Polymerizable composition, composition solution, and optically anisotropic body using same

Abstract

The invention belongs to the technical field of polymerizable compositions, and particularly relates to a polymerizable composition which comprises two negative dispersion materials, namely a negative dispersion compound containing carbonic ester and a negative dispersion compound containing alkynyl. By virtue of the adaptability of the carbonic ester structure to the humid and hot environment, the optical performance fluctuation of the film material under the humid and hot conditions is effectively inhibited, and the long-term stable service of the film under the high-humidity and high-temperature working conditions is ensured; and by combining the ultraviolet blocking and discoloration resisting characteristics of an alkynyl structure, yellowing, embrittlement and other degradation caused by ultraviolet radiation are resisted, and the technical bottleneck that a traditional composition is difficult to consider complex environment tolerance is broken through.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polymerizable compositions, in particular to a polymerizable composition, a composition solution and an optically anisotropic body using the same. BACKGROUND

[0002] In the related technical field of optical films and the like, as the application scenarios continue to expand, such as in outdoor optical devices, automobile window films, display device protection and the like, the film material needs to simultaneously withstand the dual tests of ultraviolet irradiation and temperature and humidity environments.

[0003] At present, the conventional film composition has obvious shortcomings in actual use: on the one hand, if the composition lacks a specific structure to resist the influence of temperature and humidity environments, under high temperature and humidity conditions, the film material is prone to optical performance degradation, such as abnormal changes in refractive index, fluctuations in light transmittance, etc., resulting in a decline in imaging quality and damage to the function of optical devices; on the other hand, when the composition lacks a key structure for ultraviolet protection, ultraviolet irradiation will cause the film material to discolor, not only affecting the appearance, but also weakening the protection of the internal device, reducing the service life and reliability of the film material.

[0004] Although the prior art attempts to improve the film composition, it is difficult to simultaneously consider the anti-discoloration ability under ultraviolet irradiation and the optical performance stability in temperature and humidity environments, and it cannot meet the stringent requirements of complex application scenarios for film materials. Therefore, it has become a technical problem to be solved in the field to develop a composition that can effectively solve the discoloration and optical performance degradation of the film under ultraviolet and temperature and humidity environments. SUMMARY

[0005] The purpose of the present application is to provide a polymerizable composition, a composition solution and an optically anisotropic body using the same to solve the above technical problems.

[0006] Therefore, the present application provides a polymerizable composition, which comprises two negative dispersion materials, namely a carbonate-containing negative dispersion compound represented by formula (1) and an alkyne-containing negative dispersion compound represented by formula (2). The formula (1) is: ; The formula (2) is: ;

[0007] In the general formula (1), L1-L2 each independently represents a single bond or an alkylene group having a carbon number of 1-30; one or more -CH2- in the alkylene group can be substituted with -O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, -COS-.

[0008] Preferably, the negative dispersion compound containing carbonate comprises a polymerizable group, the polymerizable group comprising at least one of the following groups: .

[0009] Preferably, at least one additional polymerizable compound is further included, the additional polymerizable compound comprising at least one of the compounds of Formula B-1, Formula B-2, Formula B-3: wherein Formula B-1 is: ; Formula B-2 is: ; Formula B-3 is: .

[0010] Preferably, the polymerizable compound of Formula (1) is not less than 30 wt% in the added concentration of the one polymerizable composition.

[0011] Preferably, an additive is further included, the additive comprising, but not limited to, at least one of the following: a polymerization initiator, a sensitizer, a sensitizer, a stabilizer, a leveling agent, a surfactant, a polymerization inhibitor, an antioxidant, a colorant, a dispersant, a lubricant, a hydrophobic agent, an adhesive, a flow improver, an antifoaming agent, a degassing agent, a diluent, a thixotropic agent, a gelling agent, a catalyst, a metal, a metal complex, a luminescent material.

[0012] Preferably, the additive is 0.01-10 wt%.

[0013] A polymerizable composition solution, comprising a polymerizable composition, further comprising an organic solvent.

[0014] Preferably, the organic solvent comprises at least one of the following: toluene, xylene, cumene, mesitylene, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, tetrahydrofuran, 1,2-dimethoxyethane, anisole, N,N-dimethylformamide, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, gamma-butyrolactone, and chlorobenzene.

[0015] Preferably, the organic solvent content is 30-95 wt%.

[0016] An optically anisotropic body, comprising a polymer film formed by curing a polymerizable composition solution.

