CN116903466A - Alkynyl-containing polymerizable compound and optical film application thereof - Google Patents
Alkynyl-containing polymerizable compound and optical film application thereof Download PDFInfo
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- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
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- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
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- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
- C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
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- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
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- C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
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Abstract
An alkynyl-containing polymerizable compound selected from the group consisting of compounds of the general formula (1) is provided. Further provided are a polymerizable liquid crystal composition and an optically anisotropic body each containing the polymerizable compound. The polymerizable compound forms an optical anisotropic body with uneven orientation, and the yellowing performance is obviously improved under ultraviolet light.
Description
Technical Field
The invention belongs to the technical field of light control, and particularly relates to an alkynyl-containing polymerizable compound and an optical film application thereof.
Background
Polymerizable compounds (RM) are receiving increasing attention as starting materials for the preparation of various optically anisotropic bodies. The prior art generally applies an RM solution onto a substrate, aligns it, and cures it by heating or irradiating an activating energy ray, thereby forming an optically anisotropic polymer film having a uniform orientation, also called optically anisotropic body. The orientation of the film may be planar (liquid crystal molecules oriented substantially parallel to the layer), homeotropic (rectangular or perpendicular to the layer) or tilted, or cholesteric.
The optically anisotropic body preferably has at least one of the following properties: the film has the advantages of small haze value, high film thickness uniformity, less uneven orientation, high surface hardness, high adhesion, good appearance after ultraviolet irradiation and less occurrence of orientation defects.
Depending on the application field, the optically anisotropic body includes, but is not limited to, a birefringent film, 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 film (deflection plate), a polarizing element, a circular polarizing element, an elliptical polarizing element, and other various optical elements.
In the case of a birefringent film, it is necessary to add a polymerizable compound to a mother liquid crystal to obtain a polymerizable liquid crystal composition, thereby making the wavelength dispersibility of its birefringence smaller and effectively increasing the viewing angle of the display. However, the birefringent films of the prior art are prone to yellowing and non-alignment.
Therefore, there is a need to develop polymerizable compounds whose use can solve the above-mentioned technical problems.
Disclosure of Invention
The invention aims to provide an alkynyl-containing polymerizable compound and an optical film application thereof. The optical anisotropic body formed by the polymerizable compound is excellent in uneven orientation, and the yellowing performance is obviously improved under ultraviolet light.
The inventors have studied by their molecular engineering in terms of "functional-synthetic-structural" concept, and as a result found that: the foregoing technical problems can be solved by using the alkynyl-containing polymerizable compound of the general formula (1) of the present invention, thereby completing the present invention.
The present invention includes the following configurations.
An alkynyl-containing polymerizable compound, wherein the compound is selected from compounds of the general formula (1),
in the method, in the process of the invention,
P 1 and P 2 Each independently represents a polymerizable group;
L 1 and L 2 Each independently represents an alkylene group having 1 to 30 carbon atoms; the alkylene group may be linear or may have a branched group; one or more of the alkylene groups-CH 2 -can be substituted by-O-, -S-, -NH-, -NR a -, -CO-, -OCO-, -COO- -OCOO-, -SCO-, -COs-substitution;
R 1 -R 2 and R is a Each independently represents a hydrogen atom, a C1-30 alkyl group, a C1-30 haloalkyl group, a C1-30 haloalkoxy group, a C2-30 alkenyl group, a C2-30 haloalkenyl group, a C2-30 alkenyloxy group, a C2-30 haloalkenyloxy group, a C1-30 alkoxycarbonyl group, a C1-30 haloalkoxycarbonyl group, a C1-30 alkylcarbonyl group, a C1-30 haloalkylcarbonyl group, a C1-30 alkylacyloxy group, a C1-30 haloalkylacyloxy group, a C6-30 alkylaryl group, a C6-30 arylalkyl group, a C6-30 alkylaryl group, a C6-30 aryloxycarbonyl group, a C6-30 arylcarbonyloxy group, and a C6-30 aryloxycarbonyloxy group. One or more of the alkyl, alkoxy, alkenyl, alkenyloxy groups-CH 2 -can be substituted by-O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, -COS-; optionally, one or more H atoms of the alkyl, alkoxy, alkenyl, alkenyloxy groups may be substituted with halogen, cyano, hydroxy, nitro, carboxyl, carbamoyloxy, amino, sulfamoyl, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, thioisocyano, alkyl of 1 to 30 carbon atoms, haloalkyl of 1 to 30 carbon atoms, alkoxy of 1 to 30 carbon atoms, haloalkoxy of 1 to 30 carbon atoms, alkylacyloxy of 1 to 30 carbon atoms, haloalkylacyloxy of 1 to 30 carbon atoms or a polymerizable group.
