JPH05202358A - Liquid crystal composition and information display device using the same - Google Patents

Abstract

PURPOSE:To provide a liquid crystal composition containing a specific liquid crystalline copolymer and a low molecular liquid crystal compound, working in a wide temperature range including room temperature, having high film formability and high orientation by a dynamic orientation method in the bending direction, etc., and rapidly responding to the change in an electric field. CONSTITUTION:The objective composition contains (A) a liquid crystalline copolymer comprising repeating units of formula I {(a), (b) are 2-5; (d) is 0-3; (e) is 1-20; R<1> is group of formula II {R<2> is COOR<3> [R<3> is group of formula III (R<4>, R<5> are methyl, halogen; (f) 0-10; (g) is 0, 1; (h) is 1-11, but when R<5> is methyl, (h) is not 1; * is asymmetric carbon)], etc.}}, or a liquid crystalline copolymer comprising repeating units of formulas IV and V [(j) is 0-3; (k) is 2-7; R<6> is optically active alkyl of formula VI ((m) is 0-3; (n) is 2-7), etc.], the (IV/V) molar ratio between the formulas IV and V being 1/99 to 99/1, and (B) a low molecular liquid crystal compound, the molar fraction of the component A being 5-99wt.%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal composition which can be suitably used for a liquid crystal display device, a liquid crystal optical device, a liquid crystal storage device and the like. The present invention also relates to an information display body using the liquid crystal composition, which is suitable for displaying news and advertisements.

[0002]

As a liquid crystal composition used for a liquid crystal element,
A polymer liquid crystal composition composed of a polymer liquid crystal compound having an asymmetric carbon and a low molecular weight liquid crystal compound has been proposed (JP-A-63-284291). However, the exemplified side chain type polymer liquid crystal is a normal alkylate or siloxane chain, so that the side chain spacing is not sufficient, and if the molecular weight is increased, the low molecular weight liquid crystal cannot be sufficiently mixed and it becomes difficult to increase the speed. Therefore, there is a problem that it is difficult to obtain a high-speed composition while maintaining the original polymer property. Further, since the temperature range showing the chiral smectic C phase is narrow, there is a problem that it is difficult to obtain a composition which operates in a wide temperature range including room temperature even by mixing a low molecular weight liquid crystal.

As an information display body, a display including a liquid crystal display, a storage unit for holding display contents, a control unit for interfacing, a connector unit for connecting the host processor, and a battery unit for supplying power has been proposed. (Japanese Patent Application Laid-Open No. 64-70793). This display can display contents even if it is separated from the host processor. However, it requires power because the storage unit operates for display when disconnected from the host processor, must be connected to the host processor each time to change display contents, conventional liquid crystal display Since it uses, there is a problem that it is difficult to increase the area.

[0004]

DISCLOSURE OF THE INVENTION The present invention operates in a wide temperature range including room temperature, has a high orientation property with respect to a mechanical orientation method such as film forming property and bending orientation, and has a tilt angle (2θ).
The present invention is intended to provide a liquid crystal composition which can be controlled, and which responds to electric field changes at high speed.

The present invention is also capable of displaying a large area and a curved surface, can display a wide variety of contents with a simple drive control circuit, is resistant to mechanical shock, requires no external power supply, and is thin and lightweight. It is intended to provide a possible information display body.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a liquid crystalline copolymer having an alkyl chain and a siloxane chain in the main chain and a low molecular weight liquid crystal compound. It was found that the above problems can be solved by a liquid crystal composition containing a specific ratio, and the present invention has been completed based on this finding.

That is, the present invention provides a repeating unit [I] represented by the following general formula.

[Chemical 9] {In the formula, a and b are integers of 2 to 5, d is an integer of 0 to 3,
e is an integer of 1 to 20, and R ¹ is

[Chemical 10] Is. However, R ² is -COOR ³ , -OR ³ or -OCOR ³ , and R ³ is

[Chemical 11] And R ⁴ and R ⁵ are a methyl group or a halogen atom,
f is an integer of 0 to 10, g is 0 or 1 and h is an integer of 1 to 11 (when R ⁵ is a methyl group, h is not 1), and * represents an asymmetric carbon atom. } The liquid crystal copolymer or the repeating unit represented by the following general formula [I
I] and [III]

[Chemical 12] {Wherein a, b, d and e are the same as above, and j is 0
Is an integer of 3 to 3, k is an integer of 2 to 7, and R ⁶ is represented by the general formula [I
V] or an optically active alkyl group represented by the general formula [V]
An optically inactive alkyl group represented by

[Chemical 13] (However, m in the formula is an integer of 0 to 3, n is an integer of 2 to 7, and * represents an asymmetric carbon atom.). } And the molar ratio of repeating units [II] and [III] ([I
[I] / [III]) is a liquid crystalline copolymer containing (1/99) to (99/1) and a low molecular weight liquid crystal compound, wherein the liquid crystalline copolymer and the low molecular weight compound are included. The ratio of the liquid crystalline copolymer to the total of the liquid crystal compound is 5 to 99% by weight.
A liquid crystal composition is provided.

The liquid crystalline copolymer used in the present invention is
The thing consisting of the said general formula [I] or the thing which consists of general formula [II] and [III] is used. Thus, by using a side chain type polymer liquid crystal having an alkyl chain and a siloxane chain as a main chain as a liquid crystalline copolymer, it operates in a wide temperature range including room temperature and is excellent in film formability and orientation. A liquid crystal composition is obtained. Weight average molecular weight Mw of liquid crystalline copolymer
Is preferably 1000 or more, and usually 1000 to 1
0,000 is preferable. The liquid crystalline copolymer may be a dimer-oligomer liquid crystal. Specifically, examples of the liquid crystalline copolymer represented by the general formula [I] include liquid crystalline copolymers composed of the following repeating units.

