JP2696480B2 - Novel triphenylene derivative and optically anisotropic material containing it - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel compound useful as a liquid crystal material, a triphenylene derivative, a composition containing the same, or an optically anisotropic material comprising the same.

[0002]

2. Description of the Related Art In recent years, liquid crystal display elements have been widely used in word processors, personal computers, televisions and the like, and industrial activities such as materials and devices related thereto have been actively carried out. Active development research has also been conducted on liquid crystal compounds, which are fundamental materials of liquid crystal display materials, and many compounds have been developed. These compounds are considered to be used for the development of various applications other than display devices. In addition to rod-shaped liquid crystal compounds which have been well known and widely used, discotic liquid crystal compounds, so-called discotic liquid crystal compounds, have recently attracted attention.

A typical discotic liquid crystal compound is C.I. Destrade et al., Mo.
l. Cryst. Liq. Cryst. 71 volumes, 111
As described on page (1981), for example, benzene derivatives, triphenylene derivatives, truxene derivatives, phthalocyanine derivatives, and B.I. Kohne et al., Angew. Chem. 96 volumes, 70 pages (1
984), a cyclohexane derivative described in J.
M. J. Lehn et al. Chem. Soc. C
hem. Commun. , P. 1794 (1985); Zhang, J .; S. Moore et al.'S research report,
J. Am. Chem. Soc. 116, p. 2655 (1994). In general, these compounds are used as a central nucleus of a molecule, and include a linear alkyl group, an alkoxy group, and a substituted benzoyloxy derivative. It has a structure in which a group or the like is radially substituted as its side chain.

[0004] The discotic liquid crystal phase has a columnar phase (co) in which the central cores of discotic molecules are stacked in a columnar shape by an intermolecular force.
It is known that it can be roughly classified into a lunar phase), a discotic nematic phase in which discotic molecules are randomly aggregated, and a chiral discotic nematic phase. However, W. H. Phys by de jeu
ical properties of liquid
crystalline materials (19
80 by Gordon and Break, S
As described in Science Publishers, columnar phases are often found, while discotic nematic phases are rarely found.

The fact that the triphenylene-based discotic liquid crystal of the present invention has negative birefringence is described in B.S. Mou
et al. [Mol. Cryst. Liq. C
ryst. 84, p. 193 (1982)]. In order to apply this property as an optical compensation sheet, all the molecules constituting the thin film are statistically arranged in one direction at room temperature. It is necessary. Moreover,
A discotic liquid crystal is composed of an alignment region (domain) having a specific direction microscopically, similar to a conventional liquid crystal composed of rod-like molecules, and is a so-called multi-layer that does not exhibit optical anisotropy macroscopically. Due to the nature of forming domains, in many cases the thin films do not exhibit favorable optical properties that can be used for optical compensation sheets.

By the way, as is known for a rod-like compound which is a typical structure of a liquid crystal, the liquid crystal phases to be formed and the transition temperature between the phases often change remarkably due to a slight difference in the structure. This is not limited to the rod-shaped liquid crystal compound, and the same applies to the discotic liquid crystal compound. It is known that such a change in the phase transition temperature is also caused by mixing of compounds, and therefore, the discovery of an excellent mixture is also as important as the discovery of a novel compound. The required liquid crystal phase and the transition temperature between each phase differ depending on the target device.Therefore, by preparing a wide variety of compounds, the range of choice can be expanded for the first time, and it is possible to meet various purposes. Become. It is also very important from a practical point of view to provide a compound in which a polymerizable functional group is introduced in the molecule in order to fix a required liquid crystal phase state.

However, as for discotic liquid crystal compounds, many compounds have not yet been known, and little is known about excellent mixtures. This is the same for the triphenylene derivative which is a particularly attractive compound. Destrad
e, et al. Phsique, Vol. 40, No. 4, C3-1
7 (1979) and C.I. Vauchier et al., Mo
l. Cryst. Liq. Cryst. 66 volumes, 103
Only a few examples are described on page (1981), and the discovery of more useful mixtures is desired.

[0008]

Accordingly, an object of the present invention is to provide a novel triphenylene derivative useful as a liquid crystal material,
In particular, it is an object of the present invention to provide a liquid crystalline compound having a polymerizable functional group, a mixture containing the same, and an optically anisotropic material comprising the same.

[0009]

In this regard, in this regard, we have studied various discotic liquid crystals in detail, and have found that a liquid crystal having a property of forming a discotic nematic liquid crystal phase or a uniaxial columnar phase, in particular, a triphenylene derivative. Is an attractive compound that is easy to synthesize and easily forms a monodomain discotic nematic phase which is advantageous for use as an optical element. Particularly, is a compound represented by the following general formulas (1), (2) and The inventors have found that a thin film of a compound having a triphenylene-based carbon skeleton structure represented by the general formula (3) has preferable characteristics as an optically anisotropic material, and have completed the present invention.

The present inventors have conducted intensive studies, and as a result,
[1] It has been found that the object of the present invention can be achieved by a compound represented by the following general formula (1), (2) or (3). General formula (1)

[0011]

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[0012] In the ^{formula, R 11} preliminary ^{R 12} represents a hydrogen atom or a methyl group ^{independently, R 13} represents an alkoxy group substituent P1 or terminally substituted with a substituent P1, substituents P1 ^{R 14} And R ¹⁵ each independently represent a hydrogen atom or an unsubstituted alkyl group;
¹⁶ represents a hydrogen atom, a 2-chloroethyl group, a methoxyethoxyethyl group or an unsubstituted alkyl group;
Represents 0 or 1.