m, n and p each independently represent an integer of 0 to 4; q each independently represents an integer of 0 to 3, m, n, p and q.gtoreq.gtoreq.2, a plurality of R 2 May be the same or different.
As a polymerizable compound described above and below, wherein each of the sub-ranges of alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, haloalkoxycarbonyl, alkylcarbonyl, haloalkylcarbonyl, alkylacyloxy, or haloalkylacyloxy, and the like, and combinations thereof, can be 1-28, 1-26, 1-24, 1-22, 1-20, 1-18, 1-16, 1-14, 1-12, 1-10, 1-8, 1-6, 1-4, 1-2, and the like; the alkenyl, haloalkenyl, alkenyloxy, haloalkenyloxy groups may have a carbon number ranging from 2 to 28, from 2 to 26, from 2 to 24, from 2 to 22, from 2 to 20, from 2 to 18, from 2 to 16, from 2 to 14, from 2 to 12, from 2 to 10, from 2 to 8, from 2 to 6, from 2 to 4, from 2 to 3, and combinations thereof.
As compounds in the above and below, the polymerizable groups are selected from the following groups:
wherein R is 3 And R is R 1 -R 2 The definitions are the same.
Advantageously, R 3 Each independently represents a hydrogen atom, a halogen group, a cyano group, a C1-30 alkyl group, a C1-30 haloalkyl group, a C1-30 alkoxy group, a C1-30 haloalkoxy group, a C2-30 alkenyl group, a C2-30 haloalkenyl group, a C2-30 alkenyloxy group, a C2-30 haloalkenyloxy group, a C1-30 alkoxycarbonyl group, a C1-30 haloalkoxycarbonyl group, a C1-30 alkylcarbonyl group, a C1-30 haloalkylcarbonyl group, a C1-30 alkylacyloxy group, or a C1-30 haloalkylacyloxy group.
As a polymerizable compound in the context, wherein P 1 And P 2 Each independently represents a group of (P-1) and (P-2); preferably, P 1 And P 2 Each independently represents a group of (P-1).
In a specific embodiment, P 1 And P 2 Each independently represents an acrylate group.
As the polymerizable compound described above and below, wherein L 1 And L 2 Each independently represents an alkylene group having 1 to 20 carbon atoms; the alkylene group is linear; one or more of the alkylene groups-CH 2 -may be substituted by-O-, -CO-, -OCO-, -COO-, -OCOO-.
Preferably L 1 And L 2 Each independently represents an alkylene group having 1 to 16 carbon atoms. Advantageously, the alkylene group is linear. Advantageously, one or more of the-CH's in the alkylene group 2 -may be substituted by-O-, -CO-.
More preferably L 1 And L 2 Each independently represents an alkylene group having 2 to 10 carbon atoms.
Further preferably L 1 And L 2 Each independently represents an alkylene group having 3 to 8 carbon atoms.
Most preferably L 1 And L 2 Each independently represents an alkylene group having 4 to 6 carbon atoms.
As the context of the polymerizable compounds, wherein R 1 Represents 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; one or more of the alkyl, alkoxy, alkenyl, alkenyloxy groups-CH 2 -may be substituted by-O-, -S-, -CO-, -OCO-, -COO-.
