below polymerizable composition, and, if necessary, an orientation film.
In one embodiment, a substrate, an orientation film, if necessary, and a polymer film formed by curing a polymerizable composition solution are sequentially laminated to form an optically anisotropic body.
In another embodiment, a substrate, an orientation film if necessary, and a polymer film formed by curing a polymerizable composition solution are sequentially stacked, and then a second orientation film if necessary, and a second polymer film formed by curing a polymerizable composition solution described above and below or a polymerizable composition solution different therefrom are sequentially stacked thereon.
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. Further, as the polymer base material, for example, there may be: cellulose derivatives, polyolefins, polyesters, polyolefins, polycarbonates, polyacrylates, polyarylates, polyethersulfones, polyamides, polyimides, polyphenylene sulfides, polyphenylene oxides or polystyrenes, and the like.
The process suitability based on optically anisotropic bodies is, in particular, from the viewpoint of heat resistance and chemical stability, preferably polyester, polystyrene, polyolefin, cellulose derivative, polyarylate, polycarbonate.
The alignment film material as the optically anisotropic body includes, but is 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 compound, arylvinyl compound, and the like.
As the orientation treatment, stretching treatment, rubbing treatment, polarized ultraviolet and visible light irradiation, ion beam treatment, or the like may be mentioned. Preferably, the orientation treatment is rubbing treatment or polarized uv-vis irradiation.
As a coating method for obtaining the optically anisotropic body of the present invention, a method known in the art, such as a coater method, a bar coating method, a spin coating method, a gravure printing method, a flexographic printing method, an ink jet method, a die coating method, a CAP coating method, and dipping, can be used. After the polymerizable composition solution is applied, it is dried.
In the solution polymerization of the polymerizable composition of the present invention, it is desirable to rapidly perform polymerization, and therefore it is preferable to perform polymerization by irradiating with an active energy ray such as ultraviolet visible light or an electron ray. In the case of using ultraviolet visible light, a polarized light source may be used, and an unpolarized light source may be used.
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 planar alignment state, a retardation film having birefringence in the plane with respect to the substrate can be obtained.
When the polymerizable compound and the polymerizable chiral compound in the polymerizable composition solution are polymerized in a planar orientation state, a retardation film having birefringence out of plane with respect to the substrate can be obtained.
When the polymerizable compound and the polymerizable discotic compound in the polymerizable composition solution are polymerized in a state of planar orientation, a retardation film having birefringence in both in-plane and out-of-plane with respect to the substrate can be obtained.
When the substrate has the same retardation, the retardation film of the present invention can be obtained as a birefringent retardation film by adding the birefringence of the retardation film to the birefringence of the substrate. The birefringence of both may be in the same direction or in different directions in the plane of the substrate.
The inventors have found that polymerizable compounds based on 2, 7-dihydroxyfluorene achieve unexpected technical effects in obtaining the optically anisotropic body of the present invention with specific properties.
Detailed Description
In the present invention, technical terms are further explained and defined in detail.
The term "liquid crystal" or "mesogenic compound" denotes a compound that forms a mesogenic or liquid crystalline phase under certain conditions.
The term "polymerizable mesogen" or "polymerizable compound", abbreviated RM, denotes polymerizable liquid crystalline or mesogenic compounds, especially monomeric compounds.
The term "mono-reactive" or "di-reactive" means that the polymerizable mesogen or polymerizable compound has one or two polymerizable groups.
The term "polymerizable group" means a group which is polymerized by means of light, heat or a catalyst to form a polymer of higher molecular weight.
The term "film" denotes a rigid or flexible coating or layer having mechanical stability; optionally, the membrane may be present alone; located over the support substrate; or sandwiched between two substrates.
The term "R" or "Re" denotes an optical retardation amount, particularly a phase retardation amount between ordinary light and extraordinary light.
The term "Rλ"or" Reλ"represents the amount of phase retardation when light is incident perpendicularly to the film surface at a wavelength of λ nm.
The term "Rin"or" Rein"indicates the phase delay amount at the initial time.