[0017] The beneficial effects of the present application are: The application effectively inhibits the fluctuation of the optical performance of the film material under the temperature and humidity conditions, and guarantees the long-term stable service of the film under the high-humidity and high-temperature working conditions, by virtue of the adaptability of the carbonate structure to the humid heat environment; and the ultraviolet blocking and discoloration resistance characteristics of the alkynyl structure resist the yellowing, embrittlement and other deterioration caused by ultraviolet radiation, and break through the technical bottleneck that the traditional composition is difficult to consider the complex environmental resistance. DETAILED DESCRIPTION

[0018] The technical solutions in the embodiments of the present application will be clearly described below. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art belong to the scope of protection of the present application.

[0019] In the description of the specification, the description of the terms "one embodiment", "some embodiments", "exemplary embodiment", "example", "specific example" or "some examples" means that the specific features, structures, materials or characteristics described in combination with the embodiment or example are included in at least one embodiment or example of the present application. In the specification, the exemplary description of the above terms does not necessarily mean the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0020] The present embodiment first provides a polymerizable composition comprising two negative dispersion materials, which are a carbonate-containing negative dispersion compound as shown in formula (1) and an alkynyl-containing negative dispersion compound as shown in formula (2), respectively. The formula (1) is: ; The formula (2) is: ; In the general formula (1), L1-L2 each independently represents a single bond or an alkylene group with a carbon number of 1-30; one or more -CH2- in the alkylene group can be substituted by -O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, -COS-; The carbonate-containing negative dispersion compound comprises a polymerizable group, and the polymerizable group includes at least one of the following groups: ; As a preferred example of the present application, the polymerizable compound of formula (1) has an addition concentration of not less than 30wt%, 40wt%, 50wt% or 60wt%, for example, 35wt%, 45wt%, 55wt%, 65wt% in the polymerizable composition.

[0021] In the present embodiment, an additive is also included, which includes, but is not limited to, at least one of a polymerization initiator, a sensitizer, a sensibilizer, a stabilizer, a leveling agent, a surfactant, a polymerization inhibitor, an antioxidant, a colorant, a dispersant, a lubricant, a hydrophobic agent, an adhesive, a flow improver, an antifoaming agent, a degassing agent, a diluent, a thixotropic agent, a gelling agent, a catalyst, a metal, a metal complex, a luminescent material.

[0022] In the present embodiment, the content of the additive is 0.01 to 10% by weight, and as a preferable example of the present application, the content can be 0.02 to 8% by weight, 0.05 to 5% by weight, or 0.1 to 3% by weight of the total amount of the polymerizable composition.

[0023] The polymerizable composition can be used for the production of 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 devices, communication devices, automobile parts, aircraft parts, mechanical parts, pesticides, and foodstuffs;

[0024] In order to improve the storage stability of the polymerizable composition of the present application, a stabilizer can also be added thereto. As the stabilizer which can be used, there can be mentioned, for example, hydroquinones, hydroquinone monoalkyl ethers, t-butyl catechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, and the like. When a stabilizer is used, the amount of addition is preferably in the range of 0.005 to 1% by mass, more preferably 0.02 to 0.8% by mass, and further preferably 0.03 to 0.5% by mass, relative to the composition.

[0025] In addition, when the polymerizable composition of the present application is used for applications such as films, optical elements, functional pigments, pharmaceuticals, cosmetics, coating agents, synthetic resins, and the like, a metal, a metal complex, a dye, a pigment, a colorant, a fluorescent material, a phosphorescent material, a surfactant, a leveling agent, a thixotropic agent, a gelling agent, a polysaccharide, an ultraviolet absorber, an infrared absorber, an antioxidant, an ion exchange resin, a metal oxide such as titanium oxide, and the like can also be added according to the purpose.

