JP5093820B2 - Liquid crystal display device and liquid crystal composition - Google Patents

Description

  The present invention relates to a liquid crystal display device and a liquid crystal composition.

Since liquid crystal display devices have characteristics such as low drive voltage, low power consumption, and light weight, they are used not only for clock display panels and mobile phone displays, but also for computers and television displays. .
In current mainstream liquid crystal display devices, driving methods such as a TN (twisted nematic) mode, a VA (vertical alignment) mode, and an IPS (in-plane switching) mode are adopted. Depending on the type of these driving methods, a liquid crystal material is used. The physical properties required for the liquid crystal (for example, the temperature range and viscosity of the liquid crystal phase) differ. Therefore, in order to satisfy desired physical properties, a mixed liquid crystal containing two or more kinds of liquid crystal components is generally used as a liquid crystal material instead of a single component liquid crystal material. It is also known that various physical properties can be improved by incorporating fine particles in a liquid crystal material (see, for example, Patent Document 1).

By the way, in any of the above-described liquid crystal display devices, means for controlling the alignment of liquid crystal molecules is required, and means for forming an alignment film made of polyimide or the like is generally used. For example, in a TN or IPS mode liquid crystal display device, alignment of liquid crystal molecules is controlled in a direction parallel to the substrate by an alignment film subjected to rubbing treatment. On the other hand, in a VA mode liquid crystal display device that does not require rubbing, the alignment of liquid crystal molecules is controlled in a direction perpendicular to the substrate by an alignment film.
Here, sectional views of a conventional general VA mode liquid crystal display device are shown in FIGS. FIG. 3 shows a case where the planar electrode 6 is used, and FIG. 4 shows a case where the comb electrode 7 is used. As can be seen from these drawings, the conventional general VA mode liquid crystal display device includes liquid crystal molecules 3 sandwiched between substrates 1a and 1b such as a pair of opposed glass substrates and substrates 1a and 1b. An alignment film 8 that controls the alignment of liquid crystal molecules is formed on the surfaces of the substrates 1a and 1b that are in direct contact with the liquid crystal layer 2. The substrate 1a is provided with a color filter layer 4 for realizing a desired color and an overcoat layer 5 for protecting the color filter layer 4, and the liquid crystal layer 2 is sealed with a sealing material 9. ing.

In the VA mode liquid crystal display device using the planar electrode 6, (A) When the electric field is OFF, the liquid crystal molecules (n-type liquid crystal molecules) 3 in the liquid crystal layer 2 are perpendicular to the substrates 1a and 1b by the alignment film 8. When aligned and (B) when the electric field is ON, the liquid crystal molecules (n-type liquid crystal molecules) 3 are aligned perpendicular to the lines of electric force (arrows in the figure), that is, aligned parallel to the substrates 1a and 1b.
In the VA mode liquid crystal display device using the comb-shaped electrode 7, (A) When the electric field is OFF, the liquid crystal molecules (p-type liquid crystal molecules) 3 in the liquid crystal layer 2 are perpendicular to the substrates 1 a and 1 b by the alignment film 8. When aligned and (B) when the electric field is ON, the liquid crystal molecules (p-type liquid crystal molecules) 3 are aligned parallel to the lines of electric force (arrows in the figure), that is, aligned parallel to the substrates 1a and 1b.

However, in the conventional general liquid crystal display device represented by the VA mode liquid crystal display device as shown in FIGS. 3 and 4, the alignment film 8 is formed to control the alignment of the liquid crystal molecules 3. There are various problems resulting from the formation of 8. For example, when the alignment film 8 is formed, the manufacturing yield on printing decreases due to dust or pinholes, and the investment cost of the formation process of the alignment film 8 increases as the size of the glass substrate in the manufacturing process increases. There's a problem. Therefore, development of other liquid crystal alignment control means is strongly desired.
As another liquid crystal alignment control means, a method of dispersing nanoparticles in a liquid crystal material has been proposed (see Non-Patent Document 1).

Japanese Patent Laid-Open No. 2005-247921

Shug-June Hwang, 4 others, “Characteristics of nanoparticle-doped homeotropic liquid crystal devices”, Journal of Physics D: Journal of Physics D: Applied Physics), 2009, Vol. 42, No. 2, 052102

However, the method of Non-Patent Document 1 has a problem that the contrast of the liquid crystal display device is lowered because the nanoparticles dispersed in the liquid crystal material aggregate and light leakage occurs from the aggregated portion.
SUMMARY An advantage of some aspects of the invention is that it provides a liquid crystal display device capable of controlling liquid crystal alignment without degrading characteristics such as contrast.
Another object of the present invention is to provide a liquid crystal composition capable of providing a liquid crystal display device having the above characteristics.

As a result of diligent research to solve the above-mentioned problems, the present inventors have found that a dendrimer having a specific structure compatible with a liquid crystal component is added to a liquid crystal layer based on the finding that the dendrimer is useful for controlling liquid crystal alignment. It was found that the liquid crystal alignment can be controlled while preventing precipitation and aggregation of the dendrimer, and the present invention has been completed.
That is, the present invention is a liquid crystal display device including a liquid crystal layer containing a dendrimer having a specific structure compatible with a liquid crystal component.
The present invention also provides a liquid crystal composition comprising a dendrimer having a specific structure and two or more liquid crystal components.

According to the present invention, it is possible to provide a liquid crystal display device capable of controlling liquid crystal alignment without degrading characteristics such as contrast.
Moreover, according to the present invention, a liquid crystal composition capable of providing a liquid crystal display device having the above-described characteristics can be provided.

It is sectional drawing of the VA mode liquid crystal display device of this invention using the planar electrode in the case of (A) electric field OFF and (B) electric field ON. It is sectional drawing of the VA mode liquid crystal display device of this invention using the comb-shaped electrode in the case of (A) electric field OFF and (B) electric field ON. It is sectional drawing of the conventional VA mode liquid crystal display device using the planar electrode in the case of (A) electric field OFF and (B) electric field ON. It is sectional drawing of the conventional VA mode liquid crystal display device using the comb-shaped electrode in the case of (A) electric field OFF and (B) electric field ON. It is a figure showing the manufacturing process flow of the liquid crystal display device using the liquid-crystal composition of this invention, and the manufacturing process flow of the conventional liquid crystal display device.

Embodiment 1 FIG.
The liquid crystal display device of the present invention includes a liquid crystal layer containing a dendrimer compatible with a liquid crystal component. Here, the dendrimer is a dendritic polymer having a structure regularly branched from the center, and means a polymer composed of a central part called a core and a side chain part called a dendron.
Hereinafter, the liquid crystal display device of the present invention will be described in detail with reference to the drawings. The liquid crystal display device of the present invention can adopt a known liquid crystal display device configuration other than the configuration of the liquid crystal layer, and is not limited to the following configuration. Further, if this configuration of the liquid crystal layer is employed, the alignment film may not be formed, but the liquid crystal alignment control may be performed in combination with the alignment film. Even in this case, it is possible to perform liquid crystal alignment control without degrading characteristics such as contrast. Here, the alignment film is a film for controlling the alignment state of the liquid crystal, and generally means a film made of a resin such as polyimide.