The present invention will be further described with reference to the following synthetic examples and examples, but the present invention is not limited to the application thereof. Unless otherwise indicated, percentages in the examples are uniformly percentages by mass.
Synthesis example 1: synthesis of Compound A
Figure BDA0003326934100000101
Adding 10g of 2, 7-dihydroxy-9H-fluorene, 22g of 6-chlorohexanol acrylate, 100g of DMF, 31g of potassium carbonate and 0.1g of potassium iodide into a reaction bottle, heating to 70 ℃, reacting for 4 hours until the end, adding the reaction liquid into 400g of water, adding 200g of dichloromethane, stirring, separating, collecting the lower organic layer, washing twice with water, concentrating, pulping with a methanol-toluene mixed solvent, and drying to obtain 18g of compound A, wherein the content: 97.4%, yield: 69.5 percent.1H NMR(400MHz,DMSO-d6)：δ7.76(d,2H.),7.06(s,2H.),6.89(d,2H.),6.27(d,2H.),6.03(t,2H.),5.61(d,2H.),4.15(s,2H.),4.03(t,4H.),3.98(t,4H),1.76(m,4H),1.63(m,4H.),1.41(m,8H.)。
Synthesis example 2: synthesis of Compound B
Figure BDA0003326934100000111
Synthesis of intermediate B-1:
Figure BDA0003326934100000112
4-hydroxy butyl acrylate, dichloromethane and pyridine, dropwise adding a dichloromethane solution of triphosgene, preserving heat for 1 hour after the dropwise adding is finished, dropwise adding water, separating liquid, collecting a lower layer, and concentrating dry dichloromethane to obtain an intermediate 1 for later use.
Synthesis of Compound B:
Figure BDA0003326934100000113
adding 10g of 2, 7-dihydroxy-9H-fluorene, 31.3g of intermediate 1 and 100g of dichloromethane into a reaction bottle, then dropwise adding 23g of diisopropylethylamine at the temperature of 0-5 ℃, adding water after complete reaction, separating liquid, washing with water once, drying and concentrating, crystallizing by using a toluene-ethanol mixed solvent, and drying to obtain 21.4g of a compound B, wherein the content is as follows: 97.6%, yield: 78.7 percent.1H NMR(400MHz,DMSO-d6)：δ7.91(d,2H.),7.42(s,2H.),7.23(d,2H.),6.29(d,2H.),6.05(t,2H.),5.61(d,2H.),4.24(t,4H.),4.13(s,2H.),3.98(t,4H.),1.63(m,8H.)。
Synthesis example 3: synthesis of Compound C
Figure BDA0003326934100000121
10g of 2, 7-dihydroxy-9, 9-dimethylfluorene and 27.4g of intermediate 1 of synthesis example 2 and 100g of dichloromethane are added into a reaction bottle, then diisopropylethylamine 20.5g is dropwise added at the temperature of 0-5 ℃, water is added after the reaction is completed, liquid separation and water washing are carried out once, drying and concentration are carried out, a toluene ethanol mixed solvent is crystallized, and the dried compound C is 20.7g, the content: 98.1%, yield: 82.7 percent.1H NMR(400MHz,DMSO-d6)：δ7.90(d,2H.),7.41(s,2H.),7.22(d,2H.),6.27(d,2H.),6.02(t,2H.),5.61(d,2H.),4.21(t,4H.),3.96(t,4H.),1.74(s,6H.),1.63(m,8H.)。
Example 4:
durability test
The retardation (R) of each cured film was measured using an Axoscan ellipsometerin). Analysis of R Using a light Source with a wavelength of 550nmin. To determine the delay dispersion ratio Rin-450/Rin-550The retardation of the materials was measured at wavelengths of 450nm and 550nm, and if not otherwise stated, each film was then placed in an oven at 85 ℃ for a total time of 100 hours, and if not otherwise stated, after 100 hours the film was removed from the oven and cooled to room temperature, and the retardation curve was again recorded, the durability passing the R before and after the oven testinAnd Rin-450/Rin-550Is quantized.
