CN117720437A - Negative dispersion optical film and compound - Google Patents

Negative dispersion optical film and compound Download PDF

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CN117720437A
CN117720437A CN202311098649.7A CN202311098649A CN117720437A CN 117720437 A CN117720437 A CN 117720437A CN 202311098649 A CN202311098649 A CN 202311098649A CN 117720437 A CN117720437 A CN 117720437A
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group
carbon atoms
independently represents
polymerizable
polymerizable compound
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郑飞翔
殷勇
靳灿辉
谭玉东
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Shandong Hetong New Material Co ltd
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Shandong Hetong New Material Co ltd
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Abstract

There is provided a biphenyl nitrile group-containing polymerizable compound selected from the group consisting of compounds of the general formula (1). 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

Negative dispersion optical film and compound
Technical Field
The invention belongs to the technical field of light modulation and control, and particularly relates to a negative dispersion optical film and a compound.
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), a negative dispersion optical film, an optical compensation film, a vision-expanding film, a reflection film, a selective reflection 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 negative dispersion optical films, 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 negative dispersion optical film of the prior art is liable to cause yellowing and uneven orientation.
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 a polymerizable compound containing biphenyl nitrile groups 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 aforementioned technical problems can be solved by using the biphenyl nitrile group-containing polymerizable compound of the general formula (1) of the present invention, thereby completing the present invention.
The invention comprises the following components:
a biphenyl nitrile group-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;
A 1 and A 2 Each independently representsAnd->One or more of the group consisting of;
Z 1 and Z 2 Each independently represents a single bond, -OCO-, -COO-, -OCOO-, -CH 2 O-、-OCH 2 -、-CF 2 O-、-OCF 2 -one or more of the group consisting of;
x and y each independently represent an integer of 1 to 3;
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 via-O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, -COS-substitution; 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;
k each independently represents an integer of 0 to 10; m and p each independently represent an integer of 0 to 4; n represents an integer of 0 to 3; k. when m, n and p are more than or equal to 2, a plurality of R 1 And R is 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, 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, or a carbon atomA haloalkenyl group having 2 to 30 carbon atoms, an alkenyloxy group having 2 to 30 carbon atoms, a haloalkenyloxy group having 2 to 30 carbon atoms, an alkoxycarbonyl group having 1 to 30 carbon atoms, a haloalkoxycarbonyl group having 1 to 30 carbon atoms, an alkylcarbonyl group having 1 to 30 carbon atoms, a haloalkylcarbonyl group having 1 to 30 carbon atoms, an alkylacyloxy group having 1 to 30 carbon atoms or a haloalkylacyloxy group having 1 to 30 carbon atoms.
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 a polymerizable compound, where Z 1 And Z 2 Each independently represents a single bond, -OCO-, -COO-, -CH 2 O-、-OCH 2 -、-CF 2 O-、-OCF 2 -one or more of the group consisting of.
Preferably Z 1 And Z 2 Each independently represents-OCO-, -COO-, -CH 2 O-、-OCH 2 -、-CF 2 O-、-OCF 2 -one or more of the group consisting of.
More preferably, Z 1 And Z 2 Each independently represents-OCO-, -COO-, -CH 2 O-、-OCH 2 -one or more of the group consisting of.
As the context implies, wherein x and y each independently represent an integer from 1 to 2. Advantageously, x and y represent 2.
As the context of the polymerizable compounds, wherein R 1 -R 2 And R is a Each independently 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 -R 2 And R is a Each independently 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 -R 2 And R is a Each independently represents an alkyl group having 2 to 20 carbon atoms or an alkoxy group having 2 to 20 carbon atoms.
Further preferably, R 1 -R 2 And R is a Each independently represents an alkyl group having 3 to 15 carbon atoms or an alkoxy group having 3 to 15 carbon atoms.