FIG. 1 is a cross-sectional view of a VA mode liquid crystal display device of the present invention using a planar electrode. 1A shows a case where the electric field is OFF, and FIG. 1B shows a case where the electric field is ON. The liquid crystal display device includes a pair of opposed substrates 1a and 1b such as glass substrates, and a liquid crystal layer 2 formed between the substrates 1a and 1b. A color filter layer 4 for realizing a desired color, an overcoat layer 5 for protecting the color filter layer 4, and a planar electrode 6 are sequentially formed on the substrate 1a, and a planar type is formed on the substrate 1b. An electrode 6 is formed. The liquid crystal layer 2 is in direct contact with the planar electrode 6 formed on the substrates 1a and 1b and is sealed with a sealing material 9.
In this VA mode liquid crystal display device, (A) when the electric field is OFF, the liquid crystal molecules (negative liquid crystal molecules) 3 in the liquid crystal layer 2 are aligned perpendicular to the substrates 1a and 1b, and (B) when the electric field is ON. The liquid crystal molecules (negative type liquid crystal molecules) 3 are aligned perpendicular to the lines of electric force (arrows in the figure), that is, aligned parallel to the substrates 1a and 1b.

FIG. 2 is a cross-sectional view of the VA mode liquid crystal display device of the present invention using comb-shaped electrodes. 2A shows the case where the electric field is OFF, and FIG. 2B shows the case where the electric field is ON. The liquid crystal display device includes a pair of opposed substrates 1a and 1b such as glass substrates, and a liquid crystal layer 2 formed between the substrates 1a and 1b. A color filter layer 4 for realizing a desired color and an overcoat layer 5 for protecting the color filter layer 4 are sequentially formed on the substrate 1a, and a comb-shaped electrode 7 is formed on the substrate 1b. Has been. The liquid crystal layer 2 is in direct contact with the comb-shaped electrode 7 formed on the substrate 1 b and is sealed with a sealing material 9. Note that an FFS (fringe field switching) mode (see, for example, Japanese Patent Application Laid-Open No. 2008-51846) can be used for the comb electrode structure.
In this VA mode liquid crystal display device, (A) when the electric field is OFF, the liquid crystal molecules (positive liquid crystal molecules) 3 in the liquid crystal layer 2 are aligned perpendicular to the substrates 1a and 1b, and (B) when the electric field is ON. The liquid crystal molecules (positive liquid crystal molecules) 3 are aligned parallel to the lines of electric force (arrows in the figure), that is, aligned parallel to the substrates 1a and 1b.

In these liquid crystal display devices, the dendrimer 10 is blended in the liquid crystal layer 2 in order to control the alignment of the liquid crystal molecules 3 as described above.
The dendrimer 10 used in the liquid crystal layer 2, which is compatible there shall liquid crystal component. When the dendrimer 10 that is incompatible with the liquid crystal component is blended in the liquid crystal layer 2, it is precipitated without dissolving in the liquid crystal layer 2, and uniform alignment controllability (vertical alignment) cannot be obtained in the liquid crystal display device. This is not preferable because the contrast of the film is lowered.
Here, the dendrimer 10 having compatibility with the liquid crystal component means that when the dendrimer 10 is blended with the liquid crystal component and is raised to a temperature equal to or higher than the phase transition temperature of the liquid crystal component in an oven to form an isotropic phase, It means that it is dissolved (that is, the mixture of the liquid crystal component and the dendrimer is transparent), and no precipitation of the dendrimer is confirmed even after returning to room temperature (for example, 25 ° C.).

The dendrimer 10 with a liquid crystal component compatibility, alkyl groups, those having at least one selected from the group consisting of alkoxy groups and fluorine at its end. This is because the dendrimer 10 is excellent in compatibility with not only a single component cyano liquid crystal but also a mixed liquid crystal containing two or more liquid crystal components. In particular, mixed liquid crystals generally used in practical liquid crystal display devices are designed so that impurities are difficult to dissolve from the viewpoint of ensuring the reliability of the liquid crystal display device, so that additives are difficult to dissolve. However, this dendrimer 10 exhibits good compatibility with mixed liquid crystals.
Dendrimers 10 used in the present invention is the table by the lower Stories formula (I).

  In the above formula (I), R is represented by the formula (II).

  In the above formula (II), A is

(Wherein R ¹ is an alkyl or alkoxy group having 1 to 12 carbon atoms, or fluorine), X is a direct bond, —COO— group or —N═N— group, and B is

And n is an integer of 3-12.
The dendrimer 10 having such a structure can be obtained by reacting a polyfunctional amine compound providing a core portion with an acrylate derivative providing a side chain portion in an organic solvent.
Examples of the polyfunctional amine compound include polypropylene tetramine dendrimer, generation 1.0 and polypropylene octaamine dendrimer, generation 2.0. DAB-Am- manufactured by Aldrich Commercial products such as 4 and DAB-Am-8 can also be used. The polyfunctional amine compound can also be synthesized using ethylenediamine and acrylonitrile as starting materials.
The acrylic ester derivative may be appropriately selected depending on the dendrimer 10 to be synthesized. For example, when the dendrimer 10 represented by the above formula (I) is synthesized, it is represented by the following formula (III). A compound can be used as a raw material.

In the above formula (III), X, A, B and n are as defined above.
The reaction ratio of the polyfunctional amine compound and the acrylate derivative is 1.0 to 3.0 mol, preferably 1.1 to 1.5 mol of the acrylate derivative with respect to 1 mol of the polyfunctional amine compound. Is a mole.

As the organic solvent, conventionally known ones can be used. For example, halogenated hydrocarbon solvents such as 1,2-dichloroethane and chloroform; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; tetrahydrofuran, Examples include cyclic ether solvents such as dioxane; aromatic hydrocarbon solvents such as toluene and xylene; and aprotic polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide. It is done. These organic solvents can be used individually or in mixture of 2 or more types.
Further, the amount of the organic solvent may be appropriately adjusted according to the amount of the polyfunctional amine compound or the acrylate derivative, and is not particularly limited.

The reaction temperature is −50 to 150 ° C., preferably 25 to 80 ° C. When the reaction temperature is lower than −50 ° C., the reaction rate may be significantly reduced. Moreover, when reaction temperature exceeds 150 degreeC, stability of a polyfunctional amine compound or an acrylate derivative may fall.
The reaction time is 2 to 200 hours, preferably 48 to 100 hours. If the reaction time is less than 2 hours, the reaction may not proceed sufficiently. If the reaction time exceeds 200 hours, it takes too much time and is not practical.
After completion of the reaction, the target dendrimer 10 can be obtained by removing the solvent. Moreover, you may refine | purify by adding poor solvents, such as methanol, ethanol, isopropyl alcohol, hexane, toluene, and heating and removing a supernatant liquid.