Adhesion test
The adhesion of the film to the substrate was tested using the Nichiban 305 tape test. The tape 305 is therefore adhered to a polymer film and then torn off sharply, and if the film is not removed, adhesion is considered to pass. The composition has the following components that X represents complete separation from the substrate, Delta represents certain adhesiveness, and o represents complete adhesiveness with the substrate.
The photoinitiators used are shown in the table below.
Figure BDA0003326934100000131
The mixtures used are described in the table below.
The compounds other than the compound related to the present invention are all commercially available compounds.
Mixture CM-1
Figure BDA0003326934100000132
Figure BDA0003326934100000141
Mixture CM-2
Figure BDA0003326934100000142
Figure BDA0003326934100000151
Mixture CM-3
Figure BDA0003326934100000152
Control mixture CM-4:
Figure BDA0003326934100000161
experiment 4.1 the mixture CM-1 was dissolved at 33.3% solids in toluene/cyclopentanone (7: 3) and the solution was overcoated with alignment layer on a TAC substrate using Meyer rod # 05. The film was annealed at 65 ℃ for 120 seconds and cured under nitrogen using a fusion H bulb lamp (75% power, 10 m/min). The film was laminated to a pressure sensitive adhesive and covered with a green glass, so the total film stack was TAC/polymer film/pressure sensitive adhesive/glass, and the film was subjected to a durability test.
Experiment 4.2 the mixture CM-2 was dissolved at 33.3% solids in toluene/cyclopentanone (7: 3) and the solution was overcoated with alignment layer on a TAC substrate using Meyer rod # 05. The films were annealed at 65 ℃ for 120 seconds and cured using a fusion H bulb lamp (75% power, 10m/min) under nitrogen atmosphere, laminated to the pressure sensitive adhesive and covered with a green glass, so the total film stack was TAC/polymer film/pressure sensitive adhesive/glass and subjected to durability experiments.
Experiment 4.3 the mixture CM-3 was dissolved at 33.3% solids in toluene/cyclopentanone (7: 3) and the solution was overcoated with alignment layer on a TAC substrate using Meyer rod # 05. The film was annealed at 65 ℃ for 120 seconds and cured under nitrogen using a fusion H bulb lamp (75% power, 10 m/min). The film was laminated to a pressure sensitive adhesive and covered with a green glass, so the total film stack was TAC/polymer film/pressure sensitive adhesive/glass, and the film was subjected to a durability test.
Experiment 4.4 the mixture CM-4 was dissolved at 33.3% solids in toluene/cyclopentanone (7: 3) and the solution was overcoated with alignment layer on a TAC substrate using Meyer rod # 05. The film was annealed at 65 ℃ for 120 seconds and cured under nitrogen using a fusion H bulb lamp (75% power, 10 m/min). The film was laminated to a pressure sensitive adhesive and covered with a green glass, so the total film stack was TAC/polymer film/pressure sensitive adhesive/glass, and the film was subjected to a durability test.
See table 1 below for results.
TABLE 1
Figure BDA0003326934100000171
Example 5:
to evaluate the storage stability, the stable storage concentration of the evaluation compound was measured. The storage stability concentration is defined as: the compound to be evaluated was added in an amount of 5% to 50% in increments to the mother liquid crystal, and the prepared composition was left at 10 ℃ for 10 weeks to have a maximum concentration of the compound at which crystal precipitation did not occur. The maximum added concentration of the compound means that the storage concentration is high and the compound does not crystallize even when stored for a long time.
The evaluation compounds were determined to be the following commercially available compounds:
Figure BDA0003326934100000181
the liquid crystal composition as the mother liquid crystal M is as follows:
M-1
Figure BDA0003326934100000182
M-2
Figure BDA0003326934100000183
Figure BDA0003326934100000191
M-3
Figure BDA0003326934100000192
comparative example M-4:
Figure BDA0003326934100000201
see table 2 for results.
