WO2008053800A1 - Liquid crystal containing liquid-crystal-compatible particles and liquid-crystal display - Google Patents

Abstract

A liquid crystal containing liquid-crystal-compatible particles which can be operated in the duty mode even in a low-temperature region; and a liquid-crystal display employing the liquid crystal. The liquid crystal containing liquid-crystal-compatible particles contains liquid-crystal-compatible particles obtained by adding a solution of ions of at least one metal to a mixture solution comprising molecules of at least one liquid crystal, a secondary alcohol represented by the following general formula (1), and an organic solvent with refluxing to react them. The liquid-crystal display is provided with a liquid-crystal cell having, enclosed therein, the liquid crystal containing liquid-crystal-compatible particles. (In the formula, R1 and R2 may be the same or different and each represents an optionally substituted hydrocarbon group, provided that R1 and R2 may be bonded to each other to form a ring.)

Description

 Specification

 Liquid crystal compatible particle-containing liquid crystal and liquid crystal display device

 Technical field

 The present invention relates to a liquid crystal containing liquid crystal compatible particles and a liquid crystal display device using the liquid crystal, for example, a liquid crystal display device used as a display panel for automobiles.

 Background art

 [0002] Conventionally, liquid crystal-compatible particles are known in which liquid crystal molecules are bonded around a nucleus composed of metal nanoparticles such as palladium nanoparticles having a diameter in the range of 0.5 to; OOnm. Yes. The liquid crystal compatible particles can be produced, for example, by irradiating a solution obtained by dissolving a palladium salt such as palladium nitrate and liquid crystal molecules in a solvent such as ethanol with ultraviolet rays to reduce the palladium salt. (See Japanese Unexamined Patent Publication No. 2003-149683).

 [0003] The liquid crystal compatible particles are dissolved or dispersed in a matrix liquid crystal to form liquid crystal compatible particle-containing liquid crystal, and the liquid crystal cell of the liquid crystal display device is configured by using the liquid crystal compatible particle-containing liquid crystal. The amount of light transmission can be changed depending on the frequency of the voltage applied to the liquid crystal display device. The liquid crystal material exhibiting drive frequency dependency has a problem in that the threshold is! /, The value is frequency dependent, and therefore the duty is driven when the duty is driven! /, And the display unevenness due to the value unevenness occurs!

 In addition, the liquid crystal compatible particle-containing liquid crystal containing the liquid crystal compatible particles has a high viscosity in a low temperature region of 0 ° C. or less, for example, when a liquid crystal cell of a liquid crystal display device is configured. There is an inconvenience that it is difficult to perform drive display.

 [0005] Furthermore, not only the nanoparticle-added liquid crystal display device, but all liquid crystal display devices have a disadvantage that the "response" becomes slow at low temperatures. In particular, with DUTY drive, a sufficient voltage difference cannot be applied to the liquid crystal, so the overall response tends to be slow, and the effect of low temperature response degradation is serious.

 Disclosure of the invention

 Problems to be solved by the invention

[0006] The present invention eliminates such inconvenience and configures a liquid crystal cell of a liquid crystal display device. It is an object to provide a liquid crystal-compatible particle-containing liquid crystal capable of high-speed and DUTY drive display even in a low temperature region of 0 ° C. or lower.

[0007] Another object of the present invention is to provide a liquid crystal display device using the liquid crystal containing the liquid crystal compatible particles.

 Means for solving the problem

In order to achieve this object, the liquid crystal-compatible particle-containing liquid crystal of the present invention comprises at least one liquid crystal molecule, a secondary alcohol represented by the following general formula (1), and an organic solvent. Liquid crystal compatible particles obtained by adding and reacting at least one metal ion solution while refluxing the mixed solution obtained by mixing, wherein the metal nano particles are obtained by reducing the metal ions. Liquid crystal compatible particles comprising particles and the liquid crystal molecules bonded around the metal nanoparticles with the metal nanoparticles as nuclei are characterized by comprising.