[0013]

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In the formula, R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group, and R ²³ has a substituent P
2 represents an alkoxy group substituted by 2
²⁴ and R ²⁵ each independently represent a hydrogen atom or an unsubstituted alkyl group, and R ^{26 of the} substituent P2 represents a hydrogen atom, a 2-chloroethyl group, a methoxyethoxyethyl group or an unsubstituted alkyl group.

[0015]

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In the formula, R ³¹ and R ³² each independently represent a hydrogen atom or a methyl group, and R ³³ has a substituent P
3 represents an alkoxy group substituted by 3
³⁴ and R ³⁵ each independently represent a hydrogen atom or an unsubstituted alkyl group, and R ^{36 of the} substituent P3 represents a hydrogen atom, a 2-chloroethyl group, a methoxyethoxyethyl group or an unsubstituted alkyl group. In addition, [2] an optically anisotropic material containing at least one of the compounds represented by the above general formulas (1), (2) and (3), further [3] the above [2] It has been found that the present invention is achieved by a retardation film for a liquid crystal display element using an optically anisotropic material.

Hereinafter, the general formula (1) will be described in detail.
I will tell. R¹¹, R¹²Are each independently a hydrogen atom or methyl
Represents a hydroxyl group. When n is 0, the substituent P1 is an unsaturated double
Represents a bonding group. The substituent R¹⁴, R ^FifteenAre each independently water
Elemental atom, alkyl group (for example, methyl, ethyl, n-pro
Pill, isopropyl, n-butyl, pentyl, hex
, Heptyl, octyl, nonyl, methyl,
Lower alkyl groups such as ethyl are preferred, and methyl
Is preferred. ) And R¹⁴Is a methyl group and R^FifteenIs a hydrogen source
Child or R¹⁴, R^FifteenPreferably use a combination of hydrogen atoms
Good.

The substituent R ¹⁶ is a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl, ethyl, n-propyl,
Examples thereof include isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, 2-chloroethyl, 3-methoxyethyl, and methoxyethoxyethyl. Lower alkyl groups such as methyl and ethyl are preferable, and methyl is more preferable. ), A hydrogen atom and a lower alkyl group are preferred, and a hydrogen atom is more preferred.

The alkoxy residue substituted by the terminal substituent P1 is an alkyleneoxy group (for example, an alkyleneoxy group such as ethyleneoxy, propyleneoxy, butyleneoxy, pentyleneoxy, hexyleneoxy, heptyleneoxy, etc.). A substituted alkyleneoxy group containing an ether bond such as ethoxy). However, the terminal substituent P1 may be directly bonded to the aromatic ring.

[0020] When n is 1, the terminal substituent P1 in R ¹³ represents a so-called vinyl ether group, the substituents R ^14, R ¹⁵ of the substituents P1 each independently represent a hydrogen atom, an alkyl group (e.g. methyl, Ethyl, n-propyl, isopropyl, n
-Butyl, pentyl, hexyl, heptyl, octyl,
Nonyl is preferred, and lower alkyl groups such as methyl and ethyl are preferable, and methyl is more preferable. ) And R
^It is preferable that ¹⁴ is a methyl group and R ¹⁵ is a hydrogen atom, or that both R ¹⁴ and R ¹⁵ are hydrogen atoms.

The substituent R ¹⁶ is a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl,
Heptyl, octyl, nonyl, 2-chloroethyl, include main bets <br/> ethoxy ethyl, methyl, preferably a lower alkyl group such as ethyl, more preferably methyl. Represents a hydrogen atom, a lower alkyl group is preferable,
Further, a hydrogen atom is preferred. Therefore, as the substituent P1, an unsubstituted vinyloxy group which is generally a functional group having high polymerization activity is preferably used.

The alkoxy residue substituted by the terminal substituent P1 includes an alkyleneoxy group (eg, ethyleneoxy, propyleneoxy, butyleneoxy, pentyleneoxy, hexyleneoxy, heptyleneoxy), an alkyleneoxy-substituted alkoxy group (eg, Represents ethyleneoxyethoxy).

Hereinafter, specific examples of the compound of the present invention represented by the general formula (1) are shown, but the present invention is not limited thereto.

[0024]

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[0025]

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[0026]

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[0027]

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Next, the general formula (2) will be described in detail. R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group.

The terminal substituent P2 in R ²³ represents a so-called acryl group. The substituents R ²⁴ and R ²⁵ of the substituent P2 each independently represent a hydrogen atom or an alkyl group (eg, methyl, ethyl,
n-propyl, isopropyl, n-butyl, pentyl,
Hexyl, heptyl, octyl and nonyl are mentioned, and lower alkyl groups such as methyl and ethyl are preferable, and methyl is more preferable. ) Wherein R ²⁴ is methyl and R ²⁵ is a hydrogen atom, or a combination of both R ²⁴ and R ²⁵ is a hydrogen atom.

The substituent ^{R 26} is a hydrogen atom, a substituted or unsubstituted alkyl group (e.g. methyl, ethyl, n- propyl, isopropyl, n- butyl, pentyl, hexyl,
Heptyl, octyl, nonyl, 2-chloroethyl, include main bets <br/> ethoxy ethyl, methyl, preferably a lower alkyl group such as ethyl, more preferably methyl. ) And a hydrogen atom is preferable. Therefore, the substituent P
The 2 generally unsubstituted acryloxy group, methacryloxy group, polymerization activity high functional group such as crotonyl group is preferably used.