[0009]

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17]

The liquid crystalline copolymer of the general formulas [II] and [III] has a molar ratio ([II] / [III]) of repeating units [II] and [III] of (1 /
What is 99)-(99/1) is used. Within this range, ([II] / [III]) is preferably (40 /
60) to (95/5). Such a general formula [I
I] and [III] in the liquid crystalline copolymer, in the formula, a is 2 or 3, b is 5-a, d is 0 or 1, and e is 2 to 3.
Those which are integers of 20 are preferred. Specific examples include the liquid crystalline copolymers shown below.

[0011]

[Chemical 18]

As the low molecular weight liquid crystal compound used in the present invention, known low molecular weight liquid crystal compounds can be preferably used without particular limitation. A mixture of two or more low molecular weight liquid crystal compounds may be used to adjust the temperature range showing the liquid crystal phase of the obtained liquid crystal composition, the tilt angle, the response time to changes in the electric field, and the like. Although it is difficult to define the molecular weight of the low molecular weight liquid crystal compound, the low molecular weight liquid crystal compound used in the present invention is a liquid crystal compound having no repeating unit structurally, and includes a monomer liquid crystal compound.

When the low-molecular liquid crystal compound has the same structure in the molecule as the mesogen group of the liquid crystalline copolymer contained in the liquid crystal composition, the tilt angle (2
It is preferable because the electric field response can be improved without significantly decreasing θ). Here, the mesogen group of the liquid crystalline copolymer means a cyclic group portion obtained by removing the spacer portion and the flexible terminal group from the side chain of the liquid crystalline copolymer. As such a low molecular weight liquid crystal compound,

(1) The mesogen group alone is the same as the mesogen group of the liquid crystalline copolymer,

(2) Those having the same structure in the molecule as the side chain mesogenic group to the flexible terminal group of the liquid crystalline copolymer, for example, the general formula C _x H _{2 x + 1} OR ¹ or

[Chemical 19] (In the formula, x is an integer of 6 to 14, and j, *, k, R ¹ and R ⁶ have the same meanings as described above.), And

(3) When the liquid crystalline monomer constituting the repeating unit of the liquid crystalline copolymer, that is, the liquid crystalline copolymer is composed of the repeating unit [I], the following general formula

[Chemical 20] (In the formula, a, b, e and R ¹ have the same meanings as described above.) The low molecular weight liquid crystal compound and the liquid crystalline copolymer are composed of repeating units [II] and [III]. In the case, the following general formula

[Chemical 21] (In the formula, a, b, e, j, k and R ⁶ have the same meanings as described above.) And the like.

Among the liquid crystal compositions composed of the liquid crystal copolymer having the same mesogen group and the low molecular weight liquid crystal compound as described above, particularly preferable one is that the liquid crystal copolymer is composed of the repeating unit [I] and R ¹ is

[Chemical formula 22] Wherein the low molecular weight liquid crystal compound is a tricyclic monomer constituting the repeating unit [I] of the liquid crystalline copolymer,

[Chemical formula 23] Is. ) A liquid crystal composition represented by:

The liquid crystalline copolymer is composed of repeating units [II] and [III], and the low molecular weight liquid crystal compound is a tricyclic monomer constituting the repeating unit [II] of the liquid crystalline copolymer. And the following general formula

[Chemical formula 24] A liquid crystal composition represented by Specific examples of the low molecular weight liquid crystal compound used in the present invention include the following.

[0019]

[Chemical 25]

[Chemical formula 26]

[Chemical 27]

Specific examples of the combination of the liquid crystalline copolymer having the same mesogenic group and the low molecular weight liquid crystal compound include, for example, the liquid crystalline copolymer represented by the above (k) as the liquid crystalline copolymer. When used, the low molecular weight liquid crystal compounds are preferably low molecular weight liquid crystal compounds of the following (1) to (3).

[Chemical 28] Here, 8-12 are preferable as x.

The method of mixing the liquid crystalline copolymer and the low molecular weight liquid crystal compound is not particularly limited and may be direct mixing or solution mixing. For example, as a solution mixing method, a method in which a predetermined amount of a liquid crystalline copolymer and a low molecular weight liquid crystal compound are placed in a container, dissolved in a solvent such as dichloromethane and mixed, and the solvent is evaporated is suitable. As the mixing ratio, the ratio of the liquid crystal copolymer to the total of the liquid crystal copolymer and the low molecular weight liquid crystal compound is 5
Up to 99% by weight. It is preferably 10 to 95% by weight. When the proportion of the liquid crystalline copolymer is less than 5% by weight, the film-forming property and the orientation of the liquid crystal composition are deteriorated. If it exceeds 99% by weight, the response time to changes in the electric field becomes long.

The liquid crystalline copolymer and the low molecular weight liquid crystal compound are mixed so that the liquid crystal composition has a composition exhibiting a ferroelectric liquid crystal phase or an antiferroelectric liquid crystal phase excellent in electric field response. Is preferred. Since such a composition differs depending on the compound, it cannot be unconditionally specified, but the ferroelectric liquid crystal phase or the antiferroelectric liquid crystal phase must introduce an asymmetric carbon atom into at least one of the compounds contained in the composition. Can be easily expressed with. In particular, since the liquid crystalline copolymers exemplified above exhibit a ferroelectric liquid crystal phase in a wide temperature range, a liquid crystal composition obtained by mixing an appropriate low molecular weight liquid crystal compound can be used in a wide temperature range including room temperature. Liquid crystalline phase can be exhibited.

It is also preferable to impart dichroism to the liquid crystal composition by using a mixture of dichroic dyes or a copolymer of the dye moiety and the liquid crystal moiety. As the dichroic dye, a known dye that can be used in a conventional guest-host type liquid crystal display element can be preferably used. Specific examples include anthraquinone derivatives, azo derivatives, diazo derivatives, merocyanine derivatives, and tetrazine derivatives. These may be used alone or in combination of two or more. As the color of the dye, a black dye that can easily increase the contrast is preferable.