The dendrimer 10 in the liquid crystal layer 2 is mainly at the interface between the liquid crystal layer 2 and the portion where the liquid crystal layer 2 is in contact (the planar electrode 6 in FIG. 1, the overcoat layer 5, the substrate 1b and the comb electrode 7 in FIG. 2). The liquid crystal molecules 3 in the liquid crystal layer 2 are aligned perpendicularly to the substrate.
Therefore, the content of the dendrimer 10 in the liquid crystal layer 2 may be an amount that allows the dendrimer 10 to exist at the interface between the liquid crystal layer 2 and the portion where the liquid crystal layer 2 is in contact. That is, the content of the dendrimer 10 in the liquid crystal layer 2 depends on the area of the portion in contact with the liquid crystal layer 2 and cannot be uniquely defined, but is generally 0.01 to 50% by mass. When the content of the dendrimer 10 is less than 0.01% by mass, the amount of the dendrimer 10 present at the interface between the liquid crystal layer 2 and the portion where the liquid crystal layer 2 is in contact is too small, and the long-term control of the alignment of the liquid crystal molecules 3 is long. Reliability may be reduced. On the other hand, if the content of the dendrimer 10 exceeds 50% by mass, the amount of the liquid crystal material decreases, and desired performance as a liquid crystal display device such as an increase in response time or an increase in driving voltage may not be obtained. is there.

  The liquid crystal layer 2 including the dendrimer 10 exhibits liquid crystallinity at room temperature from the viewpoint of practicality of the liquid crystal display device, and the phase transition temperature from the liquid crystal phase to the isotropic phase or another liquid crystal phase is 50 ° C. or higher and 120 ° C. or lower. Preferably there is.

The liquid crystal material used for the liquid crystal layer 2 is not particularly limited, but is preferably a mixed liquid crystal containing two or more liquid crystal components. This mixed liquid crystal is prepared by mixing several liquid crystal components to meet the desired physical properties (for example, refractive index anisotropy, dielectric anisotropy, viscosity, phase transition temperature, etc.) according to the intended use. Therefore, although it is difficult to define uniquely, a mixed liquid crystal generally called a fluorine-based mixed liquid crystal or a cyano-based mixed liquid crystal can be used. Among these, it is preferable to use a fluorine-based mixed liquid crystal that is currently generally used in liquid crystal display devices. Here, the fluorinated mixed liquid crystal means a mixed liquid crystal containing one or more kinds of fluorinated liquid crystals, and the cyano mixed liquid crystal means a mixed liquid crystal containing one or more kinds of cyano liquid crystals.
The above-mentioned mixed liquid crystals are generally known and commercially available. For example, fluorine-based mixed liquid crystals are commercially available under the trade names ZLI-4792 (p-type) and MLC-6608 (n-type). Sold by the company. The cyano mixed liquid crystal is sold by Chisso Petrochemical Co., Ltd. under the trade name JC-5066XX (p-type).

  In the VA mode liquid crystal display device of the present invention, the liquid crystal layer 2 is blended with the dendrimer 10 having compatibility with the liquid crystal component, thereby contacting the liquid crystal layer 2 and the liquid crystal layer 2 (in FIG. 1, the planar electrode 6 and FIG. 2). Then, the dendrimer 10 is mainly present at the interface with the overcoat layer 5, the substrate 1b, and the comb-shaped electrode 7), so that the alignment of the liquid crystal molecules 3 can be controlled. That is, since the dendrimer 10 exists at the interface between the liquid crystal layer 2 and the portion in contact with the liquid crystal layer 2 and provides the same function and effect as the alignment film, the conventional VA using the planar electrode 6 as shown in FIG. Unlike the mode liquid crystal display device, the alignment of the liquid crystal molecules 3 can be controlled without providing the alignment film 8. Further, since the dendrimer 10 is compatible with the liquid crystal component, the dendrimer 10 is not precipitated in the liquid crystal layer 2 or aggregated and dispersed, and the contrast of the liquid crystal display device is not lowered. In addition, when the alignment film 8 is not provided, the liquid crystal layer 2 can be brought into direct contact with the planar electrode 6 or the comb electrode 7. The driving voltage can also be reduced. Furthermore, by reducing the space of the alignment film 8, it is not necessary to consider the variation in the position of the end of the alignment film 8 due to printing. In other words, the adhesive force of the sealing material 9 decreases as the sealing material 9 that bonds the substrates 1a and 1b and the alignment film 8 overlap each other. The position can be brought close to the display area, and a narrow frame of the liquid crystal display device can be achieved.

Embodiment 2. FIG.
The liquid crystal composition of the present invention includes a dendrimer having a specific structure and two or more liquid crystal components.
As described above , a dendrimer having a specific structure is excellent in compatibility with not only a single component cyano liquid crystal but also a mixed liquid crystal containing two or more liquid crystal components. And a liquid crystal composition.
Examples of the dendrimer having a specific structure and two or more liquid crystal components are as described above.

The content of the dendrimer in the liquid crystal composition of the present invention may be an amount that allows the dendrimer to exist at the interface between the liquid crystal layer and the portion in contact with the liquid crystal layer, for example, when used in the liquid crystal layer of a liquid crystal display device. . That is, the dendrimer content depends on the area of the portion in contact with the liquid crystal layer and cannot be uniquely defined, but is generally 0.01 to 50% by mass. If the dendrimer content is less than 0.01% by mass, the amount of dendrimer present at the interface between the liquid crystal layer and the portion in contact with the liquid crystal layer is too small, and the long-term reliability for the alignment control of the liquid crystal molecules decreases. Sometimes. On the other hand, when the dendrimer content exceeds 50% by mass, the amount of liquid crystal material decreases, and desired performance as a liquid crystal display device such as an increase in response time or an increase in driving voltage may not be obtained. .
In addition, the liquid crystal composition of the present invention may contain various known additives generally blended in the liquid crystal composition in order to achieve desired physical properties as long as the effects of the present invention are not impaired.

  The liquid crystal composition of the present invention can be produced by a known method using the above components, for example, by mixing each component. The liquid crystal composition of the present invention thus produced exhibits liquid crystallinity at room temperature from the viewpoint of practicality, and the phase transition temperature from the liquid crystal layer to the isotropic phase or another liquid crystal phase is 50 ° C. or higher and 120 ° C. The following is preferable.

  When the liquid crystal composition of the present invention is used as a liquid crystal layer of a liquid crystal display device, a dendrimer is mainly present at the interface between the liquid crystal layer and a portion in contact with the liquid crystal layer, and the same effect as that of the alignment film (that is, liquid crystal molecules Orientation control). Therefore, if the liquid crystal composition of the present invention is used, the alignment film may not be provided. In addition, since the liquid crystal composition of the present invention uses a dendrimer that is highly compatible with two or more liquid crystal components, the liquid crystal composition is used for a liquid crystal display device without causing precipitation or aggregation of the dendrimer in the liquid crystal composition. In this case, the contrast is not lowered.

  FIG. 5 shows a manufacturing process flow of a liquid crystal display device using the liquid crystal composition of the present invention and a manufacturing process flow of a conventional liquid crystal display device. In addition, since this flow is exemplary, a method for manufacturing a liquid crystal cell by a method other than ODF (liquid crystal dropping injection method), for example, a method using a capillary phenomenon (that is, between substrates that have been bonded in advance). It is not meant to exclude the method of injecting the liquid crystal composition.