[0026] In addition to the above, the polymer obtained by polymerizing the polymerizable composition of the present application without orientation can be used as a light scattering plate, a depolarizing plate, a moire fringe preventing plate. In addition, the polymer obtained by polymerizing after orientation has optical anisotropy, and such an optically anisotropic body can be produced by supporting the polymerizable composition containing the compound of the present application on a substrate subjected to rubbing treatment with cloth or the like, a substrate on which an organic thin film is formed, or a substrate having an alignment film on which Si02 is obliquely vapor-deposited, or by sandwiching a dry substrate therebetween, and then polymerizing the polymerizable composition, thereby producing; As a method of supporting the polymerizable composition on a substrate, spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, dipping, printing, and the like can be exemplified. Further, an organic solvent can be added to the polymerizable composition at the time of coating. As the organic solvent, a hydrocarbon-based solvent, a halogenated hydrocarbon-based solvent, an ether-based solvent, an alcohol-based solvent, a ketone-based solvent, an ester-based solvent, an aprotic solvent, and the like can be used, and, for example, toluene or hexane can be exemplified as the hydrocarbon-based solvent, monochloromethane can be exemplified as the halogenated hydrocarbon-based solvent, tetrahydrofuran, acetyloxy-2-ethoxy alkyl, or internal diol monomethyl ether can be exemplified as the ether-based solvent, methanol, ethanol, or isopropanol can be exemplified as the alcohol-based solvent, acetone, methyl ethyl ketone, cyclohexanone, γ-butyrolactone, or N-methylpyrrolidone can be exemplified as the ketone-based solvent, ethyl acetate or cellosolve can be exemplified as the ester-based solvent, and dimethylformamide or acetonitrile can be exemplified as the aprotic solvent. These can be used alone or in combination, and can be appropriately selected in consideration of their vapor pressure and solubility of the polymerizable composition. As a method of volatilizing the added organic solvent, natural drying, heating drying, pressurized drying, pressurized heating drying can be used. In order to further improve the coatability of the polymerized liquid crystal material, it is also effective to provide an intermediate layer such as a polyimide film on the substrate, or to add a leveling agent to the polymerizable liquid crystal material. The method of providing an intermediate layer such as a polyimide film on the substrate is effective for improving the adhesion between the polymer obtained by polymerizing the polymerizable material and the substrate; As the orientation treatment other than the above, flow orientation of the liquid crystal material, or use of an electric field or a magnetic field can be utilized. These orientation means can be used alone or in combination. Further, as an orientation treatment method instead of rubbing, a photo-alignment method can also be used. As the shape of the substrate, in addition to a flat plate, a curved surface can also be used as a component. The material constituting the substrate can be used without limitation as an organic material, an inorganic material. As the organic material to be the substrate material, for example, polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, triacetyl cellulose, cellulose, polyether ether ketone, and the like can be used, and, as the inorganic material, for example, silicon, glass, calcite, and the like can be exemplified.

[0027] When the polymerizable composition containing the compound of the present application is polymerized, a method of polymerizing it by irradiation of active energy rays such as ultraviolet rays or electron rays is preferred because it is desirable to proceed with the polymerization rapidly. When ultraviolet rays are used, a polarized light source can be used, or a non-polarized light source can be used. In addition, when the polymerization is performed in a state in which the liquid composition is interposed between two substrates, the substrate on at least the irradiation side must have appropriate transparency with respect to the active energy rays. A means in which, after the polymerization of only a specific portion is performed using a mask at the time of light irradiation, the orientation state of the non-polymerized portion is changed by changing the conditions such as an electric field, a magnetic field, or a temperature, and the non-polymerized portion is further polymerized by irradiation of active energy rays can also be used. In addition, the temperature at the time of irradiation is preferably within a range in which the liquid crystal state of the polymerizable composition of the present application is maintained. In particular, when an optically anisotropic body is produced by photopolymerization, it is necessary to polymerize it at a temperature as close to room temperature as possible, that is, typically at a temperature of 25°C, from the viewpoint of avoiding the induction of undesirable thermal polymerization. The intensity of the active energy rays is preferably 0.1 mW / cm2to 2 W / cm2. When the intensity is 0.1 mW / cm2or less, a large amount of time is required in order to complete the photopolymerization, and the productivity deteriorates, and when the intensity is 2 W / cm2or more, there is a risk that the polymerizable compound or the polymerizable composition will deteriorate.

[0028] With respect to the optically anisotropic body obtained by polymerization, heat treatment can also be performed in order to reduce initial changes in characteristics and to exhibit stable characteristics. The temperature of the heat treatment is preferably in the range of 50°C to 250°C, and the heat treatment time is preferably in the range of 30 seconds to 12 hours.

[0029] The optically anisotropic body produced by such a method can be used as a monomer 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 can be used by being attached to another substrate.

[0030] The present embodiment also proposes a polymerizable composition solution including a polymerizable composition, and further including an organic solvent, the organic solvent being required to have good solubility with respect to the polymerizable composition and to be able to be removed by drying at 100°C or lower; The organic solvent includes 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 tetrahydrofuran, 1,2-dimethoxyethane, and anisole; amide solvents such as N,N-dimethylformamide and N-methyl-2-pyrrolidone; and chlorobenzene. The organic solvent can be used alone, or two or more kinds thereof can be used in combination. Based on the solution stability, it is preferable to use one or more of ketone solvents, ether solvents, ester solvents and aromatic solvents, and in the present embodiment, the organic solvent is selected from cyclopentanone.