Generally, the electric field response of the liquid crystal composition can be improved by increasing the fraction of the low molecular weight liquid crystal compound, but the film-forming property of the liquid crystal composition and the mechanical strength when used as a liquid crystal display device are improved. It may decrease. In such a case, it is preferable to use a liquid crystal composition containing 2 to 30% by weight of the non-liquid crystal polymer substance. As the non-liquid crystal polymer substance, for example, polyacrylic acid, polymethacrylic acid, polyacrylate, polymethacrylate, polyacrylamide, polyvinyl alcohol, polyvinyl acetate, polycarbonate, a polyester obtained by a condensation reaction of a dicarboxylic acid derivative and a diol derivative, Examples thereof include a polyamide obtained by a condensation reaction of a dicarboxylic acid derivative and a diamine derivative, and a polyamide obtained by a condensation reaction of a dicarboxylic acid derivative with a monoalcohol and a monoamine derivative. In particular, acrylic thermoplastic resins such as PMMA (polymethyl methacrylate) and PBMA (polybutyl methacrylate) are preferable.

The present invention also provides a liquid crystal display device comprising the above liquid crystal composition sandwiched between flexible substrates with electrodes, a receiving unit for receiving the display contents of the liquid crystal display device from outside by a radio signal, and a receiving unit. It is an object of the present invention to provide an information display body characterized by including a drive circuit for driving a liquid crystal display element according to a signal and a power supply section for supplying power to the drive circuit.

The information display body of the present invention is one in which a liquid crystal display element, a receiving section, a drive circuit and a power supply section are integrated, and it is preferable that the entire information display body is integrated by a protective cover or the like. A liquid crystal display device is formed by sandwiching the above liquid crystal composition between flexible substrates with electrodes. As the flexible substrate, those normally used for liquid crystal display elements can be preferably used. Examples thereof include crystalline polymers such as uniaxially or biaxially stretched polyethylene terephthalate, non-crystalline polymers such as polysulfone and polyether sulfone, polyolefins such as polyethylene and polypropylene, polyamides such as polycarbonate and nylon. By using such a flexible substrate, the display surface of the liquid crystal display element can be formed into a curved surface, and a liquid crystal display element capable of high speed, large area, and curved surface display can be obtained. Further, it is possible to obtain a liquid crystal display element whose display does not disappear even after the power is turned off.

As the electrodes formed on the flexible substrate, those usually used for liquid crystal display elements can be preferably used, and transparent or semitransparent electrodes are preferable. For example, a film made of a NESA film or an ITO film can be used.
The electrode pattern may be a stripe pattern for dot matrix display, a pattern for segment display, or a mixture thereof, depending on the display content required.

As a method for sandwiching the above liquid crystal composition with a flexible substrate with an electrode, a known method can be applied without particular limitation. In particular, since a flexible substrate is used, a method of continuously applying the liquid crystal composition to the electrode surface of the flexible substrate with an electrode and laminating the liquid crystal composition on the counter substrate is preferable because of excellent productivity. Further, the liquid crystal display device is preferably subjected to horizontal alignment treatment so that the smectic layer normal of the liquid crystal composition is in the vertical direction of the liquid crystal display device. By doing so, the viewing angle in the lateral direction is improved, and the visibility can be improved even when the information display body is installed on a train, a bus, or the like. The alignment treatment method is not particularly limited,
Bending orientation method excellent in continuous and high-speed productivity (Japanese Patent Application Laid-Open No. 2-10
The use of a mechanical alignment method such as that described in Japanese Patent No. 322) is preferable because an alignment control film such as a rubbing film can be eliminated.

Further, the information display body of the present invention may include a plurality of liquid crystal display elements. For example, if the limit of the production apparatus of the liquid crystal display element is 30 cm in width, it is possible to form an information display body having an information display surface of 90 cm in width by arranging three liquid crystal display elements of that width.

As the receiving unit for receiving the display content of the liquid crystal display device from the outside by a radio signal, it is preferable to use, for example, an antenna unit and a receiving circuit. The receiving unit receives the content transmitted from the outside and displays the content on the liquid crystal display element. As the antenna part, in order to reduce the size of the entire device, a antenna having a thickness of 10 mm or less formed by forming a conductor on a flat or curved dielectric sheet is preferable. A metal foil or tape is suitable as the conductor. A loading coil or an impedance conversion circuit may be used to further reduce the size of the antenna unit. When used in a moving body such as a bus or train, the direction of the transmitting station changes, so a high-gain antenna with a small directivity, such as a vertical dipole antenna or a diversity antenna,
An antenna unit including a ground plane antenna, a sleeve antenna, a loop antenna, a whip antenna, an umbrella type antenna, etc. is preferably used. When the electric field strength is sufficiently high, a part of the antenna section may be connected to a vehicle body such as a bus or train. As the receiving circuit, one configured by a known method can be preferably used. The format of data transfer is also arbitrary, but when used in a moving body such as a bus or train, frequency modulation (FM) that is less susceptible to external noise is preferable.

As the drive circuit for driving the liquid crystal display element in accordance with the signal from the receiving section, the same drive method and circuit as those for the low molecular weight ferroelectric liquid crystal can be used.
In the case of the dot matrix method, for example, Japanese Patent Laid-Open No. 1-
The methods described in Japanese Patent No. 26543 and Japanese Patent Application Laid-Open No. 1-97445 can be preferably used. In the case of the segment method, a known method can be preferably used. These circuit configurations have a drive driver I for existing TN cells.
C or various general-purpose ICs can be used, but when a solar battery or a thin battery is used as a power source, it is preferable to use a CMOS IC or the like with low power consumption. These circuits may be integrated with the liquid crystal display element.