The alkoxy residue substituted by the terminal substituent P2 is an alkyleneoxy group (for example, an alkyleneoxy group such as ethyleneoxy, propyleneoxy, butyleneoxy, pentyleneoxy, hexyleneoxy, heptyleneoxy, etc.). A substituted alkyleneoxy group containing an ether bond such as ethoxy).

Hereinafter, specific examples of the compound of the present invention represented by the general formula (2) are shown, but the present invention is not limited thereto.

[0033]

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[0034]

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Next, the general formula (3) will be described in detail. R ³¹ and R ³² each independently represent a hydrogen atom or a methyl group.

The terminal substituent P3 for R ³³ represents a so-called oxirane groups. The substituents R ³⁴ and R ³⁵ of the substituent P 3 each independently represent a hydrogen atom or an alkyl group (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl). , Methyl, lower alkyl groups such as ethyl are preferred,
Further, methyl is preferred. ), And both R ³⁴ and R ³⁵ are preferably hydrogen atoms.

The substituents ^{R 36} a hydrogen atom, a substituted or unsubstituted alkyl group (e.g. methyl, ethyl, n- propyl, isopropyl, n- butyl, pentyl, hexyl,
Heptyl, octyl, nonyl, 2-chloroethyl, include main bets <br/> ethoxy ethyl, methyl, preferably a lower alkyl group such as ethyl, more preferably methyl. ), And a lower alkyl group such as a hydrogen atom, methyl, ethyl and n-propyl is preferred.

The alkoxy residue substituted by the terminal substituent P3 includes an alkyleneoxy group (eg, ethyleneoxy, propyleneoxy, butyleneoxy, pentyleneoxy, hexyleneoxy, heptyleneoxy), an alkyleneoxy-substituted alkoxy group (eg, Represents ethyleneoxyethoxy).

Hereinafter, specific examples of the compound of the present invention represented by the general formula (3) are shown, but the present invention is not limited thereto.

[0040]

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[0041]

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The triphenylene derivative of the present invention generally means three more benzene rings around the benzene ring as shown in the general formulas (1), (2) and (3). It refers to a condensed structure, and among the reported liquid crystal compounds, most of the compounds have an alkoxy group, an alkanoyloxy group, or a benzoyloxy group substituted at the 2,3,6,7,10,11-position. The feature of the triphenylene derivative is that a monodomain discotic nematic phase is easily formed as compared with other discotic liquid crystals. In order to be optically anisotropic, at least the optical axis must be tilted in a certain direction. For this purpose, the formation of multi-domain, which is a general property of liquid crystal, is suppressed and a mono-domain liquid crystal phase is formed. Is necessary. Therefore, it is considered that the triphenylene derivative which easily forms a monodomain discotic nematic phase is a group of compounds having a relatively large possibility as an optically anisotropic element for the above-described reason.

Next, with respect to the composition according to claim 4,
That is, it is described that the liquid crystalline compound of the present invention can exhibit useful properties as a mixture as well as used alone. An object of the present invention is to provide a useful liquid crystal compound as described at the beginning,
One of the more specific objects is to cause the liquid crystal compound of the present invention to have a monodomain optically uniaxial alignment state to express an optically significant function, and use it as an optical functional element. To provide.

It is not always easy to satisfy all of the various requirements for such an optical function element with a single liquid crystal. For example, the phase transition temperature for taking a certain preferred liquid crystal phase is too high and the type of support used is limited, or the liquid crystal phase is thermally unstable and the durability is unsatisfactory. In some cases, the tilt angle is not a preferable angle and the best optical characteristics cannot be obtained. In such a case, we used the liquid crystalline compound of the present invention, as described at the beginning, other discotic liquid crystalline compounds having a similar structure, and not only discotic compounds but also conventional rod-like nematic liquid crystalline compounds. Alternatively, they have found that the physical properties can be adjusted by mixing a cholesteric liquid crystal compound.

As the compound to be mixed, not only a liquid crystalline or non-liquid crystalline high molecular compound but also various low molecular compounds are used. Examples of the polymer compound include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleic anhydride copolymer, polyvinyl alcohol, N-methylolacrylamide, styrene, vinyl toluene copolymer, chlorosulfonated polyethylene, Nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, polyethylene, polypropylene, polycarbonate, silylate polymer, various liquid crystal polymers, etc. .

As the low molecular weight compound, a monomer used for forming the above-mentioned high molecular substance having a polymerizable group is preferably used. For example, ethylene glycol
1,4-diacrylate, ethylene glycol-1,4
-Diglycidyl ethers and commercially available UV curable resin monomers. In addition, cationic, anionic and nonionic surfactants are also used.

The mixing ratio of the compound represented by the general formula (1), (2) or (3) in the composition is preferably the general formula (1) or (2). ) Or the content of the compound represented by the general formula (3) is from 50% to less than 100% by weight, and more preferably from 60% to less than 100%.

Hereinafter, the operation of the optically anisotropic material of the present invention, that is, the phase difference film for a liquid crystal display device will be described with reference to the drawings, taking a TN type liquid crystal display device as an example. 1 and 2 show the polarization state of light propagating through the liquid crystal cell when a sufficient voltage equal to or higher than the threshold voltage is applied to the liquid crystal cell. Since the transmittance characteristic of light when a voltage is applied particularly greatly contributes to the viewing angle characteristics of the contrast, the description will be made by taking a voltage application as an example. FIG. 1 is a diagram illustrating a polarization state when light is vertically incident on a liquid crystal cell. Natural light L0 is polarization axis PA
When the light is perpendicularly incident on the polarizing plate A having the following formula, the light transmitted through the polarizing plate PA becomes linearly polarized light L1.