[0031] The content of the organic solvent is 30 to 95 wt%, 40 to 90 wt%, 50 to 85 wt% or 60 to 80 wt%, for example 25 wt%, 45 wt%, 55 wt% or 75 wt%; In the preparation of the polymerizable composition solution, in order to facilitate the dissolution of the polymerizable composition, heating and / or stirring are advantageously performed.

[0032] The present embodiment also proposes an optically anisotropic body comprising a polymer film formed by curing the polymerizable composition solution, and an alignment film present as necessary; In one embodiment, the substrate, the alignment film present as necessary, and the polymer film formed by curing the polymerizable composition solution are sequentially laminated, thereby forming the optically anisotropic body.

[0033] As the substrate of the optically anisotropic body, there are included, but not limited to, glass substrates, metal substrates, ceramic substrates, polymer substrates; For example: cellulose derivatives, polyolefins, polyesters, polyolefins, polycarbonates, polyacrylates, polyarylates, polyethersulfones, polyamides, polyimides, polyphenylene sulfide, polyphenyl ether or polystyrene.

[0034] Based on the process applicability of the optically anisotropic body, especially based on the consideration of heat resistance and chemical stability, it is preferable to be polyester, polystyrene, polyolefin, cellulose derivative, polyarylate, polycarbonate.

[0035] As the alignment film material of the optically anisotropic body, there are included, but not limited to, polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenyl ether, polyarylate, polyethylene terephthalate, polyethersulfone, epoxy resin, acrylic resin, epoxy-acrylic resin, coumarin, chalcone, cinnamate, anthraquinone, azo compound, aryl ethylene compound.

[0036] As the orientation treatment, it can be stretching treatment, rubbing treatment, polarized ultraviolet-visible light irradiation, ion beam treatment, etc.; the preferred orientation treatment is preferably rubbing treatment or polarized ultraviolet-visible light irradiation.

[0037] As the coating method for obtaining the optically anisotropic body of the present application, the 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, immersion, etc. can be used. After coating the polymerizable composition solution, it is dried.

[0038] When the polymerizable composition solution of the present application is subjected to polymerization, it is desirable to rapidly perform the polymerization, and thus it is preferable to polymerize it by a method of irradiating active energy rays such as ultraviolet visible light or electron rays. In the case of using ultraviolet visible light, either a polarized light source or a non-polarized light source can be used.

[0039] As the optically anisotropic body of the present application, a birefringent film is advantageously used. The birefringent film of the present application is produced in the same manner as the optically anisotropic body of the present application.

[0040] To verify the effects of the present application, the following verification procedures are now performed: In the polymerizable composition, the negative dispersion compound containing a carbonate has the following structure: 1-1: ; 1-2: ; 1-3: ; The compound (2-1) containing an alkynyl group is selected as follows: ; The above polymerizable composition will be compared with the following three products: including Formula B-1:

[0041] Formula B-2: ; Formula B-3: .

[0042] Further, provided is a liquid crystal composition as a mother liquid crystal (M) containing 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; ; ; ;

[0043] The alignment film is coated with a polyimide solution, dried at 100°C with a glass substrate having a thickness of 0.7 mm, and after ten minutes, baked at 200°C for 60 minutes to obtain a coated film. The obtained coated film is subjected to rubbing treatment, which is performed using a commercially available rubbing device.

[0044] A composition (including two kinds of polymerizable compounds) which was the evaluation target was prepared by adding 40% to a mother liquid crystal M, and modulating a polymerizable composition, adding 1% of a photopolymerization initiator Irgacure 907 (manufactured by BASF Corporation), 0.1% of 4-methoxyphenol, and 80% of chloroform, and modulating a coating solution. The coating solution was applied to a rubbed glass substrate by a spin coating method. After drying at 80°C for 1 minute, further drying at 120°C for 1 minute, and then irradiation of ultraviolet rays at an intensity of 40 mW / cm2 for 25 seconds using a high-pressure mercury lamp, a film which was the evaluation target was produced.

[0045] The degree of unevenness was evaluated by polarizing microscope observation for the obtained polymer. Ten pieces of a film to which the compound which was the evaluation target was added were produced, and the number of unevenness was counted. The number of unevenness observed in the ten pieces of the film was totaled, and if the number of unevenness was 0, it was rated as excellent, if the number of unevenness was 1, it was rated as good, if the number of unevenness was 1 to 10, it was rated as fair, and if the number of unevenness was more than ten, it was rated as poor.