In the conventional manufacturing process of a liquid crystal display device, in order to form an alignment film for liquid crystal alignment control, generally, (1) application of polyimide (hereinafter referred to as PI) on a substrate, and (2) temporary baking. , (3) main firing, (4) rubbing treatment, and (5) substrate cleaning after the rubbing treatment (steps within a dotted frame in FIG. 5) had to be performed. Depending on the driving method, the (4) rubbing process and (5) the substrate cleaning process after the rubbing process may not be performed.
On the other hand, in the manufacturing process of the liquid crystal display device using the liquid crystal composition of the present invention, since the liquid crystal alignment can be controlled by the dendrimer contained in the liquid crystal composition, it is not necessary to form an alignment film. Further, the rubbing process may not be performed. Therefore, since the steps (1) to (5) required when forming the alignment film or performing the rubbing process are not required, the manufacturing method can be simplified and the capital investment can be greatly reduced. In addition, there is no problem that the manufacturing yield on printing is reduced by pinholes or that the investment cost of the alignment film forming process increases with the increase in the size of the glass substrate in the manufacturing process.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
<Synthesis of Dendrimer A>
A dendrimer in which R in the above formula (I) is represented by the following formula (IV) was synthesized as follows.

Synthesis of 6- [4- (4-hexylphenyldiazedyl) phenoxy] hexanol In a 200 ml three-necked flask, 4- (4-hexylphenyldiazenyl) phenol (5.0 g, 17.7 mmol), 6-bromohexanol ( 4.9 g, 18 mmol), potassium carbonate (2.45 g, 17.7 mmol) and ethanol (20 ml) were added and dissolved, and the mixture was heated to reflux for 48 hours. After completion of heating and refluxing, ethanol was removed under reduced pressure, and the resulting residue was dissolved in diethyl ether, and this solution was washed with water three times. Next, anhydrous sodium sulfate was added to this solution to remove water, and then diethyl ether was distilled off under reduced pressure. The resulting residue was recrystallized from n-hexane, yielding orange needle crystals. Obtained in 3.9 g (58% yield). The needle-like crystals, by ^{IR, 3289cm -1 (OH),} 2919cm -1 (C-H), 1473cm -1 (N = N), characteristic absorption of 1253cm ^-1 (PhO-) was observed.

Synthesis of 6- [4- (4-hexylphenyldiazedyl) phenoxy] hexyl acrylate In a 100 ml three-necked flask, 6- [4- (4-hexylphenyldiazedyl) phenoxy] hexanol (3.5 g, 9. 2 mmol), triethylamine (0.92 g, 9.2 mmol) and THF (30 ml) were dissolved and cooled to 0 ° C. with ice. To this solution was added acryloyl chloride (1.2 g, 14 mmol) using a syringe, and the mixture was stirred at room temperature for 24 hours. The resulting white solid was filtered off and the filtrate was concentrated under reduced pressure, and then the resulting residue was purified by column chromatography (stationary phase: silica gel, mobile phase: chloroform) to obtain a yellow solid in a yield of 3.4 g ( (Yield 85%). The yellow solid by ^{IR, 2935cm -1 (C-H} ), 1716cm -1 (C = O), 1473cm -1 (N = N), characteristic absorption of 1261cm ^-1 (PhO-) was observed. Further, the elemental analysis value of this yellow solid coincided with the value calculated as C ₂₇ H ₃₆ N ₂ O ₃ within a range of 0.5%. (Calculated value to C: 74.28%, H: 8.31%, N: 6.42%, measured value to C: 74.48%, H: 8.61%, N: 6.35%)

Synthesis of Dendrimer A In a 100 ml eggplant flask, DAB-Am-8 (0.39 g, 0.51 mmol), 6- [4- (4-hexylphenyldiazedyl) phenoxy] hexyl acrylate (4.9 g) manufactured by Aldrich 11 mmol) and THF (20 ml) were added and heated at 50 ° C. for 72 hours. Next, after concentrating this solution under reduced pressure, the residue was dissolved in a small amount of THF, added to 400 ml of hexane, the supernatant was removed by decantation, and the precipitate was collected. This procedure was repeated twice to obtain a pasty orange solid in a yield of 3.9 g (yield 98%). The orange solid by ^{IR, 2931cm -1 (C-H} ), 1735cm -1 (C = O), 1457cm -1 (N = N), characteristic absorption of 1253cm ^-1 (PhO-) was observed. The elemental analysis value of the orange solid coincided with the value calculated as C ₄₇₂ H ₆₇₂ N ₄₆ O ₄₈ within a range of 0.5%. (Calculated value-C: 73.07%, H: 8.73%, N: 8.30%, measured value-C: 72.86%, H: 8.49%, N: 8.40%) When the DSC measurement of this orange solid was performed, Tg at −13 ° C. and endothermic peaks at 33 ° C. and 83 ° C. were observed in the temperature rising process, and exothermic peaks were observed at 81 ° C. and 28 ° C. in the temperature decreasing process. Tg was observed at -29 ° C.

<Synthesis of Dendrimer B>
A dendrimer in which R in the above formula (I) is represented by the following formula (V) was synthesized as follows.

Synthesis of 6- [4- (trans-4-pentylcyclohexyl) phenoxy] hexanol Into a 200 ml eggplant flask was added 4- (trans-4-pentylcyclohexyl) phenoxyphenol (10 g, 41 mmol), 6-bromohexanol (8.8 g). 49 mmol), potassium carbonate (11 g, 80 mmol) and 2-butanone (50 ml) were dissolved and heated to reflux for 60 hours. After the heating to reflux was completed, the residue obtained by removing 2-butanone under reduced pressure was dissolved in ethyl acetate, and this solution was washed three times with water. Next, anhydrous sodium sulfate was added to this solution to remove water, and then ethyl acetate was distilled off under reduced pressure. The resulting residue was recrystallized from n-hexane, yielding 6.2 g of white crystals. (Yield 44%). With this white crystal, characteristic absorptions of 3340 cm ⁻¹ (OH), 2922 cm ⁻¹ (C—H), and 1245 cm ⁻¹ (PhO—) were observed by IR.

Synthesis of 6- [4- (trans-4-pentylcyclohexyl) phenoxy] hexyl acrylate In a 200 ml three-necked flask, 6- [4- (trans-4-pentylcyclohexyl) phenoxy] hexanol (6.0 g, 17 mmol), triethylamine (2.2 g, 22 mmol) and THF (50 ml) were dissolved and cooled to 0 ° C. with ice. To this solution, acryloyl chloride (1.9 g, 21 mmol) was slowly added using a syringe and stirred at room temperature for 12 hours. The resulting white solid was filtered off and the filtrate was concentrated under reduced pressure. The obtained residue was dissolved in ethyl acetate and washed with 100 ml of water three times. Next, anhydrous magnesium sulfate was added to the organic phase to remove water, followed by concentration under reduced pressure. Next, the residue was purified by column chromatography (stationary phase: silica gel, mobile phase: hexane / chloroform (volume ratio 50: 1)) to obtain a colorless transparent liquid in a yield of 6.4 g (yield 93%). . In this liquid, characteristic absorptions of 2920 cm ⁻¹ (C—H), 1716 cm ⁻¹ (C═O), and 1245 cm ⁻¹ (PhO—) were observed by IR.