Preferably, R 1 Represents 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, or a haloalkoxy group having 1 to 30 carbon atoms. One or more of the alkyl and alkoxy groups-CH 2 -may be substituted by-O-, -S-.
More preferably, R 1 Represents an alkyl group having 2 to 20 carbon atoms or an alkoxy group having 2 to 20 carbon atoms.
Further preferably, R 1 Represents an alkyl group having 3 to 15 carbon atoms or an alkoxy group having 3 to 15 carbon atoms.
Most preferably, R 1 Represents an alkyl group having 4 to 10 carbon atoms or an alkoxy group having 4 to 10 carbon atoms.
As the context of the polymerizable compounds, wherein R 2 -R 3 And R is a Each independently represents a hydrogen atom, halogen, cyano, hydroxy, nitro, carboxyl, carbamoyloxy, amino, alkyl of 1 to 10 carbon atoms, haloalkyl of 1 to 10 carbon atoms, alkoxy of 1 to 10 carbon atoms, haloalkoxy of 1 to 10 carbon atoms.
Preferably, R 2 -R 3 And R is a Independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a haloalkoxy group having 1 to 6 carbon atoms.
More preferably, R 2 -R 3 And R is a Each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a haloalkoxy group having 1 to 4 carbon atoms.
Further preferably, R 2 -R 3 And R is a Each independently represents a hydrogen atom, halogen, cyano, methyl, trifluoromethyl, methoxy, trifluoromethoxy.
Most preferably, R 2 -R 3 And R is a Each independently represents a hydrogen atom.
As the context said polymerizable compound, wherein m, n, p and q each independently represent an integer from 0 to 3; preferably represents an integer from 0 to 2; more preferably 0 or 1; and, most preferably, represents 0.
In yet another aspect, the present invention provides a composition comprising a polymerizable compound as described above and at least one second polymerizable compound.
As the context of the polymerizable liquid crystal composition, wherein the second polymerizable compound is selected from compounds of the formulae (B-1) and/or (B-2),
the polymerizable liquid crystal composition described above and below further contains a mother liquid crystal.
Advantageously, as a parent liquid crystal as described above and below, it is commercially available.
The polymerizable liquid crystal composition described above and below further contains an additive.
As the additive, there are included, but not limited to, polymerization initiator, sensitizer, stabilizer, leveling agent, surfactant, polymerization inhibitor, antioxidant, colorant, dispersant, lubricant, hydrophobing agent, adhesive, flow improver, defoamer, deaerator, diluent, thixotropic agent, gelling agent, catalyst, metal complex, luminescent material, and the like.
Advantageously, the content of additives is from 0.01 to 10% by weight, preferably from 0.02 to 8% by weight, more preferably from 0.05 to 5% by weight, and most preferably from 0.1 to 2% by weight, based on the total weight of the polymerizable composition.
The polymerizable liquid crystal composition described above and below further includes an organic solvent.
As the organic solvent described above and below, it is preferable that the solubility to the polymerizable liquid crystal composition is good and that it can be dried and removed at 100 ℃ or less.
The organic solvent is not particularly limited, but is preferably an organic solvent in which the polymerizable liquid crystal composition exhibits 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 tetrahydrothiophene, 1, 2-dimethoxyethane, 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 described 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 solvent, an ether solvent, an ester solvent, and an aromatic solvent.
As the above and below described polymerizable liquid crystal composition, the organic solvent content is 25 to 95wt%, preferably 30 to 90wt%, more preferably 35 to 85wt%, and most preferably 40 to 80wt%, based on the total weight of the polymerizable liquid crystal composition.
In preparing the polymerizable liquid crystal composition solution, heating and/or stirring are advantageously performed in order to promote dissolution of the polymerizable liquid crystal composition.
Further, the above-described polymerizable liquid crystal composition is applied to a substrate and cured to form a cured product.