As a power supply section for supplying power to the drive circuit, it is preferable to use a solar cell or a film-shaped thin cell in order to make the entire apparatus thin and lightweight. When a solar cell is used, it can be combined with an appropriate secondary battery to reduce the effect of illuminance change at the place of use. By thus incorporating the power supply unit in the device, it is possible to increase the degree of freedom of installation location by eliminating the need for external power supply work. A liquid crystal display element or a receiving unit may be connected to the power supply unit if necessary. An inexpensive amorphous silicon type solar cell or the like can be preferably used as the solar cell. For example, a CMOS-IC normally requires a voltage of about 3V, but a solar cell that generates a voltage required for a circuit is used, or a plurality of solar cells are connected in series to obtain a required voltage. To Since the output voltage of a solar cell changes when the illuminance at the place of use changes, it can be stabilized by providing a constant voltage circuit or combining an appropriate secondary battery such as a NiCd battery. In addition to solar cells, film-type thin cells are suitable because they do not impair the lightness and thinness. As the film battery, a commercially available battery such as "Denfill" manufactured by Kimoto Co., Ltd. is preferably used.

[0033]

EXAMPLES The present invention will be described below based on examples, but the present invention is not limited to these examples. Examples 1 to 12 Liquid crystalline copolymers (1) to (4) and low molecular weight liquid crystal compounds A to H shown below were used, and these were mixed as shown in Table 1 to obtain one type of liquid crystalline copolymer. A liquid crystal composition consisting of one low-molecular liquid crystal compound and exhibiting a ferroelectric liquid crystal phase was prepared. Here, mixing of the liquid crystalline copolymer and the low molecular weight compound was carried out by placing a predetermined amount of each in a container, adding 100 ml of dichloromethane at room temperature to dissolve and mix, and then evaporating dichloromethane. ..

Liquid crystalline copolymer [1]

[Chemical 29] Weight average molecular weight Mw = 4130 Tilt angle 2θ = 73 ° (I: isotropic phase, SmC ^* : chiral smectic C phase, g: glass state)

Synthesis Example 1 Synthesis of Liquid Crystalline Copolymer [1]

[Chemical 30] 0.1 mol of 1,5-hexadien-3-ol and 0.17 mol of sodium hydride are stirred in 150 ml of THF at room temperature for 1 hour. Then 1,10-dibromodecane 0.
Introduce 3 mol and reflux for 12 hours. The reaction solution was filtered, concentrated, and purified by column chromatography to obtain the target ether (1). (Yield 63%)

[0036]

[Chemical 31] A solution of 60 mmol of the ether body (1) obtained above, 60 mmol of 4-hydroxybenzoic acid methyl ester and 0.2 mol of potassium carbonate in 150 ml of acetone was refluxed for 12 hours. The reaction solution was filtered, concentrated, and purified by column chromatography to obtain the target ether (2). (Yield 77%)

[0037]

[Chemical 32] 30 mmol of the ether compound (2) obtained in [2], 0.1 mol of sodium hydroxide, 50 ml of ethanol and 2
Reflux 0 ml of solution for 30 minutes. The reaction solution was poured into 500 ml of water, the pH was adjusted to 2 with diluted HCl water, the reaction solution was extracted with ether, dried and concentrated, and then purified by column chromatography to obtain the desired carboxylic acid derivative (3). It was (Yield 96%)

[0038]

[Chemical 33] 40 g of the carboxylic acid derivative (3) obtained in [3], 34 ml of thionyl chloride, and 130 ml of toluene were collected in a 1000-neck four-necked flask equipped with a reflux condenser and stirred to obtain a uniform solution. Next, 0.2 ml of pyridine was added, the reaction temperature was raised to 65 ° C., and heating and stirring were continued for 4 hours. After this, the reaction mixture is aspirated under reduced pressure at 65 ° C. for 1 hour and then at 80 ° C. for 3 hours.
Heated for 0 minutes to remove toluene and remaining thionyl chloride. Then, 170 ml of toluene and 11.8 ml of pyridine were added to the reaction mixture cooled to room temperature to form a uniform solution, and 170 ml of a toluene solution containing 30.5 g of optically active 1-methylbutyl 4′-hydroxybiphenyl-4-carboxylate therein. Was added dropwise over 30 minutes with stirring. After this, the reaction was completed by stirring overnight at room temperature.

The reaction mixture was filtered to remove the precipitated pyridine salt. Next, the filtrate was subjected to a rotary evaporator, 80 g of methylene chloride was added to the concentrate obtained by distilling off the solvent under reduced pressure at a bath temperature of 50 ° C., and stirred to prepare a uniform and transparent solution. This solution was fractionated by liquid chromatography using a pre-column packed with activated alumina and a main column packed with silica gel. The eluate containing the target substance was applied to a rotary evaporator, and the solvent was distilled off under reduced pressure at a bath temperature of 50 ° C. to obtain a target crude product of the diene compound (4). The crude product was transferred to a 1 liter volumetric flask and 900 ml of ethanol was added. Next, a reflux condenser was attached to the flask and stirred at 70 ° C. for 10 minutes. After confirming that the white solid was completely dissolved into a uniform solution, the flask was naturally cooled to near room temperature. Next, the flask was stoppered to prevent moisture from entering, and then placed in a refrigerator and allowed to stand for 4 hours or more. After this, the flask was taken out, the precipitated white solid was collected by suction filtration, and washed with ethanol several times. Finally, add this solid to 5
It was dried overnight in a vacuum dryer at 0 ° C. to obtain the desired diene compound (4). The yield was 44.4 g.

This diene compound exhibits liquid crystallinity and exhibits the following phase transition behavior and physical properties. (Cry: crystalline phase, SmC ^* : chiral smectic C
Phase, SmA: smectic A phase, S1: unidentified smectic phase) Response time: 41 μs (68 ° C.) Applied electric field ± 20
MV / m Tilt angle (2θ): 74 ° (68 ° C)

-Polyaddition reaction- 3.85 g of the diene compound (4) obtained above and 0.54 g of tetramethyldisiloxane were dissolved in toluene, and chloroplatinic acid hexahydrate was further added in an argon gas stream. 0 mg
Was added as a catalyst and reacted at 80 ° C. for 20 hours. After the reaction was completed, the mixture was allowed to stand to room temperature, activated carbon was added to the reaction mixture,
Next, after stirring at 50 ° C. for 10 minutes, filtration was performed to remove activated carbon. Toluene was distilled off from the reaction mixture under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 3.60 g of a target liquid crystalline copolymer.