(Wherein R ¹ and R ² represent a hydrocarbon group which may be the same or different and may have a substituent. Note that R ¹ and R ² are bonded to each other. The liquid crystal compatible particles in the present invention have a plurality of metal particles produced by reduction of one or more kinds of metal ions as a central core, and liquid crystal molecules are somehow around them. It is presumed to have a structure that is surrounded by interaction. The central core composed of a plurality of metal particles may have a random alloy structure in which a plurality of types of metal particles are randomly distributed, or one type of metal particle as a shell and another type of metal particle as a shell. It may have a core-shell structure as a core. The case of one type of metal particles is called a single particle, and the case of two types of metal particles is called a binary particle.

[0010] The metal nanoparticles have a particle size of 40 nm or less, and most of them are 5 nm or less, and are sufficiently smaller than the wavelength of light. Therefore, optical properties such as transmittance (refractive index), color tone, and sharpness of a liquid crystal display device are used. Does not affect properties. On the other hand, it is thought that the liquid crystal compatible particles containing the metal nanoparticles in the matrix liquid crystal can affect the physical properties of the liquid crystal display device such as dielectric anisotropy, elastic constant and viscosity coefficient. It is done. As a result, when the liquid crystal-compatible particle-containing liquid crystal of the present invention is used in a liquid crystal cell of a liquid crystal display device, the frequency dependency of the threshold value in the voltage-transmittance characteristic is reduced, and the DUT Y drive display is enabled At the same time, it is possible to achieve high response speed, high V, and contrast in the low temperature range below 0 ° C.

 [0012] The reason why the response speed becomes high is that, in the rise characteristics, the metal nanoparticles exhibit an increase in the dielectric constant of the entire system (that is, the Maxwell-Wagner effect) in the driving frequency region of several hundred Hz, and in particular, the molecules stand up. As the dielectric anisotropy Δε increases as the top rises, the rotational torque of the liquid crystal molecules Δ 8 Ε2 force S increases, and the elastic constant changes due to the metal nanoparticles entering between the liquid crystals. Conceivable. On the other hand, with respect to the falling characteristics, it is conceivable that the viscosity coefficient decreases due to the addition of the metal nanoparticles.

 [0013] Improvement of LC performance by improving liquid crystal materials has reached its limit, and the present invention in which the metal nanoparticles are monodispersed in a liquid crystal that is an organic liquid is one of the new breakthroughs. Be expected.

 [0014] In the liquid crystal compatible particle-containing liquid crystal of the present invention, the mixed solution is preferably refluxed at a temperature in the range of 30 to 200 ° C, and is refluxed at a temperature in the range of 40 to 150 ° C. It is particularly preferred that

In the liquid crystal-compatible particle-containing liquid crystal of the present invention, examples of the metal ions include Au ⁺ , Au ³⁺ , Ag ⁺ , Cu +, Cu ²⁺ , Ru ²⁺ , Ru ³⁺ , Ru ⁴⁺ , Rh ²⁺ , Rh ³⁺ , Pd ²⁺ , P d ⁴⁺ , Os ⁴⁺ , Ir ⁺ , Ir ³⁺ , Pt ²⁺ , Pt ⁴⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ And at least one metal ion selected from the group consisting of Co ³⁺ .

 [0016] Further, examples of the liquid crystal compatible particles obtained by the reaction of the metal ions include those having nucleus of silver-silver binary nanoparticles as a nucleus. The palladium-silver binary nanoparticles preferably contain silver in an amount of 0.05% by weight or less based on the total liquid crystal-compatible particle-containing liquid crystal. When the palladium-silver binary nanoparticles contain more than 0.05% by weight of silver based on the total liquid crystal compatible particle-containing liquid crystal, the liquid crystal compatible particle-containing liquid crystal of the present invention is used in a liquid crystal cell of a liquid crystal display device. In addition, the frequency dependency may increase, and the duty drive display may become difficult.

Furthermore, the liquid crystal-compatible particle-containing liquid crystal of the present invention is the entire liquid crystal-compatible particle-containing liquid crystal. It is preferable to contain the liquid crystal compatible particles in an amount in the range of 0.001 to 0.5% by weight relative to the liquid crystal compatible particles in an amount in the range of 0.002 to 0.2% by weight. It is particularly preferable to contain it.