When the arrangement state of the liquid crystal molecules when a sufficient voltage is applied to the TN type liquid crystal cell is schematically represented by one liquid crystal molecule, LC in the schematic diagram is obtained. When the molecular long axis of the liquid crystal molecules LC in the liquid crystal cell LCS is parallel to the light path, there is no difference in the refractive index on the incident surface (in a plane perpendicular to the light path), so that the light propagates through the liquid crystal cell. There is no phase difference between the ordinary light and the extraordinary light, and the linearly polarized light that has passed through the LC cell propagates as a linearly polarized light even though it passes through the liquid crystal cell. When the polarization axis PB of the polarizing plate B is set perpendicular to the polarization axis PA of the polarizing plate A, the light passes through the liquid crystal cell and the other linearly polarized light L2 cannot pass through the polarizing plate B, resulting in a dark state.

FIG. 2 is a diagram showing the polarization state of light when the light is obliquely incident on the liquid crystal cell. Natural light L of incident light
When 0 is obliquely incident, the polarized light L1 transmitted through the polarizing plate A
Becomes almost linearly polarized light (in practice, it becomes elliptically polarized light due to the characteristics of the polarizing plate). In this case, the refractive index anisotropy of the liquid crystal causes a difference in the refractive index on the incident surface of the liquid crystal cell, and the light L2 transmitted through the liquid crystal cell is elliptically polarized and is not completely blocked by the polarizing plate B. As described above, in oblique incidence, light is not sufficiently blocked in a dark state, which causes a significant decrease in contrast, which is not preferable.

The present invention aims to prevent such a decrease in contrast at oblique incidence and improve the viewing angle characteristics. FIG. 3 shows an example of the configuration according to the present invention. An optically anisotropic material RF having an optical axis inclined from the normal direction of the liquid crystal cell is disposed between the polarizing plate B and the liquid crystal cell. The optically anisotropic material RF is a birefringent material that is polarized more as the angle of incidence of light with respect to the optical axis increases. As in the case of FIG. 2, the elliptically polarized light L2 transmitted obliquely into the liquid crystal display element having such a configuration as in the case of FIG. A good liquid crystal display element which is modulated into the original linearly polarized light and has the same transmittance even at various oblique incident angles and has no viewing angle dependence can be realized.

It is presumed as follows that the viewing angle of the liquid crystal display device can be greatly improved by the present invention. Many TN-LCDs employ a normally white mode. In this mode, as the viewing angle is increased, the transmittance of light from the black display section is significantly increased, resulting in a sharp decrease in contrast. The black display is the state when voltage is applied,
At this time, the TN type liquid crystal cell can be regarded as a positive uniaxial optically anisotropic body whose optical axis is slightly inclined from the normal direction to the surface of the cell. In the case of the intermediate gradation, it is considered that the optical axis is further inclined from the normal direction of the LC cell.

When the optical axis of the liquid crystal cell is inclined from the direction normal to the surface of the liquid crystal cell, it is expected that an optically anisotropic body whose optical axis is in the direction of the normal will have insufficient compensation. If the liquid crystal cell can be regarded as a positive uniaxial optically anisotropic body, a negative uniaxial optically anisotropic body is preferable in order to compensate for it. For such a reason, it is presumed that the viewing angle characteristics have been greatly improved by the negative uniaxial optical anisotropic material whose optical axis is inclined from the normal direction in the present invention.

In the present invention, the term “negative uniaxiality” refers to a relation of nα <nβ = nγ, where the refractive indices in the three axial directions of a sheet having optical anisotropy are nα, nβ, and nγ in ascending order. Have Therefore, it has the characteristic that the refractive index in the optical axis direction is the smallest. However, the values of nβ and nγ do not need to be exactly equal, but it is sufficient if they are approximately equal. Specifically, nβ-nγ / nβ-nα
If <0.2, there is no practical problem. TFT, T
As a condition for greatly improving the viewing angle characteristics of the N-type liquid crystal cell, the optical axis is preferably inclined at 5 to 50 degrees from the normal direction of the sheet surface, more preferably 10 to 40 degrees, and more preferably 10 degrees. ~ 30 degrees is most preferred. Furthermore, when the thickness of the sheet is D, 100 <(nβ−nα) × D <400
It is desirable to satisfy the condition of nm.

The optically anisotropic material comprising the discotic liquid crystal of the present invention may be composed of only the discotic liquid crystal, but generally, the desired optically anisotropic material is formed on the support. It is provided with at least one liquid crystal layer exhibiting properties, and a protective film or a support may be present above and below the liquid crystal layer or between the liquid crystal layers depending on the application.

The discotic liquid crystal constituting the optically anisotropic material of the present invention may be used alone or as a mixture.
In particular, the adjustment of the phase transition temperature, the control of the optical structure of the liquid crystal phase, the improvement of the film forming property, and the like are often performed effectively by appropriately mixing the liquid crystal.

It is desirable that the support material be close to optically isotropic in addition to having good light transmittance. Therefore,
A support made of a material having a small intrinsic birefringence value sold under the trade name of glass, Zeonex (Zeon Corporation of Japan), ARTON (Japan Synthetic Rubber), Fujitac (Fuji Film) or the like is preferable. However, even for materials with large intrinsic birefringence such as polycarbonate, polyacrylate, polysulfone, and polyethersulfone, it is possible to form an optically isotropic support by controlling the molecular orientation during film formation. Which are also preferably used.