Liquid crystalline copolymer [2]

[Chemical 34] Weight average molecular weight Mw = 3700 Tilt angle 2θ = 80 °

Synthesis Example 2 Synthesis of Liquid Crystalline Copolymer [2]

[Chemical 35] Carboxylic acid derivative (3) 4 obtained in Synthesis Example 1- [3]
57.8 g of the diene compound (5) was obtained in the same manner as in Synthesis Example 1 except that 3.2 g and 37.9 g of optically active 1-methylheptyl 4′-hydroxybiphenyl-4-carboxylate were used. This diene compound exhibits liquid crystallinity and exhibits the following phase transition behavior and physical property values. Response time: 25 μs (52 ° C) Tilt angle (2θ): 81 ° (52 ° C)

-Polyaddition reaction-A target copolymer was obtained by the same method and conditions as in Synthesis Example 1 except that the diene compound (5) obtained above was used.

Liquid crystalline copolymer [3]

[Chemical 36] Weight average molecular weight Mw = 4100 Tilt angle 2θ = 82 °

Synthesis Example 3 Synthesis of Liquid Crystalline Copolymer [3]

[Chemical 37] Diene compound (4) except that the synthesis reaction was carried out by using 1-methylheptyl 4-hydroxybenzoate in the same molar amount in place of 1-methylheptyl 4'-hydroxybiphenyl-4-carboxylate in the synthesis. Was carried out in the same manner as in.

-Polyaddition Reaction- In 14 ml of dry toluene, the diene compound (4) [1.82 g (2.66 mmol)] and the diene compound (6) [0.18 g (0.30 mmol)] obtained above were added. And 1,1,3,3-tetramethyldisiloxane 0.26 g
(1.94 mmol) was stirred while flowing an argon gas and uniformly dissolved. Next, chloroplatinic acid hexahydrate 2.0
After adding mg, the mixture was heated and stirred at 80 ° C. for 20 hours. During stirring, a very small amount of argon gas was kept flowing so that moisture and oxygen did not enter the reaction vessel. After the polymerization reaction,
The reaction mixture was filtered, and toluene was distilled off from the filtrate. The obtained residue was diluted with 3 g of methylene chloride, separated and purified by column chromatography using silica gel as a packing material to obtain a target copolymer. Yield is 1.7
It was 4 g.

Liquid crystalline copolymer [4]

[Chemical 38] Weight average molecular weight Mw = 3800 Tilt angle 2θ = 76 ° Synthesis Example 4 Synthesis of liquid crystalline copolymer [4]

[0049]

[Chemical Formula 39] 15.0 g (4) of the carboxylic acid derivative (3) obtained in Synthesis Example 1
0.0 mmol), 9.52 g of thionyl chloride (80.0
(50 mmol) and 50 ml of dry toluene were charged into a flask and stirred to obtain a uniform solution. Next, pyridine 0.02m
1 was added and stirred to obtain a uniform solution. Then, the temperature was raised to 65 ° C., and the mixture was heated and stirred for 4 hours. Then, toluene and excess thionyl chloride were distilled off under reduced pressure, and 130 ml of toluene and 3.60 g of pyridine were added. Then, 7.86 g (35.4 mmol) of 1-n-hexyl 4-hydroxybenzoate dissolved in 130 ml of toluene was added dropwise over 30 minutes. Then, it stirred at room temperature for 18 hours. The reaction mixture was filtered and concentrated, and the target compound was obtained by column chromatography using silica gel and alumina as a packing material. Yield is 1
It was 4.7 g.

-Polyaddition reaction- In 20 ml of dry toluene, 2.45 g (3.82 mmol) of the diene compound (4) obtained above and 0.55 g (0.95 mmol) of the diene compound (7) and 1,1 ，
0.43 g (3.1 of 3,3-tetramethyldisiloxane)
(8 mmol) was stirred while flowing argon gas and uniformly dissolved. Next, 2.5 mg of chloroplatinic acid hexahydrate was added, and the mixture was heated with stirring at 80 ° C. for 20 hours. During stirring, a very small amount of argon gas was kept flowing so that moisture and oxygen did not enter the reaction vessel. After the polymerization reaction was completed, the reaction mixture was filtered, and toluene was distilled off from the filtrate. The obtained residue was diluted with 3 g of methylene chloride, separated and purified by column chromatography using silica gel as a packing material to obtain a target copolymer. The yield was 2.84g.

Low molecular weight liquid crystal compound A

[Chemical 40]

Low molecular weight liquid crystal compound B

[Chemical 41]

Low molecular weight liquid crystal compound C

[Chemical 42]

Low molecular weight liquid crystal compound D

[Chemical 43]

Low Molecular Weight Liquid Crystal Compound E Mixed Liquid Crystal ZLI-4655-100 manufactured by Merck & Co., Inc. (Ch: cholesteric phase)

Low molecular weight liquid crystal compound F

[Chemical 44] (N: nematic phase, SmC: smectic C
phase)

Low molecular weight liquid crystal compound G

[Chemical 45]

Low molecular weight liquid crystal compound H

[Chemical 46]

Tables 1 and 2 show the phase transition temperature, electric field response time τ _10-90 and tilt angle 2θ of the obtained liquid crystal composition. Here, the electric field response time τ _10-90 is _2μ under crossed Nicols.
The time required for the amount of change in the amount of transmitted light to reach 10% to 90% when a voltage of ± 10 V was applied to the m cell was taken as the measured value at room temperature of 25 ° C. Also, the tilt angle 2θ changes the extinction position under crossed Nicols at room temperature 25 ° C.
It was taken as the measured value when measured in.

Examples 13 to 17 In the same manner as in Example 1, as shown in Table 2, a liquid crystal composition composed of one liquid crystal copolymer and a plurality of low molecular weight liquid crystal compounds and exhibiting a ferroelectric liquid crystal phase was prepared. It was made. The results are shown in Table 2.