TABLE 2
Evaluation of Compounds Stable preservation concentration
Experiment 5-1 Inventive mother crystal M-1 30％
Experiment 5-2 Inventive mother crystal M-2 45％
Experiment 5-3 Inventive mother crystal M-3 45％
Comparative experiment 5-4 Comparative example M-4 25％
The alignment film was coated with a polyimide solution for an alignment film and a glass substrate having a thickness of 0.7mm by a spin coating method, dried at 100 ℃ for ten minutes, and then fired at 200 ℃ for 60 minutes to obtain a coating film, and the obtained coating film was subjected to a rubbing treatment using a commercially available rubbing apparatus.
In order to reduce the birefringence and improve the viewing angle, a polymerizable composition was prepared by adding 35% of a compound to be evaluated to a mother liquid crystal M, and a photopolymerization initiator Irgacure 907 (manufactured by BASF Co., Ltd.), 1%, 0.1% of 4-methoxyphenol and 80% of chloroform were added to prepare a coating solution. The coating liquid was applied by spin coatingWith the rubbed glass substrate. After drying at 80 ℃ for 1 minute, further drying at 120 ℃ for 1 minute, and then using a high pressure mercury lamp at 40mW/cm2The film to be evaluated was prepared by irradiating ultraviolet light at the intensity of (1) for 25 seconds.
The degree of unevenness of the obtained polymer was evaluated by observation with a polarization microscope. The number of films to which the compound to be evaluated was added was counted in a non-uniform manner, 10 films each were prepared. The number of unevenness observed in 10 sheets of films was counted up, and the number of unevenness was found to be excellent when the number of unevenness was 0, good when the number of unevenness was 1, medium when the number of unevenness was 1 to 10, and poor when the number of unevenness was ten or more. See table 3 for results.
TABLE 3
Evaluation of Compounds Unevenness of the flow of water
Experiment 5-1 Inventive mother crystal M-1 In
Experiment 5-2 Inventive mother crystal M-2 Superior food
Experiment 5-3 Inventive mother crystal M-3 Superior food
Comparative experiment 5-4 Comparative example M-4 In
It should be understood that the detailed description of the invention is merely illustrative of the spirit and principles of the invention and is not intended to limit the scope of the invention. Furthermore, it should be understood that various changes, substitutions, deletions, modifications or adjustments may be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents are also within the scope of the invention as defined in the appended claims.

Claims (10)

1. A polymerizable compound selected from compounds of the general formula (1),
Figure FDA0003326934090000011
in the formula (I), the compound is shown in the specification,
P1and P2Each independently represents a polymerizable group;
L1and L2Each independently represents a single bond, -O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, -COS-, -OCOO-, -NHCO-, -CONH-, -OCH2-、-CH2O-、-SCH2-、-CH2S-、-OCF2-、-CF2O-、-SCF2-、-CF2S-、-CH＝CHOCO-、-CH＝CHCOO-、-OCOCH＝CH-、-COOCH＝CH-、-CH2CH2OCO-、-CH2CH2COO-、-OCOCH2CH2-、-COOCH2CH2-、-CH2OCO-、-CH2COO-、-OCOCH2-、-COOCH2-, -CH ═ CH-, -N ═ CH-, -CH ═ N-, -N ═ N-, -CH ═ CF-, -CF ═ CH-, -N ═ CF-, -CF ═ N-, -C ≡ C-, or alkylene having a carbon number of 1 to 30; one or more-CH's in said alkylene group2May be substituted by-O-, -S-, -NH-, -NRa-, -CO-, -OCO-, -COO-, -SCO-, -COS-substitution;
C1and C2Each independently represents-CO-, -OCO-, -COO-, -SCO-, -COS-, -NHCO-, -CONH-, -CH2-、-CF2-；
R independently represents H, C1-30 alkyl, C1-30 haloalkyl, C1-30 alkoxy, C1-30 haloalkoxy, C2-30 alkenyl, C2-30 haloalkenyl, C2-30 alkenyloxy, C2-30 haloalkenyloxy, C1-30 alkoxycarbonyl, C1-30 haloalkoxycarbonyl, C1-30 alkylcarbonyl, C1-30 haloalkylcarbonyl, C1-30 alkylacyloxy or C1-30 haloalkoyloxy; raEach independently represents an alkyl group having 1 to 30 carbon atoms.