Examples of the material for the protective film include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleimide anhydride copolymer, polyvinyl alcohol, N-methylolacrylamide, styrene
Vinyl toluene copolymer, chlorosulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, polyethylene, polypropylene, polycarbonate, etc. And organic substances such as a silane coupling agent. In addition, a Langmuir-Blodgett method (LB) such as ω-tricosanoic acid, dioctadecyldimethylammonium chloride and methyl stearate is used.
) Can also be used.

Further, it is a well-known fact in the case of a rod-shaped liquid crystal that a protective film provided in advance on a support often has a large effect on the molecular orientation at the time of forming a liquid crystal layer. Is almost always used. This is one of the techniques preferably used in the present invention, and a SiO oblique deposition film is a typical metal oblique deposition film, and a rubbed polyimide film is a typical organic alignment film. In addition, a rubbed modified poval, a rubbed glass substrate treated with a silylating agent, a rubbed gelatin film, a rubbed glass substrate, or the like is used.

Other than the above methods for obliquely aligning the discotic liquid crystal coated on the substrate, there are magnetic field alignment and electric field alignment. In this method, after applying the discotic liquid crystal to the substrate, a zone for applying a magnetic field or an electric field at a desired angle is required, but the zone itself needs to be adjusted to a temperature at which a discotic nematic phase is formed. is there.

The liquid crystal layer constituting the optically anisotropic material of the present invention can be formed as a thin film on a support by a coating method such as vapor deposition, spin coating, dip coating or extrusion coating. In particular, in the liquid crystal of the present invention, the tendency that the optical axis is aligned in the direction of application is often observed at the stage of application.

Accordingly, the liquid crystal thin film is formed on a suitable support in a state where at least one interface is in contact with the gas phase, that is, by a general coating method. An optically anisotropic material having desired optical properties can be obtained by performing heat treatment for a certain period of time while forming a tick nematic phase or a uniaxial columnar phase, and then cooling.

[0063]

EXAMPLES Examples of the synthesis of the liquid crystal compound used in the present invention, examples of preparing an optically anisotropic material using the liquid crystal compound and a composition containing the same, and evaluation examples of the performance thereof will be described below.

The liquid crystal compound of the present invention was generally synthesized by the following route. That is, the synthesis of hexahydroxytriphenylene using 1,2-dimethoxybenzene as a starting material, the synthesis of acid chlorides or mixed acid anhydrides of side chain substituents, and their condensation. In this example, hexahydroxytriphenylene and Invention TP-5, TP-29, TP
-55 and TP-85 are exemplified below.

[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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Example 1 (Synthesis of Liquid Crystal Compound) Synthesis of TP-A2,3,6,7,10,11-hexamethoxytrife
Synthesis of Nylene (TP-A) In a 2 L three-necked flask cooled with ice, ferric sulfate hexahydrate was added.
455g and warm water 193mL, put the mechanical stirrer
After vigorously stirring the mixture to dissolve it completely,
58.7 g of toxicbenzene were added. Then, under water cooling,
882 mL of concentrated sulfuric acid was gradually added. 24 hours later, ice water
Slowly pour into 9 L and after 5 hours, pour the reaction mixture
The mixture was filtered through a filter, and 48.1 g of crude crystals of TP-A (83
%). Synthesis of TP-B2,3,6,7,10,11-hexahydroxytrif
Synthesis of Enylene (TP-B) 48.1 g of TP-A in 850 mL of dichloromethane
And 150 g of boron tribromide was gradually added.
Two hours later, the mixture was poured into 7 L of ice water and filtered through Celite.
Take out the target substance containing celite and redissolve it in methanol
After filtration, the filtrate was concentrated under reduced pressure. Got
The residue was filtered under reduced pressure, and acetonitrile and dichloromethane were added.
Washing with a mixed solvent gave 32.7 g (86%) of the desired product.
Was. Synthesis of TP-54- (7-octenyloxy) -benzoic acid (TP-5
Synthesis of C) In a 500 mL three-necked flask, p-hydroxybenzoic acid was added.
33.2 g, 8-bromo-1-octene 57.3 g, charcoal
Potassium salt 41.5 g and N, N-dimethylacetamide
200 mL was added and stirred at 120 ° C. for 5 hours. cooling
Thereafter, the reaction mixture was poured into 200 mL of water, and 500 mL of vinegar was added.
The mixture was extracted with ethyl acid and washed twice with 100 mL of water. anhydrous
After drying over magnesium sulfate, filtration was performed. Decompress the solvent
After concentration, dissolve in methanol (100 mL) and add potassium hydroxide.
20 mL of methanol solution of 16.8 g
And heated to reflux for 2 hours. After cooling, the resulting crystals were filtered under reduced pressure.
And washed with water. After drying, 63.3 g of TP-5C
(85%).2,3,6,7,10,11-hexa (4- (7-octane
(Tenyloxy) benzoyloxy) triphenylene (T
Synthesis of P-5) 4.5 g of TP-5C and 5 g in a 100 mL three-necked flask
mL of thionyl chloride was added, and the mixture was heated under reflux for 2 hours. reaction
After completion, excess thionyl chloride was distilled off under reduced pressure. this
0.7 g TP-B and 20 mL pyridine
Then, the mixture was stirred at room temperature for 4 hours. Remove excess pyridine under reduced pressure
After distillation, purified using silica gel chromatography
Thus, 2.73 g (75%) of TP-5 was obtained. TP-5 identification data IR (cm^{ー 1}): 3080,2940,2860,1740,1605,1580,151
0,1470 1420,1315,1250,1170,1120,1070,1010,900,840,760,695 Phase transition temperature measurement by DSC and polarizing microscope observation Crystal phase-112 ° C-N_DLiquid crystal phase-180 ° C-etc.
Isotropic liquid