Examples 18 to 20 In the same manner as in Example 1, as shown in Table 3, liquid crystal compositions comprising a plurality of liquid crystalline copolymers and one low molecular weight liquid crystal compound and exhibiting a ferroelectric liquid crystal phase were prepared. It was made. The results are shown in Table 3.

Example 21 In the same manner as in Example 1, as shown in Table 3, a liquid crystal composition comprising a plurality of liquid crystal copolymers and a plurality of low molecular weight liquid crystal compounds and exhibiting a ferroelectric liquid crystal phase was prepared. .. The results are shown in Table 3.

Examples 22 to 23 In the same manner as in Example 1, as shown in Table 3, a liquid crystal composition consisting of one liquid crystalline copolymer and one low molecular weight liquid crystal compound and showing an antiferroelectric liquid crystal phase. Was produced. The results are shown in Table 3.

[0064]

[Table 1]

[Table 2]

[Table 3]

Example 24 The liquid crystal composition prepared in Example 11 was mixed with 4% by weight of black dye NKX-1033 manufactured by Nihon Sensitive Dye, and the phase transition temperature of the obtained liquid crystal composition was as follows. It was The electric field response time τ _10-90 of this liquid crystal composition was 11.
The tilt angle 2θ was 0 ° and the tilt angle 2θ was 71 °.

Example 25 When 5% by weight of a black dye LCD-465 manufactured by Nippon Kayaku was mixed in the liquid crystal composition prepared in Example 14, the phase transition temperature of the obtained liquid crystal composition was as follows. It was The electric field response time τ _10-90 of this liquid crystal composition is 9 m.
and the tilt angle 2θ was 64 °.

Example 26 The liquid crystal composition prepared in Example 3 was mixed with 20% by weight of toluene.
As a solution, using a micro gravure coater, a PES (polyethersulfone) substrate with ITO electrodes made by Sumitomo Bakelite (width 150 mm, thickness 100 μm, length 20)
The solution was applied to the ITO electrode surface of m). The thickness of the liquid crystal layer after evaporation of the solvent was about 2.5 μm. Then, a similar substrate not coated with anything is laminated using two rolls (width 200 mm, diameter 80 mm made of silicon rubber and iron) so that the ITO electrode surface is in contact with the liquid crystal layer, An unoriented element was used. Furthermore, the unorientation element 1 was subjected to an orientation treatment using a bending orientation device composed of three rolls 3 (iron having a width of 200 mm and a diameter of 100 mm) as shown in FIG. 1 to obtain an orientation element 2. Here, the line speed is v = 8m
/ Min, the surface temperature of each roll is T ₁ = 110 ° C., T ₂ = 90
C. and T ₃ = 85 ° C. After this alignment treatment, a length of 20 cm was cut out from a long alignment element to obtain a desired liquid crystal display element. When this was placed between orthogonal polarizing plates and a DC voltage of ± 10 V was applied between the electrodes at 25 ° C., black and yellow were changed, and the contrast ratio was about 110. In a bright state, that is, when the color was yellow, the color was extremely uniform over the entire surface of the liquid crystal display element.

Comparative Example 1 Using only the low molecular weight liquid crystal compound B, a device was formed in the same manner as in Example 26, and an alignment treatment was performed. Orientation condition is v = 8m /
Min, T ₁ = 100 ° C., T ₂ = 85 ° C., T ₃ = 80 ° C. The thickness of the liquid crystal layer was about 2 μm. Then, a length of 20 cm was cut out in the same manner as in Example 26, placed between orthogonal polarizing plates, and a DC voltage of ± 10 V was applied between the electrodes at 25 ° C., and black and light yellow were changed, and the contrast ratio was changed. Was 30. In addition, dark yellow and white mottled parts were observed in the light yellow of the bright state, and it was clear that the film thickness was not uniform. In addition, a large number of zigzag defects were observed under a polarizing microscope, and it was found that the liquid crystal compound had a low orientation even though the liquid crystal layer was thinner than the liquid crystal display element obtained in Example 26. From the above, Example 26 containing only 20% by weight of the liquid crystalline copolymer
It is clear that even in the case of the liquid crystal composition prepared in (1), a sufficiently high film-forming property and orientation can be obtained as compared with the case of using only the low molecular weight liquid crystal compound.

Example 27 The liquid crystal display device manufactured in Example 26 was bent at room temperature (25 ° C.) in a direction perpendicular to the bending direction during the alignment treatment, and the liquid crystal composition had a radius of curvature of 4 cm. Orientation was destroyed. Then, PMMA (polymethylmethacrylate, manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 120,000) was added to the liquid crystal composition in an amount of 5% by weight to prepare a 20% by weight toluene solution in the same manner as in Example 26, using the same method as in Example 26, A liquid crystal display device was produced under the same alignment conditions. The contrast ratio of the obtained liquid crystal display device was 95. Also,
When this liquid crystal display element was bent in a direction perpendicular to the bending direction during the alignment treatment, the alignment of the liquid crystal composition was maintained until the radius of curvature reached 2 cm. From this fact, when the liquid crystal display device has insufficient strength, such as when the fraction of the polymer liquid crystal in the liquid crystal composition is small, a small amount of a non-liquid crystal polymer substance is mixed so that the contrast is not significantly reduced. It has been revealed that the strength of the liquid crystal display device can be improved.