Coating methods, including but not limited to, applicator methods, bar coating methods, spin coating methods, gravure printing methods, flexographic printing methods, inkjet methods, die coating methods, CAP coating methods, dipping, and the like, are well known in the art. After the polymerizable liquid crystal composition is applied, it is cured (dried).
Advantageously, the curing is carried out in a polymeric manner. In polymerizing the polymerizable liquid crystal composition, it is desirable to rapidly perform polymerization, and therefore, it is preferable to polymerize the composition by irradiation with active energy rays such as ultraviolet-visible light or electron rays. In the case of using ultraviolet-visible light, a polarized light source may be used, or an unpolarized light source may be used.
Substrates of the cured product include, but are not limited to, glass substrates, metal substrates, ceramic substrates, polymeric substrates. Further, as the polymer substrate, for example, there may be mentioned: cellulose derivatives, polyolefins, polyesters, polyolefins, polycarbonates, polyacrylates, polyarylates, polyethersulfones, polyamides, polyimides, polyphenylene sulfides, polyphenylene oxides or polystyrenes, and the like.
Preferred are polyesters, polystyrenes, polyolefins, cellulose derivatives, polyarylates, polycarbonates, from the standpoint of process suitability, in particular from the standpoint of heat resistance and chemical stability.
In still another aspect, the present invention also provides an optically anisotropic body comprising a substrate and a polymer film formed from a cured product of the above-described polymerizable liquid crystal composition, and an alignment film if necessary.
Advantageously, the base material, the alignment film, if necessary, and the polymer film formed from the cured product of the polymerizable liquid crystal composition are sequentially laminated to form an optically anisotropic body.
Oriented film materials including, but not limited to, polyimides, polysiloxanes, polyamides, polyvinyl alcohols, polycarbonates, polystyrenes, polyphenylene oxides, polyarylates, polyethylene terephthalates, polyethersulfones, epoxy resins, acrylic resins, epoxy acrylic resins, coumarins, chalcones, cinnamates, anthraquinones, azo compounds, aryl vinyl compounds, and the like. Polyimide is preferred for process suitability, especially for heat resistance and chemical stability.
Advantageously, the orientation film is obtained by an orientation treatment. The orientation treatment may be a stretching treatment, a rubbing treatment, polarized ultraviolet visible light irradiation, an ion beam treatment, or the like. Preferably the orientation treatment is preferably a rubbing treatment or polarized uv-vis irradiation.
In yet another aspect, the present invention provides an optically anisotropic body formed from the cured product described above and below and/or the use of the optically anisotropic body in an optical, optoelectronic, electronic, semiconductor component or device.
Applications described in the context include, but are not limited to, birefringent films, optical retardation films (retardation films), optical compensation films, vision-expanding films, reflective films, selective reflective films, anti-reflective films, brightness enhancement films, liquid crystal alignment films, polarizing films (deflection plates), polarizing elements, circular polarizing elements, elliptical polarizing elements.
Preferably, the application is a birefringent film.
The birefringent films described above and below are excellent in terms of uneven orientation, and the yellowing properties are also significantly improved under ultraviolet light. Thus, each of the compounds described above and below may be used as a component of the polymerizable composition. Further, the optically anisotropic body using the polymerizable liquid crystal composition containing the compound of the present invention can be used for applications such as optical films.
Detailed Description
In the present invention, technical terms are further explained and defined in detail.
The term "liquid crystal" or "mesogenic compound" refers to a compound that forms a mesogenic or liquid crystal phase under certain conditions.
The term "polymerizable mesogenic" or "polymerizable compound" is abbreviated as RM and denotes polymerizable liquid crystal or mesogenic compounds, in particular monomeric compounds.
The term "single reactive" or "double reactive" means that the polymerizable mesogenic or polymerizable compound has one or two polymerizable groups.
The term "polymerizable group" means a group that is polymerized by means of light, heat, or a catalyst to form a polymer of higher molecular weight.