Synthesis of TP-29 4- (5-vinyloxypentyloxy) benzoic acid (T
Synthesis of P-29C) A 500 mL three-necked flask was charged with 33.2 g of ethyl P-hydroxybenzoate, 58.0 g of 5-bromopentyl vinyl ether, 41.5 g of potassium carbonate, and 200 mL of N, N-dimethylacetamide. Stirred for 5 hours. After cooling, the reaction mixture was poured into 200 mL of water, extracted with 500 mL of ethyl acetate, and washed twice with 100 mL of water. After drying over anhydrous magnesium sulfate, filtration was performed. After concentrating the solvent under reduced pressure, it was dissolved in 100 mL of methanol, and a methanol solution of 16.8 g of potassium hydroxide in 20 m
L was gradually added dropwise, and the mixture was heated under reflux for 2 hours. After cooling, the resulting crystals were separated by filtration, and the crystals were dissolved in 1 L of water. Concentrated hydrochloric acid 25.
7 mL was added, and the precipitated crystals were filtered under reduced pressure and washed with water. After drying, 4- (5-vinyloxypentyloxy)
64.3 g (90%) of benzoic acid were obtained (TP-29C).

2,3,6,7,10,11-hexa (4
-(5-vinyloxypentyloxy) benzoyloxy
B) Synthesis of triphenylene (TP-29) In a 300 mL three-necked flask, 5.72 g of TP-29 was added.
C, 6.7 mL of triethylamine and 60 mL of 1,2 dimethoxyethane were added, and 2.75 g of methanesulfonic acid chloride was slowly added dropwise at 0 ° C., followed by stirring for 2 hours. Return to room temperature and add 4-dimethylaminopyridine 0.3
g and TP-B (0.65 g) were added and stirred for 6 hours. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure and purified by silica gel column chromatography to obtain TP-29.
8 g (82%) were obtained. Identification data of TP-29 IR (cm ^-1 ): 2960,2955,2880,1765,1690,1625,160
5,1520,1495,1480,1435 1420,1375,1360,1290,1260,1220,1195,1140,1110,1080,
1050,1030,880,810,780,740

Synthesis of TP-55 4- (6-acryloyloxyhexyloxy) benzoic acid
Synthesis of acid (TP-55C) In a 500 mL three-necked flask, 33.2 g of ethyl P-hydroxybenzoate and 54.3 of 6-bromohexanol.
g, 41.5 g of potassium carbonate and 200 mL of N, N-dimethylacetamide were added and stirred at 120 ° C. for 5 hours. After cooling, the reaction mixture was poured into 200 mL of water and 500
Extracted with mL of ethyl acetate and washed twice with 100 mL of water. After drying over anhydrous magnesium sulfate, filtration was performed. After the solvent was concentrated under reduced pressure, it was dissolved in 100 mL of methanol, and 20 mL of a methanol solution of 16.8 g of potassium hydroxide was gradually added dropwise, followed by heating under reflux for 2 hours. After cooling, the resulting crystals were separated by filtration, and the crystals were dissolved in 1 L of water. 25.7 mL of concentrated hydrochloric acid was added, and the precipitated crystals were filtered under reduced pressure and washed with water. After drying, 61.5 g (86%) of 4- (6-hydroxyhexyloxy) benzoic acid was obtained. 9.53 g of 4- (6-hydroxyhexyloxy) benzoic acid, 5.33 g of N, N-dimethylaniline, and 100 mL of dioxane were put into a 300 mL three-necked flask, and 3.98 g of acrylic acid chloride was slowly added dropwise at 60 ° C. Stirred for 6 hours. After cooling, the mixture was poured into ice water (200 mL), the precipitated crystals were filtered by suction, washed with hexane, and dried, and then 9.4 g of TP-55C was dried.
(80%).

2,3,6,7,10,11-hexa (4
-(6-acryloyloxyhexyloxy) benzoy
Synthesis of (Roxy) triphenylene (TP-55) In a 300 mL three-necked flask, 5.67 g of TP-55 was added.
C, 6.7 mL of triethylamine and 60 mL of 1,2-dimethoxyethane were added, and 2.75 g of methanesulfonic acid chloride was slowly added dropwise at 0 ° C., followed by stirring for 2 hours. Return to room temperature and add 4-dimethylaminopyridine 0.3
g and 0.65 g of TP-B were added and stirred for 6 hours. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure and purified using silica gel column chromatography to obtain TP-55 in 3.2.
g (80%).