Example 28 9.2 g of the liquid crystal composition prepared in Example 17 and 0.8 g of PMMA (polymethyl methacrylate, manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 120,000) as a thermoplastic resin were added to 30 g of dichloromethane. 25 wt% solution,
Striped PES substrate with ITO electrode (width 300m
m, thickness 100 μm, length 10 m) ITO
The electrode surface was coated with a microgravure coater. After evaporation of the solvent, a pair of pressure rolls (width 500 mm, diameter 80 m
IT made of chrome-plated iron and rubber)
A substrate of the same kind in which the stripe direction of the O electrode was perpendicular was laminated so that the ITO electrode surface was in contact with the liquid crystal layer. The thickness of the liquid crystal layer was about 3 μm. Immediately thereafter, a uniaxial orientation treatment was carried out by a bending orientation apparatus composed of three rolls shown in FIG. Here, all the rolls were made of chrome-plated iron with a diameter of 80 mm, and the roll interval was 1 mm. Further, the line speed was v = 2 m / min, and the surface temperature of each roll was T ₁ = 90 ° C., T ₂ = 80 ° C., T ₃ = 80 ° C., and the liquid crystal composition was rapidly transformed into an isotropic phase by the first roll. Bending deformation was given while heating and further cooling with the second and third rolls to the SmA phase. By this alignment treatment, a horizontal alignment state was obtained in which the smectic layer normal of the liquid crystal composition was in the vertical direction of the liquid crystal display element, that is, in the axial direction of the roll.

After the main alignment treatment, about 5 minutes after the adhesive was cured from the long alignment element, two pieces each having a length of 800 mm were cut out, and the two liquid crystal display elements were sandwiched between parallel polarizing plates. An information display body as shown in FIG. 2 was constructed. In this information display body, a liquid crystal display element 5, an antenna unit 6, a receiving circuit 7, a drive circuit 8 and a solar cell 9 are integrated, and the entire information display body is put together by a protective case 4 made of plastic. The display area of the display portion formed by the two liquid crystal display elements 5 is 600 mm × 800 mm. The antenna portion 6 is composed of a shortened dipole antenna, and has a thickness of 5 mm provided by copper foil on a sheet-shaped flat surface made of polyimide. The signal from the antenna unit 6 is connected to the receiving circuit 7 and further transmitted to the drive circuit 8, and information is displayed on the liquid crystal display element 5 by the drive signal from the drive circuit 8 according to the signal. Further, a commercially available product made of amorphous silicon was used for the solar cell 9 serving as a power source. The voltage is 4.5
It is V.

When an attempt was made to display with this information display,
It was confirmed that it works well not only outdoors but at the brightness of the fluorescent lights in the room at night. A contrast of 20 or more was secured with the reflection type. In addition, since a thin ferroelectric polymer liquid crystal display element is used and the alignment direction (direction of the smectic layer normal) is set to the vertical direction, it is excellent in visibility from an oblique side,
A contrast of 10 or more could be secured up to ± 80 °, and there was no change in the dark blue display color.

The weight of this information display body is only 2.1 kg, and the overall size is 800 mm × 1000 mm × 20 m.
It is very lightweight and thin. Next, when the information display body was set at 90 ° in the horizontal direction and the visibility from the lateral direction was examined in the same manner, the contrast of 10 at an angle of ± 40 ° or more was observed.
The display color gradually changed from blue to light brown. From this, it was clear that it is preferable for the information display body to have the alignment direction in the vertical direction of the liquid crystal display element.

Example 29 Using the ferroelectric polymer liquid crystal composition produced in Example 1, an information display body as shown in FIG. 3 was manufactured as a prototype. The manufacturing method of the liquid crystal display element was the same as in Example 26. The liquid crystal display device was oriented so that the smectic layer normal of the liquid crystal composition was in the vertical direction of the liquid crystal display device.

The protective case 4 has a diameter of 1500 mm and a height of 4
It had a cylindrical shape of 00 mm, the liquid crystal display element 5 was provided on the side surface thereof, and the antenna section 6 including a diversity antenna and the solar cell 9 were provided on the upper portion. Also, a receiving circuit and a driving circuit were installed inside the cylindrical case. 10 is a leg.

When information was displayed on this information display, sufficient display was possible outdoors and indoors. Further, since the flexible substrate is used, it is possible to display on a curved surface as in this embodiment, and it is possible to perform versatile display with an unexpectedness. Further, since the alignment direction of the liquid crystal composition was the vertical direction of the liquid crystal display element, the visibility from the horizontal direction was excellent, and even though it was a curved surface, all the displayed characters could be recognized and there was no color unevenness.

Furthermore, since the power consumption was very small as a whole, the solar cell was manufactured by Kimoto Co., Ltd.
It was replaced with (film type battery 54 mm x 85 mm x 0.5 mm), but it operated for more than one year. The weight of the information display body excluding the legs was as light as about 1.8 kg.

Liquid crystalline copolymer [5]

[Chemical 47] Weight average molecular weight Mw = 2800 Tilt angle 2θ = 74 °

Synthesis Example 5 Synthesis of Liquid Crystalline Copolymer [5] -Polyaddition Reaction-As a silane compound, 1,1,3,3,5,5,7,7-
A target copolymer was obtained by the same method and conditions as in Synthesis Example 1 except that 1.14 g of octamethyltetrasiloxane was used.

Liquid crystalline copolymer [6]

[Chemical 48] Weight average molecular weight Mw = 2600 Tilt angle 2θ = 83 °

Synthesis Example 6 Synthesis of Liquid Crystalline Copolymer [6] -Polyaddition Reaction-Diene compound (5) obtained in Synthesis Example 2 as a diene compound.
4.07 g, 1,1,3,3,5, as a silane compound
5,7,7-octamethyltetrasiloxane 1.14 g
A target copolymer was obtained by the same method and conditions as in Synthesis Example 1 except that was used.

Low Molecular Weight Liquid Crystal Compound I Mixed Liquid Crystal CS-1015 manufactured by Chisso Corporation

Low molecular weight liquid crystal compound J

[Chemical 49] Sx: unidentified smectic phase (because it is an unstable phase, measurement was performed while changing the temperature at 2 ° C./min).

Low molecular weight liquid crystal compound K

[Chemical 50] Low molecular liquid crystal compound L

[Chemical 51]

Examples 30 to 34 In the same manner as in Example 1, as shown in Table 4, a liquid crystal composition consisting of one liquid crystalline copolymer and one low molecular weight liquid crystal compound and exhibiting a ferroelectric liquid crystal phase was prepared. It was made. The results are shown in Table 4.