 Next, a liquid crystal display device of the present invention is characterized by comprising a liquid crystal cell in which liquid crystal containing liquid crystal compatible particles containing the liquid crystal compatible particles is enclosed.

 [0019] According to the liquid crystal display device of the present invention, by using the liquid crystal containing liquid crystal compatible particles, the frequency dependency is reduced in a low temperature region of 0 ° C or lower, and DUTY drive display becomes possible. At the same time, high! /, High response speed and high contrast can be demonstrated.

 In the liquid crystal display device of the present invention, the liquid crystal cell preferably contains a chiral agent together with the liquid crystal containing the liquid crystal compatible particles. The liquid crystal cell can adjust the twist angle of the liquid crystal-compatible particle-containing liquid crystal by containing the chiral agent.

Yes

[0021] In the liquid crystal display device of the present invention, it is preferable that the twist angle of the liquid crystal containing the liquid crystal compatible particles in the liquid crystal cell is in the range of 180 to 270 °. The twisted angle of less than 180 ° there is a problem with the steepness of the transmittance change (sharpness) is poor with respect to voltage, problems force ^s with hysteresis on the voltage one transmittance characteristic exceeds 270 ° occurs.

 [0022] In the liquid crystal display device of the present invention, as the liquid crystal compatible particles, for example, those having nucleus of silver and silver binary nanoparticles as a core can be used.

 [0023] Further, the liquid crystal display device of the present invention is, for example, a dot matrix panel using DUTY driving.

 BEST MODE FOR CARRYING OUT THE INVENTION

Next, embodiments of the present invention will be described in more detail with reference to the accompanying drawings. FIG. 1 is an explanatory cross-sectional view showing a structural example of the liquid crystal display device of the present invention. FIG. 2 is a graph showing voltage-transmittance characteristics in the liquid crystal display device of the first embodiment of the present invention, FIG. 3 is a photograph of the appearance when an image is displayed on the liquid crystal display device, and FIG. FIG. 5 is a micrograph of a liquid crystal cell of the liquid crystal display device immediately after the image is displayed on the liquid crystal display device and the image is switched at 10 ° C. FIG. 6 is a comparative example with respect to the embodiment. It is a microscope picture of the liquid crystal cell of the liquid crystal display device. FIG. 7 is a graph showing the voltage transmittance characteristics in the liquid crystal display device of the second embodiment of the present invention, FIG. 8 is a micrograph of the liquid crystal cell of the liquid crystal display device, and FIG. 6 is a micrograph of a liquid crystal cell of a liquid crystal display device of a comparative example. FIG. 10 is an explanatory sectional view showing another configuration example of the liquid crystal display device of the present invention. FIG. 11 is a graph showing the temperature dependence of responsiveness when DUTY driving is performed in the liquid crystal display device of the third embodiment of the present invention. FIGS. 12 to 15 are graphs showing voltage-transmittance characteristics in the liquid crystal display devices of the fourth to seventh embodiments of the present invention. FIG. 16 is a graph showing voltage-transmittance characteristics in a liquid crystal display device according to a reference example of the present invention, and FIG.

 The liquid crystal display device of the present invention includes, for example, a super twist nematic (STN) LCD, a twist

) Can be used for various liquid crystal display devices such as LCD and polymer network type (PN) LCD 1S Simple matrix display device in STN mode or TN mode, TN mode, IPS mode, especially when used as a liquid crystal display device for vehicles It is preferable to use an active matrix (TFT, etc.) display device by using!

 In the present embodiment, as shown in FIG. 1, a case of a super twist nematic liquid crystal display device (ST N—LCD) 1 will be described. The liquid crystal display device 1 of this embodiment includes a pair of parallel and transparent glass substrates 2a and 2b, and transparent electrode films 3a and 3b provided in a predetermined pattern on the inner surfaces of the glass substrates 2a and 2b facing each other. And the insulating films 4a and 4b provided on the inner surface facing each other of the transparent electrode films 3a and 3b and the inner surfaces facing each other of the insulating films 4a and 4b are substantially the same as the transparent electrode films 3a and 3b. Alignment films 5a and 5b provided in the following pattern. The transparent electrode films 3a and 3b are provided in stripes orthogonal to each other.