Synthesis of Dendrimer B In a 20 ml eggplant flask, DAB-Am-8 (0.16 g, 0.21 mmol) manufactured by Aldrich, 6- [4- (trans-4-pentylcyclohexyl) phenoxy] hexyl acrylate (4.0 g, 10 mmol) and THF (5 ml) were added and heated at 50 ° C. for 72 hours. Next, after concentrating this solution under reduced pressure, the residue was dissolved in a small amount of chloroform, added to 100 ml of methanol, the supernatant was removed by decantation, and the precipitate was recovered. This operation was purified twice to obtain a pasty pale yellow solid in a yield of 0.45 g (yield 30%). The pale yellow solid by ^{IR, 2921cm -1 (C-H} ), 1736cm -1 (C = O), characteristic absorption of 1247cm ^-1 (PhO-) was observed. The elemental analysis value of the pale yellow solid agreed with the value calculated as C ₄₅₆ H ₇₃₆ N ₁₄ O ₄₈ within a range of 0.5%. (Calculated value-C: 76.25%, H: 10.33%, N: 2.73%, measured value-C: 76.09%, H: 10.52%, N: 2.80%) The molecular weight of the pale yellow solid was measured by MALDI-TOF-MS. As a result, the measured value m / Z = 7181.2 (M + H) with respect to the theoretical value m / Z = 7183 (M + H). Further, when DSC measurement of this pale yellow solid was performed, Tg was observed at −24 ° C. during the temperature rising process, and endothermic peaks were observed at 14 ° C. and 73 ° C., and heat generation was generated at 69 ° C. and 15 ° C. during the temperature falling process. A peak, Tg, was observed at -26 ° C.

<Synthesis of Dendrimer C>
A dendrimer in which R in the above formula (I) is represented by the following formula (VI) was synthesized as follows.

Synthesis of 3- [4- (trans-4-pentylcyclohexyl) phenoxy] propanol In a 300 ml eggplant flask, 4- (trans-4-pentylcyclohexyl) phenol (15 g, 61 mmol), 3-bromo-1-propanol (10 g) 73 mmol), potassium carbonate (17 g, 122 mmol) and 2-butanone (80 ml) were dissolved and heated to reflux for 60 hours. After the heating to reflux was completed, the residue obtained by removing 2-butanone under reduced pressure was dissolved in 300 mL of ethyl acetate, and this solution was washed with 100 mL of water three times. Next, anhydrous sodium sulfate was added to this solution to remove water, and then ethyl acetate was distilled off under reduced pressure. The resulting residue was recrystallized from hexane to yield 12.2 g (yield) of white crystals. 66%). The white crystals were found to be 7.2 to 7.0 ppm (d, 2H, ArH), 6.9 to 6.8 ppm (d, 2H, ArH), 4.1 ppm by ¹ H-NMR (CDCl ₃ , 400 MHz). _{(t, 2H, OCH 2)} , 3.85ppm (q, 2H, PhCH 2), 2.4ppm (m, 1H, ArCH), 1.9~1.2ppm (m, 20H, CH 2), 0. A δ of 85 ppm (t, 3H, CH ₃ ) was observed. Further, characteristic absorptions of 3340 cm ⁻¹ (OH), 2922 cm ⁻¹ (CH), and 1245 cm ⁻¹ (PhO—) were observed by IR.

Synthesis of 3- [4- (trans-4-pentylcyclohexyl) phenoxy] propyl acrylate In a 300 ml eggplant flask, 3- [4- (trans-4-pentylcyclohexyl) phenoxy] propanol (10 g, 33 mmol), triethylamine (3 4 g, 33 mmol) and THF (100 ml) were dissolved and cooled to 0 ° C. with ice. To this solution, acryloyl chloride (4.4 g, 49 mmol) was added using a syringe and stirred at room temperature for 24 hours. The residue obtained by removing the solvent under reduced pressure was dissolved in 300 mL of ethyl acetate, and this solution was washed with 100 mL of water three times. Next, anhydrous magnesium sulfate was added to the solution to remove moisture, and the solution was concentrated under reduced pressure. The residue was purified by column chromatography (stationary phase: silica gel, mobile phase: chloroform) to obtain a white solid in a yield of 8.6 g (yield 73%). This white solid was found to be 7.2 to 7.0 ppm (d, 2H, ArH), 6.9 to 6.8 ppm (d, 2H, ArH), 6.4 by ¹ H-NMR (CDCl ₃ , 400 MHz). ˜5.8 ppm (m, 3H, OCHCH ₂ ), 4.3 ppm (t, 2H, OCH ₂ ), 4.0 ppm (q, 2H, PhCH ₂ ), 2.4 ppm (m, 1H, ArCH), Δ of 9 to 1.2 ppm (m, 20H, CH ₂ ) and 0.85 ppm (t, 3H, CH ₃ ) were observed. Further, characteristic absorptions of 2920 cm ⁻¹ (C—H), 1715 cm ⁻¹ (C═O), and 1245 cm ⁻¹ (PhO—) were observed by IR.

Synthesis of Dendrimer C In a 200 ml two-necked flask, DAB-Am-8 (0.48 g, 0.57 mmol), 3- [4- (trans-4-pentylcyclohexyl) phenoxy] propyl acrylate (6.5 g) manufactured by Aldrich 18 mmol) and THF (10 ml) were added, and the mixture was stirred at 50 ° C. for 7 days under a nitrogen atmosphere. Next, after concentrating this solution under reduced pressure, the residue was dissolved in a small amount of chloroform and added to methanol, and the supernatant was removed by decantation to collect a precipitate. This operation was purified by repeating three times to obtain 2.1 g (yield 57%) of a pale yellow solid. This pale yellow solid was found to be 7.2 to 6.7 ppm (m, 64 H, ArH), 4.2 ppm (t, 32 H, OCH ₂ ), 3.95 ppm (t by ¹ H-NMR (CDCl ₃ , 400 MHz). , 32H, PhOCH ₂ ), 2.74 ppm (t, 32H, N—CH ₂ ), 2.6 to 2.2 ppm (t, 100H, N—CH ₂ , CH ₂ C═O, ArCH), 1.9 Δ of ˜0.9 ppm (m, 332H, CH ₂ ) and 0.85 ppm (t, 48H, CH ₃ ) were observed. Further, characteristic absorptions of 2923 cm ⁻¹ (C—H), 1735 cm ⁻¹ (C═O), and 1243 cm ⁻¹ (PhO—) were observed by IR. Further, the molecular weight of the pale yellow solid measured by MALDI-TOF-MS was measured m / Z = 6531.69 (M + Na) with respect to the theoretical value m / Z = 6531.82 (M + Na). . Furthermore, the elemental analysis value of this pale yellow solid agreed with the value calculated as C ₄₀₈ H ₆₄₀ N ₁₄ O ₄₈ within a range of 0.5%. (Calculated value-C: 75.28%, H: 9.91%, N: 3.01%, measured value-C: 75.26%, H: 10.10%, N: 2.85%) As a result of DSC measurement of this pale yellow solid, endothermic peaks were observed at 17 ° C. and 78 ° C. during the temperature rising process, and exothermic peaks were observed at 74 ° C. and 15 ° C. during the temperature lowering process.