Examples 35 to 38 In the same manner as in Example 1, as shown in Table 4, a liquid crystal composition comprising one liquid crystalline copolymer and a plurality of low molecular weight liquid crystal compounds and exhibiting a ferroelectric liquid crystal phase was prepared. It was made. The results are shown in Table 4.

Examples 39 to 41 In the same manner as in Example 1, as shown in Table 4, a liquid crystal composition comprising a plurality of liquid crystalline copolymers and one low molecular weight liquid crystal compound and exhibiting a ferroelectric liquid crystal phase was prepared. It was made. The results are shown in Table 4.

Example 42 In the same manner as in Example 1, a liquid crystal composition showing a ferroelectric liquid crystal phase composed of a plurality of liquid crystal copolymers and a plurality of low molecular weight liquid crystal compounds as shown in Table 4 was prepared. .. The results are shown in Table 4.

[Table 4]

As shown in Tables 1 to 4, the film-forming property was improved by the combination of the liquid crystal copolymer having a side chain type polymer liquid crystal having an alkyl chain and a siloxane chain as the main chain and a low molecular weight liquid crystal compound. A composition having excellent orientation and fast electric field response was easily obtained.

When a low-molecular liquid crystal compound having the same structure as the mesogen group of the liquid crystalline copolymer contained in the liquid crystal composition in the molecule is used, the tilt angle 2θ is not significantly reduced and the high-speed electric field is not increased. Responsiveness was realized.

[0091]

INDUSTRIAL APPLICABILITY The liquid crystal composition of the present invention operates in a wide temperature range including room temperature, has high alignment properties with respect to film-forming properties and mechanical alignment methods such as bending alignment, and is resistant to changes in electric field. It responds at high speed. Further, the information display body of the present invention can display a large area and a curved surface, and can display a variety of contents with a simple drive control circuit,
It is resistant to mechanical shock and does not require an external power supply, and can be made thinner and lighter.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing an alignment device used in Examples.

FIG. 2 is a perspective explanatory view showing a configuration of an information display body manufactured in Example 28.

FIG. 3 is a perspective explanatory view showing a configuration of an information display body manufactured in Example 29.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Non-oriented element 2 Oriented element 3 Roll 4 Protective case 5 Liquid crystal display element 6 Antenna part 7 Receiver circuit 8 Drive circuit 9 Solar cell 10 Leg part

Claims (13)

[Claims] 1. A repeating unit [I] represented by the following general formula: {In the formula, a and b are integers of 2 to 5, d is an integer of 0 to 3,
e is an integer of 1 to 20, and R ¹ is Is. However, R ² is —COOR ³ , —OR ³ or —OCOR ³ , and R ³ is And R ⁴ and R ⁵ are a methyl group or a halogen atom,
f is an integer of 0 to 10, g is 0 or 1 and h is an integer of 1 to 11 (when R ⁵ is a methyl group, h is not 1), and * represents an asymmetric carbon atom. } The liquid crystal copolymer or the repeating unit represented by the following general formula [I
I] and [III] {Wherein a, b, d and e are the same as above, and j is 0
Is an integer of 3 to 3, k is an integer of 2 to 7, and R ⁶ is represented by the general formula [I
V] or an optically active alkyl group represented by the general formula [V]
An optically inactive alkyl group represented by: (However, m in the formula is an integer of 0 to 3, n is an integer of 2 to 7, and * represents an asymmetric carbon atom.). } And the molar ratio of repeating units [II] and [III] ([I
[I] / [III]) is a liquid crystalline copolymer containing (1/99) to (99/1) and a low molecular weight liquid crystal compound, wherein the liquid crystalline copolymer and the low molecular weight compound are included. The ratio of the liquid crystalline copolymer to the total of the liquid crystal compound is 5 to 99% by weight.
Which is a liquid crystal composition. 2. The liquid crystal composition according to claim 1, wherein the liquid crystal composition exhibits a ferroelectric liquid crystal phase or an antiferroelectric liquid crystal phase. 3. The liquid crystal composition according to claim 1, wherein the low molecular weight liquid crystal compound has the same structure in the molecule as the mesogen group of the liquid crystalline copolymer contained in the liquid crystal composition. 4. The liquid crystalline copolymer is composed of repeating unit [I], and R ¹ is Wherein the low molecular weight liquid crystal compound is a tricyclic monomer constituting the repeating unit [I] of the liquid crystalline copolymer, and has the following general formula: Is. ) The liquid crystal composition according to claim 1, which is represented by 5. The liquid crystalline copolymer has a repeating unit [II].
And [III], the low molecular weight liquid crystal compound is a tricyclic monomer constituting the repeating unit [II] of the liquid crystalline copolymer, and has the following general formula: The liquid crystal composition according to claim 1, which is represented by: 6. The liquid crystal composition according to claim 1, wherein the liquid crystal composition has dichroism. 7. The liquid crystal composition according to claim 1, wherein the liquid crystal composition contains a non-liquid crystal polymer substance. 8. A liquid crystal display device comprising the liquid crystal composition according to claim 1 sandwiched between flexible substrates with electrodes, a receiver for receiving display contents of the liquid crystal display device from outside by a radio signal, and a receiver. An information display body comprising: a drive circuit that drives a liquid crystal display element in response to a signal; and a power supply unit that supplies power to the drive circuit. 9. The information display body according to claim 6, wherein the liquid crystal display element is subjected to horizontal alignment treatment so that the smectic layer normal of the liquid crystal composition is in the vertical direction of the liquid crystal display element. 10. The information display body according to claim 6, wherein the liquid crystal display element has a curved display surface. 11. The information display body according to claim 6, comprising a plurality of liquid crystal display elements. 12. The information display unit according to claim 6, wherein the power supply unit is a solar cell or a thin film battery. 13. The information according to claim 6, wherein the receiving portion comprises an antenna portion and a receiving circuit, and the antenna portion has a thickness of 10 mm or less formed by forming a conductor on a flat or curved dielectric sheet. Display body.