 In the liquid crystal display device 1, the upper substrate 6a is formed by the glass substrate 2a, the transparent electrode film 3a, the insulating film 4a, and the alignment film 5a. The glass substrate 2b, the transparent electrode film 3b, the insulating film 4b, and the alignment film An upper substrate 6b is formed by 5b, and a liquid crystal cell 7 in which liquid crystal L containing liquid crystal compatible particles is sealed is formed between the upper and lower substrates 6a and 6b.

The alignment films 5a and 5b align the liquid crystal molecules enclosed in the liquid crystal cell 7 uniaxially and form an upper and lower substrate 6a. , 6b torsional angular force, for example, left-handed twist of 240 °. The liquid crystal cell 7 is sealed with a sealant layer 8, and a conductive material pattern 9 is formed on the outer surface of the sealant layer 8. Further, polarizing plates 10a and 10b are attached to the outer surfaces of the glass substrates 2a and 2b in a predetermined pattern.

In the liquid crystal display device 1, instead of the liquid crystal L containing liquid crystal compatible particles, liquid crystal molecules containing no liquid crystal compatible particles are sealed in the liquid crystal cell 7, and the twist angle between the upper and lower substrates 6 a and 6 b is, for example, 2 It is a two-layer configuration in which compensation cells (not shown) with exactly the same configuration are stacked, except that they are processed so as to have a right twist of 40 °. The liquid crystal display device 1 may include a compensation film instead of the compensation cell.

[0030] The liquid crystal display device 1 can be manufactured, for example, in the manner of 7 fires.

First, an ITO film is formed as a transparent electrode on the glass substrates 2a and 2b, and the transparent electrode films 3a and 3b are formed by forming a desired pattern in a photolithography process. Next, insulating films 4a and 4b are formed by flexographic printing on the display portions on the glass substrates 2a and 2b on which the transparent electrode films 3a and 3b are formed.

 The insulating films 4a and 4b are not necessarily formed, but are desirably formed to prevent a short circuit between the upper and lower transparent electrode films 3a and 3b. The insulating films 4a and 4b are not limited to flexographic printing, but may be formed by vapor deposition using a metal mask.

 Next, alignment films 5a and 5b having substantially the same pattern are formed on the insulating films 4a and 4b.

 In the case of STN—LCD, it is desirable that the alignment films 5a and 5b have a high pretilt angle (the tilt angle of the liquid crystal molecules from the substrate plane).

 Next, rubbing treatment is performed on the alignment films 5a and 5b. The rubbing treatment can be performed by rotating a cylindrical roll wound with cloth at high speed and rubbing the alignment films 5a and 5b. As a result of the rubbing treatment, the liquid crystal molecules sealed in the liquid crystal cell 7 can be aligned uniaxially so that the twisting angular force between the upper and lower substrates 6a and 6b is, for example, a left twist of 240 °.

[0035] Next, a sealant for bonding the upper and lower substrates 6a and 6b is printed in a predetermined pattern on the inner surface of the substrate 6a or the substrate 6b on one side, and the inside of the other substrate 6b or the substrate 6a is printed. Gap control agent is sprayed on the side by dry spraying method. Then, the upper and lower substrates 6a and 6b are overlapped at predetermined positions to form cells, and heat treatment is performed in a pressed state to perform sheeting. The sealing agent layer 8 is formed by curing the adhesive.

[0036] As the sealing agent, for example, a thermosetting sealing agent can be used, and the sealing agent may contain several weight percent of glass fiber having a size of 6 m. Further, instead of the thermosetting sealant, a photocurable sealant or a combined light / heat sealant may be used.

 [0037] The sealing agent may be printed using, for example, a force dispenser that can be used by a screen printing method. When the liquid crystal molecules L are injected into the liquid crystal cell 7 formed between the upper and lower substrates 6a and 6b, the printed pattern of the sealant is a pattern having an injection port when using the vacuum injection method, and a note when using the ODF method. A closed pattern with no entrance. As the gap control agent, for example, a force S which can use a plastic ball having a diameter of 6 m, and a silica ball may be used.