<Synthesis of Dendrimer D>
A dendrimer in which R in the above formula (I) is represented by the following formula (VII) was synthesized as follows.

Synthesis of 12- [4- (trans-4-pentylcyclohexyl) phenoxy] dodecanol In a 300 ml eggplant flask was added 4- (trans-4-pentylcyclohexyl) phenol (15 g, 61 mmol), 12-bromo-1-dodecanol (19 g). 73 mmol), potassium carbonate (17 g, 122 mmol) and 2-butanone (100 ml) were dissolved and heated to reflux for 60 hours. After the heating to reflux was completed, the residue obtained by removing 2-butanone under reduced pressure was dissolved in 300 mL of ethyl acetate, and this solution was washed with 100 mL of water three times. Next, anhydrous sodium sulfate was added to this solution to remove water, and then ethyl acetate was distilled off under reduced pressure. The resulting residue was recrystallized from hexane to yield 21.5 g (yield) of white crystals. 82%). The white crystals were found to be 7.2 to 7.0 ppm (d, 2H, ArH), 6.9 to 6.8 ppm (d, 2H, ArH), 3.9 ppm by ¹ H-NMR (CDCl ₃ , 400 MHz). (T, 2H, OCH ₂ ), 3.6 ppm (q, 2H, PhCH ₂ ), 2.4 ppm (m, 1H, ArCH), 1.9 to 1.2 ppm (m, 38H, CH ₂ ), 0. 86 ppm (t, 3H, CH ₃ ) δ was observed. Further, characteristic absorptions of 3340 cm ⁻¹ (OH), 2922 cm ⁻¹ (CH), and 1245 cm ⁻¹ (PhO—) were observed by IR.

Synthesis of 12- [4- (trans-4-pentylcyclohexyl) phenoxy] dodecyl acrylate In a 300 ml eggplant flask, 12- [4- (trans-4-pentylcyclohexyl) phenoxy] dodecanol (15 g, 35 mmol), triethylamine (3 0.5 g, 35 mmol) and THF (150 ml) were dissolved and cooled to 0 ° C. with ice. To this solution was added acryloyl chloride (4.7 g, 52 mmol) using a syringe, and the mixture was stirred at room temperature for 24 hours. The residue obtained by removing the solvent under reduced pressure was dissolved in 400 mL of ethyl acetate, and this solution was washed with 200 mL of water three times. Next, anhydrous magnesium sulfate was added to the solution to remove moisture, and the solution was concentrated under reduced pressure. The residue was purified by column chromatography (stationary phase: silica gel, mobile phase: chloroform) to obtain a white solid in a yield of 9.2 g (yield 55%). This white solid was found to be 7.2 to 7.0 ppm (d, 2H, ArH), 6.9 to 6.8 ppm (d, 2H, ArH), 6.4 by ¹ H-NMR (CDCl ₃ , 400 MHz). ˜5.8 ppm (m, 3H, OCHCH ₂ ), 4.3 ppm (t, 2H, OCH ₂ ), 4.0 ppm (q, 2H, PhCH ₂ ), 2.4 ppm (m, 1H, ArCH), Δ of 9 to 1.2 ppm (m, 38H, CH ₂ ) and 0.85 ppm (t, 3H, CH ₃ ) were observed. Further, characteristic absorptions of 2923 cm ⁻¹ (CH), 1717 cm ⁻¹ (C═O), and 1244 cm ⁻¹ (PhO—) were observed by IR.

Synthesis of Dendrimer D In a 200 ml two-necked flask, Aldrich DAB-Am-8 (0.26 g, 0.34 mmol), 12- [4- (trans-4-pentylcyclohexyl) phenoxy] dodecyl acrylate (8.0 g) 17 mmol) and THF (15 ml) were added, and the mixture was stirred at 50 ° C. for 7 days under a nitrogen atmosphere. Next, after concentrating this solution under reduced pressure, the residue was dissolved in a small amount of chloroform and added to methanol, and the supernatant was removed by decantation to collect a precipitate. This operation was purified by repeating three times to obtain 1.1 g (38% yield) of a pale yellow solid. This pale yellow solid was found to be 7.2 to 6.7 ppm (m, 64 H, ArH), 4.05 ppm (t, 32 H, OCH ₂ ), 3.9 ppm (t by ¹ H-NMR (CDCl ₃ , 400 MHz). , 32H, PhOCH ₂ ), 2.75 ppm (t, 32H, N—CH ₂ ), 2.6 to 2.2 ppm (t, 100H, N—CH ₂ , CH ₂ C═O, ArCH), 1.9 Δ of ˜0.9 ppm (m, 640H, CH ₂ ) and 0.85 ppm (t, 48H, CH ₃ ) were observed. In addition, characteristic absorptions of 2921 cm ⁻¹ (C—H), 1733 cm ⁻¹ (C═O), and 1245 cm ⁻¹ (PhO—) were observed by IR. Further, the molecular weight of the pale yellow solid measured by MALDI-TOF-MS was measured m / Z = 8552.12 (M + Na) with respect to the theoretical value m / Z = 8552.08 (M + Na). . Additionally, elemental analysis of this light yellow solid were consistent within the value and 0.5% calculated as _{C 552 H 928 N 14 O 48} . (Calculated value-C: 77.73%, H: 10.97%, N: 2.30%, measured value-C: 77.48%, H: 11.02%, N: 2.29%) As a result of DSC measurement of the pale yellow solid, endothermic peaks were observed at 74 ° C. and 82 ° C. during the temperature rising process, and exothermic peaks were observed at 79 ° C. and 72 ° C. during the temperature lowering process.

<Synthesis of Dendrimer E>
A dendrimer in which R in the above formula (I) is represented by the following formula (VIII) was synthesized as follows.

In a 300 ml eggplant flask, DAB-Am-8 (0.28 g, 0.31 mmol) manufactured by Aldrich, 4-methoxyphenyl-6-hexyloxyacrylbenzoate (6.0 g, 15 mmol) and THF manufactured by Koyo Chemical Industries, Ltd. (10 ml) was added, and the mixture was stirred at 50 ° C. for 7 days under a nitrogen atmosphere. Next, after concentrating this solution under reduced pressure, the residue was dissolved in a small amount of chloroform and added to hexane, and the supernatant was removed by decantation to collect a precipitate. This procedure was repeated three times to obtain a paste-like pale yellow solid with a yield of 1.7 g (yield 76%). This pale yellow solid was found to be 8.2 to 8.1 ppm (d, 32H, ArH), 7.1 ppm (d, 32H, ArH), 6.9 ppm (t, t) by ¹ H-NMR (CDCl ₃ , 400 MHz). 64 H, ArCH), 4.1 ppm (t, 32 H, OCH ₂ ), 4.0 ppm (t, 32 H, PhOCH ₂ ), 3.8 ppm (s, 48 H, OCH ₃ ), 2.74 ppm (t, 32 H, N) _{-CH 2), 2.6~2.2ppm (t,} 84H, N-CH 2, CH 2 C = O), 1.9~0.9ppm (m, 284H, CH 2) of δ was observed . Also, by IR, 2944 cm ⁻¹ (C—H), 1732 cm ⁻¹ (C═O), 1250 cm ⁻¹ (C—O—C), 1198 cm ⁻¹ and 1169 cm ⁻¹ (C (C═O) OC) The characteristic absorption of was observed. Further, the molecular weight of this pale yellow solid measured by MALDI-TOF-MS was measured m / Z = 717.48 (M + Na) against the theoretical value m / Z = 7170.57 (M + Na). .