Identification data of TP-55 IR (cm ^-1 ): 2950, 2870, 1740, 1730, 1610, 1605, 158
5,1520,1480,1430 1415,1375,1320,1300,1260,1200,1180,1130,1080,1010,
990,905,850 820,760,700 DSC and phase transition temperatures measured crystal phase with a polarization microscope - 132 ℃ - D _r liquid crystal phase - 143 ℃ - N _d
Liquid crystal phase-227 ° C-Isotropic liquid

Synthesis of TP-85 TP-85 was synthesized using TP-5 as a starting material. 2,3,6,7,10,11-hexa (4- (7,8-
Epoxy octyloxy) benzoyloxy) triphe
Synthesis of Nylene (TP-85) In a 100 mL three-necked flask, 3.67 g of TP-5 and m
-6.33 g of chloroperbenzoic acid and 30 mL of toluene were added, and the mixture was stirred at 60 ° C for 2 hours. After cooling, the precipitated m-
The chloroperbenzoic acid was removed and purified using silica gel chromatography to obtain 3.17 g (82%) of TP-85.
%)Obtained. Identification data of TP-85 IR (cm ^-1 ): 3050,2940,2850,1740,1605,1580,151
0,1470,1420,1320 1250,1170,1120,1070,1010,900,840,760,695 DSC and phase transition temperatures measured crystal phase with a polarization microscope - 114 ℃ - N _d the liquid crystal phase - 220 ° C. - isotropic liquid

Example 2 (Composition Containing Liquid Crystal Compound) The change in the phase transition behavior depending on the content of the composition containing the liquid crystal compound of the present invention will be described below. Polyamic acid (SE-7210 manufactured by Nissan Chemical Industries, Ltd.) was applied as an alignment film on a glass substrate (size 25 mm × 25 mm), and baked at 180 ° C. to form a polyimide film. This was rubbed with a rubbing machine to give an orientation ability. Next, the liquid crystal compound of the present invention and two kinds of other organic compounds were mixed at a ratio shown in Table 1, and this was made into a 10 wt% solution of methyl ethyl ketone.
m and dried. Mettler FP82
While heating on an HT hot stage, its phase change behavior was observed from a change in optical morphology under a polarizing microscope. Table 1 shows the results.

[0078]

[Table 1]

The structure of the organic compound to be mixed is shown below.

[0080]

Embedded image

The orientation temperature shown in the table means that the composition on the orientation film is almost non-oriented immediately after the application, but is heated on a hot stage under crossed Nicols of a polarizing microscope. This is the temperature at which the dark visual field changes uniformly and brightly and starts to show monoaxial uniaxial orientation over a wide range. As shown in Table 1, it can be seen that the alignment temperature can be variously changed while maintaining the discotic liquid crystal phase by the combination of the organic compounds to be mixed. Example 3 (Optical Anisotropic Material Based on Composition Containing Liquid Crystalline Compound) Hereinafter, a method for preparing an optically anisotropic material based on the composition including the liquid crystal compound of the present invention and its physical properties will be described. 100 μm thick film of polyether sulfone (FS-1300 manufactured by Sumitomo Bakelite Co., Ltd., size 100 mm × 100
mm) as a substrate, a 0.1 μm gelatin undercoat layer was provided, and polyamic acid (SE-7210 manufactured by Nissan Chemical Industries, Ltd.) was applied thereon as an alignment film, and baked at 180 ° C. to form a polyimide film. This polyimide film was rubbed with a rubbing machine to give an orientation ability. Table 1 of Example 2
Liquid crystal compositions LC-1, LC-6, LC-10
Were dissolved in methyl ethyl ketone, and a 10 wt% solution was applied at 1000 rpm by a spin coater to form a non-oriented layer of discotic liquid crystal. These were designated as film-like materials A, B, and C. After heating and orienting them at a predetermined temperature, they were cooled rapidly, and their optical axis inclination angles β and Δn · d were measured by ellipsometry. For the measurement, an ellipsometer (AEP-100, manufactured by Shimadzu Corporation) was used in the transmission mode to determine the angle dependence of the retardation, and from these values, the optimum triaxial refractive index and the direction of the optical axis were determined by calculation. According to observation with a polarizing microscope, the film-like substance ATP-38 was about 130 to 18
Form a discotic nematic phase at 3 ° C. Then, the film-shaped material A is brought into contact with the metal roller heated to the surface temperature of 190 ° C. from the support side for 10 seconds, and immediately thereafter, is brought into contact with the metal roller heated to the surface temperature of 170 ° C. from the support side for 30 seconds. Further, the optically anisotropic material of the present invention was obtained by continuously contacting a metal roller adjusted to a surface temperature of 20 ° C. for 10 seconds. Observation of this sheet under a polarizing microscope revealed that the sheet had a monodomain uniaxial orientation, that is, a discotic nematic phase. Further, according to the ellipsometry measurement, the optical axis inclination angle β was 35 ° and Δn · d = 125
nm. According to observation with a polarizing microscope, the film-like substance B TP-85 was about 171 to 21
Form a discotic nematic phase at 1 ° C. Then, the film-shaped material A is brought into contact with the metal roller heated to the surface temperature of 180 ° C. from the support side for 50 seconds, and immediately thereafter, is brought into contact with the metal roller adjusted to the surface temperature of 20 ° C. for 10 seconds, whereby the optical difference of the present invention is obtained. An isotropic material was obtained. Observation of this sheet under a polarizing microscope revealed that the sheet had a monodomain uniaxial orientation, that is, a discotic nematic phase. Further, by ellipsometry measurement, the optical axis tilt angle β was 70 ° and Δn
D was 155 nm LC-10 described in Film C in Table 1 was observed by a polarizing microscope,
Form a discotic nematic phase at about 109-158 ° C. Therefore, the film-shaped material A is brought into contact with the metal roller heated to the surface temperature of 115 ° C. from the support side for 30 seconds, and immediately thereafter, is brought into contact with the metal roller adjusted to the surface temperature of 20 ° C. for 10 seconds, whereby the optical difference of the present invention is obtained. An isotropic material was obtained. Observation of this sheet under a polarizing microscope revealed that the sheet had a monodomain uniaxial orientation, that is, a discotic nematic phase. Further, by ellipsometry, the optical axis inclination angle β was 44 ° and Δn · d = 120 nm. Example 4 (Performance evaluation as a retardation film for the purpose of expanding the viewing angle of a TN type liquid crystal display element) TAC 127 μm thick film (Fuji Tack, size 1)
(00 mm × 100 mm) was used as a substrate, a 0.1 μm gelatin undercoat layer was provided thereon, and a modified Poval was applied thereon as an alignment film, and the film was rubbed with a rubbing machine to give alignment ability. Liquid crystal composition LC described in Table 1 of Example 2
-10 was dissolved in methyl ethyl ketone, and a 10 wt% liquid was applied by a spin coater at 1000 rpm to form a non-oriented layer of discotic liquid crystal. Then, the same method as that for the film C is applied, that is, the film is brought into contact with the metal roller heated to a surface temperature of 115 ° C. from the support side for 30 seconds, and immediately thereafter, the metal roller is brought into contact with the metal roller adjusted to a surface temperature of 20 ° C. for 10 seconds. Thereby, the optically anisotropic material of the present invention was obtained. Observation of this sheet under a polarizing microscope revealed that the sheet had a monodomain uniaxial orientation, that is, a discotic nematic phase. Next, the above-mentioned film-like material is mounted on a TN type liquid crystal cell having a product of the difference between the refractive indexes of the extraordinary light and ordinary light of the liquid crystal and the gap size of the liquid crystal cell of 480 nm and a twist angle of 90 degrees. On the other hand, the angle dependence of the contrast in a 30 Hz rectangular wave of 0-5 V was measured by Otsuka Electronics LCD-50.
00. The position of the contrast 10 was defined as the viewing angle, and the up, down, left, and right viewing angles were determined. Also, the contrast ratio when viewed from the front was measured. Here, the measured values of only the TN liquid crystal without the film attached are also shown. The results are shown in Table 2 below. In FIG. 4, arrows indicate the rubbing direction in the retardation film and the rubbing direction in the liquid crystal cell.