 Next, a conductive material is printed at a predetermined position on the outer surface of the sealing agent layer 8 to form a conductive material pattern 9. As the conductive material, for example, the thermosetting sealant (for example, product name: ES-7500, manufactured by Mitsui Chemicals, Inc.) containing several 11% by weight of 8-11 balls having a diameter of 6.5 111 is used. I can do it. The conductive material is printed by force S, for example, by screen printing.

 [0039] Next, the glass substrates 2a and 2b are scratched by a scriber device, and divided into a predetermined size 'shape by breaking to form cells, and liquid crystal molecules L are injected into the cells. The liquid crystal molecule L can be injected by, for example, a vacuum injection method. In this case, the injection port is sealed with an end sealant.

 [0040] After that, chamfering and cleaning are performed, and the polarizing plates 10a and 10b are attached in a predetermined pattern on the outer surfaces of the glass substrates 2a and 2b, whereby a liquid crystal display device (ST N -LCD) You can get one.

 [0041] The compensation cell stacked on the liquid crystal display device 1 has a twisted angular force between the upper and lower substrates 6a and 6b of the liquid crystal molecules sealed in the liquid crystal cell 7 in the alignment films 5a and 5b, for example, a right twist of 240 °. The liquid crystal cell 7 can be manufactured in the same manner as the liquid crystal display device 1 except that the liquid crystal cell 7 is sealed and liquid crystal molecules containing no liquid crystal compatible particles are encapsulated.

[0042] Liquid crystal compatible particles enclosed in the liquid crystal cell 7 in the liquid crystal display device 1 of the present embodiment! The contained liquid crystal contains liquid crystal compatible particles in the matrix liquid crystal. The liquid crystal compatible particles contained in the liquid crystal compatible particle-containing liquid crystal are liquid crystal molecules bonded around a nucleus composed of metal nanoparticles, and include at least one liquid crystal molecule and the following general formula (1) While refluxing the mixed solution obtained by mixing the secondary alcohol represented by

It can be obtained by adding at least one metal ion solution and reacting them.

OH

(Wherein R ¹ and R ² represent a hydrocarbon group which may be the same or different and may have a substituent. Note that R ¹ and R ² are bonded to each other. The liquid crystal molecules used for obtaining the liquid crystal compatible particles include, for example, 4′-n-pentyl-4-cyanobiphenyl, 4′_n-hexyloxy-4-cyanobiphenyl. Cyanobiphenyls such as 4- (trans-4_n-pentylcyclohexyl) benzonitrile and the like; 4-butylbenzoic acid (4-cyanophenyl), 4-heptylbenzoic acid (4 Phenyl esters such as 4-cyanophenyl) carbonates such as 4-carboxyphenyl carbonate and 4-carboxyphenyl-n-butyl carbonate; 4- (4_n-pentylphenylethyl) ) Sianobenzene, 4- (4-n-pentyl) Phenylacetylenes such as nitrobenzene, benzene; phenylpyrimidines such as 2- (4-cyanphenyl) -5-n-pentylpyrimidine, 2- (4-cyanphenyl) -5-n-octylpyrimidine; Azazobenzenes such as 4'-bis (ethoxycarboninole) azobenzene; Azoxybenzenes such as 4,4, -azoxanisole, 4,4'-dihexylazoxybenzene; N- (4- Schiff bases such as methoxybenzylidene) -4-n-butylaniline and N- (4-ethoxybenzylidene) -4-n-butylaniline; benzidines such as Ν, Ν'-bisbenzylidenebenzidine; cholesteryl acetate, cholesteryl Examples thereof include cholesteryl esters such as benzoate; and liquid crystal polymers such as poly (4-phenylene terephthalamide). In addition, you may use these liquid crystal molecules individually or in mixture of 2 or more types. When the liquid crystal molecules are used as a mixture of a plurality of types of liquid crystal molecules, commercially available products can be used as they are.