The term "film" means a rigid or flexible coating or layer having mechanical stability; optionally, the film may be present alone; on top of the support substrate; or sandwiched between two substrates.
The present invention is further described below with reference to synthesis examples and examples, which are not intended to limit the scope of the invention. Unless otherwise indicated, the percentages in the examples are by mass.
Synthesis example
The polymerizable compounds Q-1 to Q-3 were synthesized, respectively.
The preparation process route of Q-1 is as follows:
50g of S-1 was added to a 1L reaction flask, 300ml of methylene chloride was added, 264g of S-2 was added, then 3.3g of DMAP was added thereto dropwise, at room temperature, to which was added a methylene chloride solution of DCC (124 g was dissolved in 200g of methylene chloride, after completion of the addition, reacted for 6 hours. Filtration, the cake was rinsed with 100g of methylene chloride, and then the filtrate was washed with water, dried, filtered, purified by column chromatography, concentrated, crystallized by adding 500g of methanol, filtered, and dried to give 151.4g, yield 84%
100g of S-3 was added to a 1L reaction flask, 500g of toluene was added, 28g of S-4 was added, and then 0.5g of cuprous iodide, 1.5g of triphenylphosphine, 1g of ditriphenylphosphine palladium dichloride, and 25g of triethylamine were added. Under the protection of nitrogen, heating to 80 ℃ for reaction for about 4 hours, after the reaction is finished, passing through a chromatographic column, concentrating chromatographic liquid, crystallizing with 200g of methanol, filtering and drying to obtain 88.5g of solid with the yield of 78%.
The nmr data were as follows: 1 H NMR(CDCl 3 )δ：0.89-0.90(t,3H),1.27-1.29(m,4H),1.61-1.62(t,2H),1.88-1.90(m,10H),3.98-3.99(t,4H),4.14-4.16(t,4H),5.82(d,2H),6.13(q,2H),6.39(d,2H),6.83-6.84(d,2H),6.91-6.92(d,4H),7.03(s,1H),7.19-7.21(d,2H),7.47-7.48(d,2H),7.99-8.01(d,4H)。
preparation of Q-2
The synthesis route and conditions are the same as those of Q-1, and the obtained Q-2 nuclear magnetic resonance data are as follows: 1 H NMR(CDCl 3 )δ：0.89-0.90(t,3H),1.28-1.31(m,4H),1.60-1.61(t,2H),1.87-1.89(m,8H),3.97-3.98(t,4H),4.13-4.15(t,6H),5.80(d,2H),6.12(q,2H),6.37(d,2H),6.80-6.81(d,2H),6.92-6.93(d,4H),7.02(s,1H),7.20-7.23(d,2H),7.45 -7.47(d,2H),7.98-8.00(d,4H)。
preparation of Q-3
The synthesis route and conditions are the same as those of Q-1, and the obtained Q-3 nuclear magnetic resonance data are as follows: 1 H NMR(CDCl 3 )δ：0.89-0.90(t,3H),1.28-1.30(m,4H),1.62-1.65(t,4H),1.87-1.95(m,16H),3.99-4.01(t,4H),4.16-4.17(t,4H),5.84(d,2H),6.15(q,2H),6.41(d,2H),6.84-6.85(d,2H),6.93-6.95(d,4H),7.04(s,1H),7.20-7.22(d,2H),7.49-7.50(d,2H),7.99-8.02(d,4H)。
examples 1 to 3 and comparative examples 1 to 3
Examples 1-3 Compounds of the invention Q-1 to Q-3 were used.
Comparative examples 1-3 use compounds B-1 to B-3 known from the prior art.
In order to evaluate the alignment unevenness and yellowing property of the birefringent film, a liquid crystal composition was provided as a mother liquid crystal (M). The liquid crystal composition comprises 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.