Most preferably, R 1 -R 2 And R is a Each independently 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 a Each independently represents a hydrogen atom, a halogen atom,Cyano, hydroxy, nitro, carboxyl, carbamoyloxy, amino, alkyl of 1-10 carbon atoms, haloalkyl of 1-10 carbon atoms, alkoxy of 1-10 carbon atoms, haloalkoxy of 1-10 carbon atoms.
Preferably, R 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 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 a Each independently represents a hydrogen atom, halogen, cyano, methyl, trifluoromethyl, methoxy, trifluoromethoxy.
Most preferably, R a Each independently represents a hydrogen atom.
As the context said polymerizable compounds, wherein each k independently represents an integer from 0 to 5; m and p each independently represent an integer of 0 to 3; n represents an integer of 0 to 2.
Preferably, k each independently represents an integer of 0 to 2; m and p each independently represent an integer of 0 to 2; n represents 0 or 1.
More preferably, k, m, n and p each represent 0.
In a preferred embodiment, as context said biphenyl nitrile group-containing polymerizable compounds, wherein said compounds are selected from the group of compounds of the general formula (2),
wherein,
P 1 and P 2 、L 1 And L 2 、R 1 And R is 2 And k, m, n and p are as defined in formula (1).
In a specific embodiment, as a polymerizable compound containing a biphenylnitrile group as described above and below, the compound is selected from the group consisting of compound P.
In yet another aspect, the present invention provides a polymerizable liquid crystal composition comprising a polymerizable compound as described above and below.
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.
In a specific embodiment, the polymerizable liquid crystal composition described above and below is one in which the mother liquid crystal contains 50% of the compound (M-1) described in JP-A-2005-015473, 30% of the compound (M-2) described in JP-A-10-87565, and 20% of the compound (M-3) described in JP-T-2002-537280.
As a polymeric liquid crystal composition described above and below, additives are optionally further included.
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 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), negative dispersion optical 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 negative dispersion optical film.
The negative dispersion optical film described above and below has excellent orientation, and the yellowing performance is obviously 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 compound P of the present invention was synthesized.
The synthetic route for compound P is as follows:
preparation of intermediate S-3
40g of Compound S-1 and 53.2g of Compound S-2 were charged into a 500ml reaction flask, and 400g of methylene chloride and 5.4g of DMAP were further added. Then, the temperature was lowered to 0℃and a methylene chloride solution of DCC (50 g dissolved in 120g of methylene chloride) was added dropwise thereto. After the completion of the dropwise addition, the temperature is raised to 25 ℃ and the reaction is carried out for 12 hours. After-treatment, suction filtration is carried out firstly, a filter cake is washed by methylene dichloride, a liquid phase is remained, 200g of 5% hydrochloric acid is used for washing the reaction liquid, and then 200g of water is used for washing twice. The organic phase is dried, passed through a silica gel column, and 0.07g of p-methoxyphenol is added to the eluate, and then desolventized under reduced pressure, and recrystallized from 800g of methanol and 80g of dichloromethane. 70g of intermediate S-3 were obtained in 80% yield.
Preparation of intermediate S-4
70g of intermediate S-3 is taken and added into a 1000ml three-necked flask, 200ml of dichloromethane, 13.9g of hydrogen peroxide, 0.5g of 4-OH-TEMPO and 2.4g of sodium dihydrogen phosphate and 200g of water are added. Heating to 35 ℃, dropwise adding sodium chlorite aqueous solution (12.9 g dissolved in 150g water), and preserving heat for 2h after the completion of the dropwise adding. And (5) carrying out suction filtration on the reaction liquid to obtain a solid. Pulping with 200g of isopropanol, suction filtration and drying gave 64.6g of intermediate S-4 in 94% yield.
Preparation of product P
60g of intermediate S-4 and 14g of compound S-5 were added to a 500ml reaction flask, 300g of methylene chloride and 2g of DMAP were added, and then the temperature was lowered to 0℃to which a methylene chloride solution of DCC (16 g dissolved in 60g of methylene chloride) was added dropwise. After the completion of the dropwise addition, the temperature is raised to 25 ℃ and the reaction is carried out for 12 hours. After-treatment, suction filtration is carried out firstly, a filter cake is washed by methylene dichloride, a liquid phase is remained, 100g of 5% hydrochloric acid is used for washing the reaction liquid in the liquid phase, and then 100g of water is used for washing twice. The organic phase is dried, passed through a silica gel column, and 0.1g of p-methoxyphenol is added to the eluate, and then desolventized under reduced pressure, and recrystallized from 600g of methanol and 60g of dichloromethane. 59g of product P were obtained in 82% yield.