<Synthesis of Dendrimer F>
A dendrimer in which R in the above formula (I) is represented by the following formula (IX) was synthesized as follows.

In a 300 ml eggplant flask, DAB-Am-8 (0.33 g, 0.43 mmol) manufactured by Aldrich, 6- (4- (4-fluorophenyl) phenyloxy) hexyl acrylate (7.0 g, manufactured by Koyo Chemical Industries, Ltd.) 20 mmol) and THF (10 ml) were added, and the mixture was stirred at 50 ° C. for 7 days under a nitrogen atmosphere. Next, after concentrating this solution under reduced pressure, the residue was dissolved in a small amount of chloroform and added to methanol, and the supernatant was removed by decantation to collect a precipitate. This procedure was repeated three times to obtain a pale yellow solid in a yield of 1.9 g (yield 72%). This pale yellow solid was analyzed by ¹ H-NMR (CDCl ₃ , 400 MHz) from 7.5 to 7.2 ppm (m, 64 H, ArH), 7.1 ppm (t, 32 H, ArH), 6.9 ppm (d, 32H, ArCH), 4.1 ppm (t, 32H, OCH ₂ ), 3.9 ppm (t, 32H, PhOCH ₂ ), 2.74 ppm (t, 32H, N—CH ₂ ), 2.6-2.2 ppm (t, 84H, N-CH 2, CH 2 C = O), 1.9~0.9ppm (m, 284H, CH 2) δ in was observed. In addition, by IR, 2940 cm ⁻¹ (C—H), 1732 cm ⁻¹ (C═O), 1235 cm ⁻¹ (C—O—C), 1182 cm ⁻¹ (C—F), 1160 cm ⁻¹ (C (C = O) OC) characteristic absorption was observed. Further, when DSC measurement of this pale yellow solid was performed, an endothermic peak was observed at 56.90 ° C. during the temperature rising process, and an exothermic peak was observed at 49.51 ° C. during the temperature lowering process.

<Synthesis of Dendrimer G>
A dendrimer in which R in the above formula (I) is represented by the following formula (X) was synthesized as follows.

In a 300 ml eggplant flask, DAB-Am-8 (0.25 g, 0.32 mmol) manufactured by Aldrich, 6- (4- (3,4,5-trifluorophenyl) phenyloxy) hexyl acrylate manufactured by Koyo Chemical Industries, Ltd. (6.0 g, 15 mmol) and THF (10 ml) were added, and the mixture was stirred at 50 ° C. for 7 days under a nitrogen atmosphere. Next, after concentrating this solution under reduced pressure, the residue was dissolved in a small amount of chloroform and added to hexane, and the supernatant was removed by decantation to collect a precipitate. This operation was purified by repeating three times to obtain 1.3 g (59% yield) of a pale yellow solid. This pale yellow solid was analyzed by ¹ H-NMR (CDCl ₃ , 400 MHz) from 7.5 to 7.2 ppm (d, 32 H, ArH), 7.1 ppm (t, 32 H, ArH), 6.9 ppm (d, 32H, ArCH), 4.1 ppm (t, 32H, OCH ₂ ), 3.9 ppm (t, 32H, PhOCH ₂ ), 2.74 ppm (t, 32H, N—CH ₂ ), 2.6-2.2 ppm (t, 84H, N-CH 2, CH 2 C = O), 1.9~0.9ppm (m, 284H, CH 2) δ in was observed. Further, by IR, 2943 cm ⁻¹ (C—H), 1732 cm ⁻¹ (C═O), 1243 cm ⁻¹ (C—O—C), 1182 cm ⁻¹ (C—F), 1118 cm ⁻¹ (C (C = O) OC) characteristic absorption was observed. Furthermore, DSC measurement of this pale yellow solid was performed, but no peak was observed in either the temperature rising process or the temperature falling process.

<Synthesis of Dendrimer H>
For comparison, a dendrimer in which R in the above formula (I) is represented by the following formula (XI) was synthesized according to the method described in JP-A No. 2000-264965.

Example 1
In Example 1, a liquid crystal composition was prepared by mixing Dendrimer A and various mixed liquid crystals.
As the mixed liquid crystal, fluorine-based mixed liquid crystal ZLI-4792 (P type, Merck Ltd.), fluorine-based mixed liquid crystal MLC-6608 (n-type, Merck Ltd.) and cyano mixed liquid crystal JC-5066XX (p-type, Chisso Petroleum) Three types of chemicals) were used. The content of dendrimer A in the liquid crystal composition was 0.1% by mass and 1% by mass.
(Example 2)
In Example 2, a liquid crystal composition was prepared by mixing Dendrimer B and various mixed liquid crystals.
As the mixed liquid crystal, fluorine-based mixed liquid crystal ZLI-4792 (P type, Merck Ltd.), fluorine-based mixed liquid crystal MLC-6608 (n-type, Merck Ltd.) and cyano mixed liquid crystal JC-5066XX (p-type, Chisso Petroleum) Three types of chemicals) were used. The content of dendrimer B in the liquid crystal composition was 0.1% by mass and 1% by mass.

(Example 3)
In Example 3, a liquid crystal composition was prepared by mixing Dendrimer C and various mixed liquid crystals.
As the mixed liquid crystal, two types of fluorine-based mixed liquid crystal ZLI-4792 (P type, Merck) and fluorine-based mixed liquid crystal MLC-6608 (n-type, Merck) were used. The content of dendrimer C in the liquid crystal composition was 0.1% by mass and 1% by mass.
Example 4
In Example 4, a liquid crystal composition was prepared by mixing Dendrimer D and various mixed liquid crystals.
As the mixed liquid crystal, two types of fluorine-based mixed liquid crystal ZLI-4792 (P type, Merck) and fluorine-based mixed liquid crystal MLC-6608 (n-type, Merck) were used. The content of dendrimer D in the liquid crystal composition was 0.1% by mass and 1% by mass.

(Example 5)
In Example 5, a liquid crystal composition was prepared by mixing Dendrimer E and various mixed liquid crystals.
As the mixed liquid crystal, two types of fluorine-based mixed liquid crystal ZLI-4792 (P type, Merck) and fluorine-based mixed liquid crystal MLC-6608 (n-type, Merck) were used. The content of dendrimer E in the liquid crystal composition was 0.1% by mass and 1% by mass.
(Example 6)
In Example 6, a liquid crystal composition was prepared by mixing Dendrimer F and various mixed liquid crystals.
As the mixed liquid crystal, two types of fluorine-based mixed liquid crystal ZLI-4792 (P type, Merck) and fluorine-based mixed liquid crystal MLC-6608 (n-type, Merck) were used. The content of dendrimer F in the liquid crystal composition was 0.1% by mass and 1% by mass.