The alignment film was coated with a polyimide solution on a glass substrate having a thickness of 0.7mm, dried at 100℃for 10 minutes, and then baked at 200℃for 60 minutes to obtain an alignment film, and the obtained alignment film was subjected to a rubbing treatment using a commercially available rubbing device.
A polymerizable liquid crystal composition was prepared by adding 40% of a compound to be evaluated to the mother liquid crystal M; further, 1% of a photopolymerization initiator Irgacure 907 (BASF corporation), 0.1% of 4-methoxyphenol and 80% of chloroform were added to prepare a coating solution.
The coating liquid was coated on the rubbed alignment film by spin coating. Drying at 80deg.C for 1min, further drying at 120deg.C for 1min, and drying with high pressure mercury lamp at 40mW/cm 2 Ultraviolet rays were irradiated for 25 seconds to prepare a birefringent film to be evaluated.
The degree of unevenness was evaluated by observation with a polarizing microscope on the obtained birefringent film. 10 birefringent films each containing the compound to be evaluated were produced, and the number of irregularities was counted. The number of irregularities observed in 10 birefringent films was counted up, and if the number of irregularities was 0, the number was 1-10, and the number was ten or more, the number was poor.
Using a xenon irradiation tester (Suntest XLS, ATLAS Co.) at 60mW/cm 2 The prepared birefringent films were subjected to a sun-drying test at 26℃and 120J. The resultant birefringent film was evaluated for yellowing property and non-uniformity of orientation.
Yellowing performance was evaluated using the Yellowness Index (YI). Calculating the difference (ΔYI) between the YI value before the sun test and the YI value after the sun test, the Yellowness Index (YI) was measured using a JASCO UV/VIS spectrophotometer V-560 and calculated by an attached color diagnostic procedure. The calculation formula is expressed as: yi=100 (1.28X-1.06Z)/Y (JIS K7373) (X, Y, Z represents tristimulus values in XYZ color system, and smaller Δyi value means less discoloration.
TABLE 1
| Film and method for producing the same | The compounds to be evaluated used |
| Example 1 | Compounds of the invention Q-1 |
| Example 2 | Compounds of the invention Q-2 |
| Example 3 | Compounds of the invention Q-3 |
| Comparative example 1 | Comparative Compound B-1 |
| Comparative example 2 | Comparative Compound B-2 |
| Comparative example 3 | Comparative Compound B-3 |
TABLE 2
| Film and method for producing the same | △YI | Non-uniform orientation |
| Example 1 | 0.5 | 0 |
| Example 2 | 0.4 | 0 |
| Example 3 | 0.5 | 0 |
| Comparative example 1 | 1.6 | 8 |
| Comparative example 2 | 2.7 | 6 |
| Comparative example 3 | 5.2 | 9 |
As can be seen from tables 1-2, the birefringent films of examples 1-3 are excellent in terms of non-uniform orientation, and also significantly improved in terms of yellowing under ultraviolet light. Thus each of the compounds of the present invention may be used as a component of a polymerizable composition. Further, the optically anisotropic body using the polymerizable liquid crystal composition containing the compound of the present invention can be used for applications such as optical films.
It should be understood that the description of the specific embodiments is merely illustrative of the principles and spirit of the invention, and not in limitation thereof. Further, it should be understood that various changes, substitutions, omissions, modifications, or adaptations to the present invention may be made by those skilled in the art after having read the present disclosure, and such equivalent embodiments are within the scope of the present invention as defined in the appended claims.