[0046] Regarding the heat and humidity durability: The test conditions regarding the heat and humidity durability were that a test was performed for 500 hours in an environment of 85°C and 85% relative humidity. The Re(550) of the optical film before the test and the Re(550) of the optical film after the test were measured, and the heat and humidity durability was evaluated based on the following criteria.

[0047] A: the change in Re(550) after the test from Re(550) before the test was less than 10% of Re(550) before the test; B: the change in Re(550) after the test from Re(550) before the test was 10% or more but less than 30% of Re(550) before the test; C: the change in Re(550) after the test from Re(550) before the test was 30% or more of Re(550) before the test; Regarding the ultraviolet resistance: Each of the produced films was subjected to a sunlight test using a xenon irradiation tester (Suntest XLS, manufactured by ATLAS Corporation) under conditions of 60 mW / cm2, 26°C, and 120 J. The discoloration and orientation failure of the obtained film were evaluated.

[0048] The yellow index (YI) of each film was measured. The difference (△YI) between the YI value before the sunlight test and the YI value after the sunlight test was calculated. The yellow index (YI) was measured using a JASCO UV / VIS spectrophotometer V-560 and calculated by a color diagnosis program attached thereto. The calculation formula is represented as: YI = 100 (1.28X - 1.06Z) / Y (JIS K7373) (X, Y, Z represent the three stimulus values in XYZ color system, and the smaller the △YI value, the less the discoloration; The composition ratio and test results are as follows:

[0049] As can be seen from the table, examples 1-3 do not discolor under UV irradiation, and their optical performance remains relatively excellent in a warm and humid environment. In comparative examples 1-3, the composition does not contain a carbonate structure, resulting in poor optical performance in a warm and humid environment. In comparative examples 4-6, the composition does not contain an alkyne structure, resulting in discoloration under UV irradiation. In summary, the composition of the present application can effectively solve the discoloration and optical performance of the film under UV and warm and humid environments.

[0050] The above describes the embodiments of the present application, and the embodiments and features in the embodiments can be combined with each other without conflict, the present application is not limited to the above specific embodiments, the above specific embodiments are only illustrative, not restrictive, and those skilled in the art can make many forms under the inspiration of the present application without departing from the scope of the present application and the scope protected by the claims, all of which belong to the protection of the present application.

Claims

1. A polymerizable composition, characterized in that: It comprises two negative dispersion materials, namely a negative dispersion compound containing carbonate as shown in formula (1) and a negative dispersion compound containing alkynyl as shown in formula (2); The formula (1) is: ； The formula (2) is: ； Wherein, in the general formula (1), L1-L2 each independently represents a single bond or an alkylene group having 1 to 30 carbon atoms; one or more -CH2- groups in the alkylene group may be substituted by -O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, or -COS-.

2. A polymerizable composition according to claim 1, characterized in that: The carbonate-containing negative dispersion compound comprises a polymerizable group, and the polymerizable group comprises at least one of the following groups: 。 3. A polymerizable composition according to claim 1, characterized in that: Also included is at least one additional polymerizable compound, the additional polymerizable compound comprising at least one of the compounds of Formula B-1, Formula B-2, and Formula B-3: Wherein, formula B-1 is: Formula B-2 is: ; Formula B-3 is: 。 4. A polymerizable composition according to claim 3, characterized in that: The polymerizable compound of formula (1) is added to the polymerizable composition at a concentration of not less than 30 wt %.

5. The polymerizable composition according to claim 1, wherein: The additives include, but are not limited to, at least one of polymerization initiator, sensitizer, sensitizer, stabilizer, leveling agent, surfactant, inhibitor, antioxidant, colorant, dispersant, lubricant, hydrophobic agent, adhesive, flow improver, defoamer, degassing agent, diluent, thixotropic agent, gelling agent, catalyst, metal, metal complex, and luminescent material.

6. A polymerizable composition according to claim 5, characterized in that: The content of the additive is 0.01-10 wt%.

7. A polymerizable composition solution, comprising a polymerizable composition according to any one of claims 1 to 6, characterized in that: Organic solvents are also included.

8. The polymerizable composition solution according to claim 7, characterized in that: The organic solvent includes at least one of toluene, xylene, isopropyl benzene, mesitylene, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, tetrahydrofuran, 1,2-dimethoxyethane, anisole, N,N-dimethylformamide, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, γ-butyrolactone and chlorobenzene.

9. The polymerizable composition solution according to claim 8, characterized in that: The content of the organic solvent is 30-95 wt%.

10. An optically anisotropic body comprising a polymer film formed by curing a solution of the polymerizable composition according to any one of claims 7 to 9.

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