(Example 7)
In Example 7, a liquid crystal composition was prepared by mixing Dendrimer G and various mixed liquid crystals.
As the mixed liquid crystal, two types of fluorine-based mixed liquid crystal ZLI-4792 (P type, Merck) and fluorine-based mixed liquid crystal MLC-6608 (n-type, Merck) were used. The content of dendrimer G in the liquid crystal composition was 0.1% by mass and 1% by mass.
(Comparative Example 1)
In Comparative Example 1, a liquid crystal composition was prepared by mixing Dendrimer H and various mixed liquid crystals.
As the mixed liquid crystal, two types of fluorine-based mixed liquid crystal ZLI-4792 (P type, Merck) and fluorine-based mixed liquid crystal MLC-6608 (n-type, Merck) were used. The content of dendrimer F in the liquid crystal composition was 0.1% by mass and 1% by mass.

  In the liquid crystal compositions of Examples 1 to 7 and Comparative Example 1, the compatibility of the dendrimer with each liquid crystal material (mixed liquid crystal) was visually evaluated. The results are shown in Table 1. In this evaluation, in the case where the dendrimer content was 0.1% by mass and 1% by mass, the compatibility was good, and the dendrimer content was 0.1% by mass and 1% by mass. In any case, the case where the compatibility was poor and separation or the like occurred is represented as x.

  As shown in Table 1, while dendrimers A to G have good compatibility with mixed liquid crystals and can be used for liquid crystal layers of liquid crystal display devices (Examples 1 to 7), dendrimers H are: It was found that the compatibility with the mixed liquid crystal was poor and the liquid crystal layer of the liquid crystal display device could not be used (Comparative Example 1).

Next, liquid crystal cells without alignment films were prepared using the liquid crystal compositions of Examples 1-7. In addition, since the liquid crystal composition of Comparative Example 1 had poor compatibility of the dendrimer with the liquid crystal material and was not suitable as a liquid crystal composition, a liquid crystal cell was not produced. Here, with respect to the p-type mixed liquid crystal, a liquid crystal cell having a chrome comb-type electrode (produced by Eetchy Co., Ltd., an interelectrode distance of 10 μm, an electrode area of 2 cm ² ) on one glass substrate was prepared, and an n-type mixed liquid crystal About, the liquid crystal cell which has an ITO transparent planar electrode (electrode area 1cm < ² >) on both the glass substrates was produced. The size of the produced liquid crystal cell was 2 cm × 2.2 cm. In each liquid crystal cell, a glass substrate (thickness 0.7 mm), a dot column spacer (model number JNPC-123-V2, manufactured by JSR Corporation, height of about 3 μm) arranged in a photolithography process is used. After applying a thermosetting sealing material (model number XN21-S, manufactured by Mitsui Chemicals, Inc.) to the periphery of the glass substrate excluding the portion to be formed, the glass substrates are overlapped with each other, and 5 at 160 ° C. under a spring-type jig pressurizing environment. Bonded by heating for hours. After bonding, each liquid crystal composition was injected into the liquid crystal cell, and the injection port was sealed with a UV adhesive (manufactured by ThreeBond, model number 3027D). The cell gap of the obtained liquid crystal cell was about 3.0 μm.

  About the obtained liquid crystal cell, the switching characteristic before the temperature raising / lowering process and after the temperature raising / lowering process was evaluated. This evaluation was performed by observing the behavior when an electric field was applied and when no electric field was applied, using a polarizing microscope (BX-50p, manufactured by Olympus Corporation). In the temperature raising / lowering process, the liquid crystal cell is placed on a hot stage (microscope heating / cooling device LK-600PM, manufactured by Linkam Co., Ltd.), and the temperature rises from room temperature at a rate of 10 ° C./min in increments of 20-30 ° C. The temperature was raised to each temperature, held for 5 minutes near the phase transition temperature, and then cooled to room temperature. Table 2 shows the results of the switching characteristics. In this evaluation, even when the dendrimer content in the liquid crystal layer was 0.1% by mass and 1% by mass, uniform vertical alignment was observed, and switching from dark field to bright field was possible. ◎, when the content of the dendrimer in the liquid crystal layer is 1% by mass, a uniform vertical alignment was observed, and switching from the dark field to the bright field was possible, and the dendrimer in the liquid crystal layer was When the content is 1% by mass, the vertical alignment is not uniform, but a switch from the dark field to the bright field is possible is represented by Δ.

  As shown in Table 2, the liquid crystal cells produced using the liquid crystal compositions of Examples 1 to 7 can be switched from dark field to bright field and have good switching characteristics. It was.

  As can be seen from the above results, according to the present invention, it is possible to provide a liquid crystal display device capable of controlling liquid crystal alignment without degrading characteristics such as contrast. Moreover, according to the present invention, a liquid crystal composition capable of providing a liquid crystal display device having the above-described characteristics can be provided.

  1a, 1b substrate, 2 liquid crystal layer, 3 liquid crystal molecule, 4 color filter layer, 5 overcoat layer, 6 planar electrode, 7 comb electrode, 8 alignment film, 9 sealing material, 10 dendrimer.

Claims (10)

A liquid crystal display device comprising a liquid crystal layer containing a dendrimer compatible with a liquid crystal component ,
The dendrimer has the following formula (I):

Wherein R is the formula (II):

And A is

(Wherein R ¹ is an alkyl or alkoxy group having 1 to 12 carbon atoms, or fluorine), X is a direct bond, —COO— group or —N═N— group, and B is

And n is an integer of 3 to 12) . 2. The liquid crystal display device according to claim 1 , wherein the liquid crystal layer has a phase transition temperature from a liquid crystal phase to an isotropic phase or another liquid crystal phase of 50 ° C. or more and 120 ° C. or less. Said liquid crystal component, a liquid crystal display device according to claim 1 or 2, characterized in that a mixed crystal containing two or more liquid crystal component. It said liquid crystal component, a liquid crystal display device according to any one of claims 1 to 3, characterized in that a fluorine-based liquid crystal mixture. The liquid crystal layer, the liquid crystal display device according to any one of claims 1 to 4, characterized in that it is held between a pair of substrates alignment film is not formed. The liquid crystal display device according to any one of claims 1 to 5, characterized in that the liquid crystal molecules of the liquid crystal layer are aligned vertically. The liquid crystal layer, the liquid crystal display device according to any one of claims 1 to 6, characterized in that in contact with the electrode. The following formula (I):

Wherein R is the formula (II):

And A is

(Wherein R ¹ is an alkyl or alkoxy group having 1 to 12 carbon atoms, or fluorine), X is a direct bond, —COO— group or —N═N— group, and B is

And n is an integer of 3 to 12) , and a liquid crystal composition comprising two or more liquid crystal components. The liquid crystal composition according to claim 8 , wherein a phase transition temperature from the liquid crystal phase to the isotropic phase or another liquid crystal phase is 50 ° C or higher and 120 ° C or lower. The liquid crystal composition according to claim 8 or 9 , wherein the two or more liquid crystal components are fluorine-based mixed liquid crystals.

Images