Claims (10)
1. An alkynyl-containing polymerizable compound, characterized in that the compound is selected from compounds of the general formula (1),
in the method, in the process of the invention,
P 1 and P 2 Each independently represents a polymerizable group;
L 1 and L 2 Each independently represents an alkylene group having 1 to 30 carbon atoms; the alkylene group may be linear or may have a branched group; one or more of the alkylene groups-CH 2 -can be substituted by-O-, -S-, -NH-, -NR a -, -CO-, -OCO-, -COO- -OCOO-, -SCO-, -COs-substitution;
R 1 -R 2 and R is a Each independently of the groundA hydrogen atom, a C1-30 alkyl group, a C1-30 haloalkyl group, a C1-30 alkoxy group, a C1-30 haloalkoxy group, a C2-30 alkenyl group, a C2-30 haloalkenyl group, a C2-30 alkenyloxy group, a C2-30 haloalkenyloxy group, a C1-30 alkoxycarbonyl group, a C1-30 haloalkoxycarbonyl group, a C1-30 alkylcarbonyl group, a C1-30 haloalkylcarbonyl group, a C1-30 alkylacyloxy group, a C1-30 haloalkylacyloxy group, a C6-30 alkylaryl group, a C6-30 arylalkyl group, a C6-30 alkylaryl group, a C6-30 arylalkyloxy group, a C6-30 arylcarbonyl group, a C6-30 aryloxycarbonyl group, a C6-30 arylcarbonyloxy group, and a C6-30 aryloxycarbonyloxy group. One or more of the alkyl, alkoxy, alkenyl, alkenyloxy groups-CH 2 -can be substituted by-O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, -COS-; optionally, one or more H atoms of the alkyl, alkoxy, alkenyl, alkenyloxy groups may be substituted with halogen, cyano, hydroxy, nitro, carboxyl, carbamoyloxy, amino, sulfamoyl, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, thioisocyano, alkyl of 1 to 30 carbon atoms, haloalkyl of 1 to 30 carbon atoms, alkoxy of 1 to 30 carbon atoms, haloalkoxy of 1 to 30 carbon atoms, alkylacyloxy of 1 to 30 carbon atoms, haloalkylacyloxy of 1 to 30 carbon atoms or a polymerizable group.
m, n and p each independently represent an integer of 0 to 4; q each independently represents an integer of 0 to 3, m, n, p and q.gtoreq.gtoreq.2, a plurality of R 2 May be the same or different.
2. The polymerizable compound of claim 1 wherein the polymerizable group is selected from the group consisting of:
wherein R is 3 And R is R 1 -R 2 The definitions are the same.
3. The polymerizable compound of claim 2, wherein P 1 And P 2 Each independently represents a group of (P-1) and (P-2); preferably, P 1 And P 2 Each independently represents a group of (P-1).
4. The polymerizable compound of claim 1, wherein L 1 And L 2 Each independently represents an alkylene group having 1 to 16 carbon atoms.
5. The polymerizable compound of claim 1, wherein R 1 Represents 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, or a haloalkoxy group having 1 to 30 carbon atoms.
6. The polymerizable compound of claim 1, wherein m, n, p, and q represent 0.
7. A polymerizable liquid crystal composition comprising the polymerizable compound according to any one of claims 1 to 6 and at least one second polymerizable compound.
8. The liquid crystal composition according to claim 7, wherein the second polymerizable compound is selected from the group consisting of compounds of the formulae (B-1) and/or (B-2),
9. an optically anisotropic body formed from the polymerizable liquid crystal composition according to claim 8.
10. The optically anisotropic body of claim 9, wherein the optically anisotropic body is selected from birefringent films.
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| PCT/CN2024/097147 WO2025016083A1 (en) | 2023-07-18 | 2024-06-04 | Alkynyl-containing polymerizable compound and optical film use thereof |
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| EP2913349B1 (en) * | 2012-10-23 | 2019-06-19 | Zeon Corporation | Polymerizable compound, polymerizable composition, polymer, and optical anistropic body |
| US9809668B2 (en) * | 2013-11-29 | 2017-11-07 | Dic Corporation | Polymerizable compound, composition, polymer, optically anisotropic body, liquid crystal display device, and organic EL device |
| US10633353B2 (en) * | 2014-12-04 | 2020-04-28 | Dic Corporation | Polymerizable compound, composition, polymer, optically anisotropic body, liquid crystal display element, and organic EL display |
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