[0082]

[Table 2]

As is apparent from the above table, in the LCD provided with the optical compensation sheet of the present invention, a remarkable improvement in the viewing angle characteristics has been achieved.

[0084]

The liquid crystal compound or its composition of the present invention can easily form a monodomain uniaxial thin film on a general liquid crystal alignment film by wet coating and heating at a relatively low temperature. This thin film is optically anisotropic, and when used together with a liquid crystal display device, it has become possible to improve the viewing angle as a retardation film.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating a polarization state of light when the light is vertically incident on a liquid crystal cell.

FIG. 2 is a diagram showing a polarization state of light when light is obliquely incident on a liquid crystal cell.

FIG. 3 is a diagram showing an example of using an optically anisotropic material for a retardation film for a liquid crystal display element.

FIG. 4 is a diagram showing a relationship between a polarization axis of a polarizing plate, a rubbing direction of a liquid crystal cell, and a rubbing direction of an optically anisotropic sheet alignment film when viewing angle characteristics are measured in Examples.

[Explanation of symbols]

TNC: TN type liquid crystal cell A, B: polarizing plate PA, PB: polarization axis L0: natural light L1, L5: linearly polarized light L2: modulated light after passing through the liquid crystal cell L3, L4: elliptically polarized light LC: TN type liquid crystal cell State of liquid crystal molecules when voltage is sufficiently applied to the electrodes RF1, RF2: retardation film for liquid crystal display element BL: backlight

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication G02B 5/30 G02B 5/30 (72) Inventor Masaki Okazaki 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji Makoto Fujisha (56) References JP-A-56-90878 (JP, A) JP-A-57-76531 (JP, A) JP-A-3-85521 (JP, A)

Claims (2)

(57) [Claims] 1. A compound represented by the following general formula (1), general formula (2) or general formula (3). General formula (1) In the formula, R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group, R ¹³ represents a substituent P1 or an alkoxy group having a terminal substituted with the substituent P1, and R ¹⁴ and R ¹⁵ of the substituent P1 Each independently represents a hydrogen atom or an unsubstituted alkyl group; R ^{16 of the} substituent P1 represents a hydrogen atom, a 2-chloroethyl group, a methoxyethoxyethyl group or an unsubstituted alkyl group; and n is 0 or 1 Represents General formula (2) In the formula, R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group, R ²³ represents an alkoxy group having a terminal substituted with the substituent P2, and R ²⁴ and R ^{24 of the} substituent P2
²⁵ each independently represents a hydrogen atom or an unsubstituted alkyl group, and R ^{26 of the} substituent P2 represents a hydrogen atom, a 2-chloroethyl group, a methoxyethoxyethyl group or an unsubstituted alkyl group. General formula (3) In the formula, R ³¹ and R ³² each independently represent a hydrogen atom or a methyl group, R ³³ represents an alkoxy group having a terminal substituted with the substituent P3, and R ³⁴ and R 3 of the substituent P3
³⁵ each independently represents a hydrogen atom or an unsubstituted alkyl group, and R ^{36 of the} substituent P3 represents a hydrogen atom, a 2-chloroethyl group, a methoxyethoxyethyl group or an unsubstituted alkyl group. 2. An optically anisotropic material comprising at least one of the compounds represented by the general formulas (1), (2) and (3) according to claim 1.