The nuclear magnetic resonance data are as follows, 1 H NMR(CDCl 3 )δ：1.45-1.47(t,8H),1.51-1.53(t,8H),1.61-1.63(t,2H)，1.78-1.79(t,8H)，1.82-1.84(t,8H),2.44-2.46(t,2H),3.94-3.96(t,4H),3.98-4.01(t,4H),4.14-4.16(d,4H),5.20-5.22(d,4H),6.15-6.17(d,2H),6.83(s,1H),6.84-6.87(d,9H),6.91-6.92(d,2H),6.94(d,1H),7.55-7.56(d,2H),7.65 -7.66(d,2H),7.62-7.63(d,2H)。
example 1 and comparative examples 1 to 3
Example 1 compound P of the present invention was 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 negative dispersion optical film, a liquid crystal composition as a mother liquid crystal (M) was provided. 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 negative dispersion optical film to be evaluated.
The degree of unevenness was evaluated by observation with a polarizing microscope on the obtained negative dispersion optical film. 10 negative dispersion optical films each containing the compound to be evaluated were produced, and the number of irregularities was counted. The number of irregularities observed in 10 negative dispersion optical films was counted up, and the number of irregularities was preferably 0, the number of irregularities was 1, the number of irregularities was good, the number of irregularities was 1 to 10, and the number of irregularities was ten or more, the number of irregularities was poor.
Using a xenon irradiation tester (Suntest XLS, ATLAS Co.) at 60mW/cm 2 The negative dispersion optical films produced were subjected to a sunburn test at 26℃and 120J. The obtained negative dispersion optical 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 Compound P of the present invention
Comparative example 1 Comparative Compound B-1
Comparative example 2 Comparative Compound B-2
Comparative example 3 Comparative Compound B-3
TABLE 2
As can be seen from table 2, the negative dispersion optical film of example 1 is excellent in terms of non-uniformity of orientation, and also significantly improved in terms of yellowing under ultraviolet light. The compounds of the present invention are therefore useful as components of polymeric compositions. Further, an optically anisotropic body using a polymerizable liquid crystal composition containing the compound of the present invention can be used for a negative dispersion optical film or the like.
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. A biphenyl nitrile group-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;
A 1 and A 2 Each independently representsOne or more of the group consisting of;
Z 1 and Z 2 Each independently represents a single bond, -OCO-, -COO-, -OCOO-, -CH 2 O-、-OCH 2 -、-CF 2 O-、-OCF 2 -one or more of the group consisting of;
x and y each independently represent an integer of 1 to 3;
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 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 groupArylalkyl, alkylaryl of 6 to 30 carbon atoms, arylalkyl of 6 to 30 carbon atoms, arylcarbonyl of 6 to 30 carbon atoms, aryloxycarbonyl of 6 to 30 carbon atoms, arylcarbonyloxy of 6 to 30 carbon atoms and aryloxycarbonyloxy of 6 to 30 carbon atoms; 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;
k each independently represents an integer of 0 to 10; m and p each independently represent an integer of 0 to 4; n represents an integer of 0 to 3; k. when m, n and p are more than or equal to 2, a plurality of R 1 And R is 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 according to claim 1, which isCharacterized in that 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 x and y represent 2.
6. The polymerizable compound of claim 1 wherein k, m, n and p each represent 0.
7. The polymerizable compound according to claim 1, wherein the compound is selected from the group consisting of compounds of the general formula (2),
wherein,
P 1 and P 2 、L 1 And L 2 、R 1 And R is 2 And k, m, n and p are as defined in formula (1).
8. A polymerizable liquid crystal composition comprising the polymerizable compound according to any one of claims 1 to 7.
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 negative dispersion optical films.
CN202311098649.7A 2023-08-29 2023-08-29 Negative dispersion optical film and compound Pending CN117720437A (en)

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CN117720437A true CN117720437A (en) 2024-03-19

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