2. The polymerizable compound of claim 1 wherein the polymerizable group is selected from the group consisting of:
Figure FDA0003326934090000021
in the formula, R3Each 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 alkanoyloxy group having 1 to 30 carbon atoms or a haloalkoyloxy group having 1 to 30 carbon atoms.
3. The polymerizable compound according to claim 1, wherein P is1And P2Each independently represents a group of (P-1) and (P-2); preferably, P1And P2Each independently represents a group of (P-1).
4. The polymerizable compound of claim 1, wherein L1And L2Each independently represents an alkylene group having 1 to 30 carbon atoms; one or more-CH's in said alkylene group2-may be substituted by-O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, -COS-;
preferably, L1And L2Each independently represents an alkylene group having 1 to 30 carbon atoms.
5. The polymerizable compound according to claim 1, wherein C1And C2Each independently represents-OCO-, -COO-.
6. The polymerizable compound according to claim 1, wherein each R independently represents H or an alkyl group having 1 to 30 carbon atoms.
7. A process for the preparation of the polymerizable compound according to any one of claims 1 to 6, which comprises: reacting a compound of formula (2) with a compound of formula (3) and a compound of formula (4) to give a compound of formula (1);
Figure FDA0003326934090000031
P1-L1-C1-X (3)；
P2-L2-C2-X (4)；
wherein, P1、P2、L1、L2And R is as defined in any one of claims 1-6; x represents a halogen.
8. A polymerizable composition comprising a compound of the general formula (1) according to any one of claims 1 to 6.
9. A polymerizable composition solution comprising the polymerizable composition according to claim 8 and an organic solvent.
10. An optically anisotropic body comprising a base material and a polymer film formed by solution-curing the polymerizable composition according to claim 9, and, if necessary, an alignment film; advantageously, the optically anisotropic body is selected from phase difference films.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115160291A (en) * 2022-07-26 2022-10-11 江苏创拓新材料有限公司 Dibenzothiophene-based polymerizable compound and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102439114A (en) * 2009-05-22 2012-05-02 默克专利股份有限公司 Liquid crystal display
KR20120088587A (en) * 2011-01-31 2012-08-08 제이엔씨 주식회사 Polymerizable liquid crystal composition and optical anisotropic body
US20160011349A1 (en) * 2013-12-20 2016-01-14 Jnc Petrochemical Corporation Infrared reflecting film and laminated film
CN106256874A (en) * 2015-06-17 2016-12-28 捷恩智株式会社 Polymerizable liquid crystal compound, polymerizable liquid crystal layer, liquid crystal film, optical compensatory element and optical element
CN110358547A (en) * 2018-04-10 2019-10-22 北京八亿时空液晶科技股份有限公司 A kind of novel polymerizable compound and its application
CN111732569A (en) * 2019-03-25 2020-10-02 捷恩智株式会社 Liquid crystalline compound having dibenzothiophene ring, liquid crystal composition, and liquid crystal display element

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102439114A (en) * 2009-05-22 2012-05-02 默克专利股份有限公司 Liquid crystal display
KR20120088587A (en) * 2011-01-31 2012-08-08 제이엔씨 주식회사 Polymerizable liquid crystal composition and optical anisotropic body
US20160011349A1 (en) * 2013-12-20 2016-01-14 Jnc Petrochemical Corporation Infrared reflecting film and laminated film
CN106256874A (en) * 2015-06-17 2016-12-28 捷恩智株式会社 Polymerizable liquid crystal compound, polymerizable liquid crystal layer, liquid crystal film, optical compensatory element and optical element
CN110358547A (en) * 2018-04-10 2019-10-22 北京八亿时空液晶科技股份有限公司 A kind of novel polymerizable compound and its application
CN111732569A (en) * 2019-03-25 2020-10-02 捷恩智株式会社 Liquid crystalline compound having dibenzothiophene ring, liquid crystal composition, and liquid crystal display element

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
REGISTRY: "2055718-59-5等", STN, pages 1 - 2 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115160291A (en) * 2022-07-26 2022-10-11 江苏创拓新材料有限公司 Dibenzothiophene-based polymerizable compound and preparation method and application thereof

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