[0044] The secondary alcohol used to obtain the liquid crystal-compatible particles is a compound represented by the general formula ( Shown in 1). In the general formula (1), R ¹ and R ² are hydrocarbon groups which may have a substituent. Examples of the hydrocarbon groups include a methyl group, an ethyl group, a propyl group, and a butyl group. Alkyl group having 1 to 7 carbon atoms such as cyclopentyl group, hexyl group and heptyl group; cycloalkyl group having 3 to 5 carbon atoms such as cyclopropyl group, cyclobutyl group and cyclopentyl group; Forces that can include alkynyl groups having 2 to 5 carbon atoms such as nyl group, cyclopropenyl group, cyclobuturyl group, cyclopentur group, etc .; alkynyl groups having 2 to 5 carbon atoms such as etulyl group, propynyl group, etc. preferably alkyl Group, alkenyl group and alkynyl group, more preferably alkyl group and alkynyl group. The hydrocarbon group includes various isomers.

In addition, R ¹ and R ² may be bonded to each other to form an unsubstituted or substituted ring! /, And the ring formed by bonding includes, for example, a cyclopropyl ring Cycloalkyl rings having 3 to 6 carbon atoms such as cyclobutyl ring, cyclopentyl ring and cyclohexyl ring; ether rings having 2 to 5 carbon atoms such as oxylan ring, oxetane ring, tetrahydrofuran ring and tetrahydropyran ring. That power S. Each ring includes various isomers.

 [0046] The hydrocarbon group and the ring formed by bonding may have a substituent! /, And the substituent may be a substituent formed through a carbon atom or an oxygen atom. Can be mentioned substituents, halogen atoms and the like.

 [0047] Examples of the substituent formed through the carbon atom include an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group; and 3 to 4 carbon atoms such as a cyclopropyl group and a cyclobutyl group. A cycloalkyl group having 2 to 3 carbon atoms such as a bulu group, a linole group, a propenyl group, or a cyclopropenyl group; an alkynyl group having 2 to 3 carbon atoms such as an ethur group or a propynyl group; And a halogenated alkyl group having 1 to 4 carbon atoms such as a romethyl group; a cyano group. The substituent includes various isomers.

 [0048] Examples of the substituent formed through the oxygen atom include a hydroxyl group; an alkoxy group having 1 to 3 carbon atoms such as a methoxyl group, an ethoxyl group, and a propoxyl group. These groups include various isomers.

[0049] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. [0050] The amount of the secondary alcohol used is preferably 0.;! To 200 g, more preferably 1 to OOg, with respect to the liquid crystal molecule lg. In addition, the secondary alcohol may be used alone or in combination of two or more of the secondary alcohols.

 [0051] The organic solvent used for obtaining the liquid crystal compatible particles is not particularly limited as long as it does not inhibit the reaction. For example, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; Esters such as methyl, ethyl acetate, butyl acetate, methyl propionate; amides such as N, N, dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; N, N, monodimethylimidazolide Ureas such as non; sulfoxides such as dimethyl sulfoxide; sulfones such as sulfolane; nitriles such as acetonitrile and propionitryl; ethers such as jetyl ether, diisopropyl ether, tetrahydrofuran and dioxane; hexane , Heptane, cyclohexane and other aliphatic hydrocarbons; benzene, tolu The ability to mention aromatic hydrocarbons such as styrene and xylene, preferably nitriles, ethers and aromatic hydrocarbons, more preferably the ability to mention ethers S . As the organic solvent, either one of the above organic solvents may be used alone, or two or more may be used in combination.

 [0052] The amount of the organic solvent to be used is preferably in the range of 10 to 500 ml, more preferably in the range of 20 to 200 ml, with respect to the liquid crystal molecule lg.

[0053] The metal ion solution used for obtaining the liquid crystal compatible particles is obtained by dissolving a metal salt (a salt made of a metal ion and a counter ion) in an organic solvent. Examples of the metal ions include transition metal ions, preferably Au ⁺ , Au ³⁺ , Ag ⁺ , C

+ 2+ _π 2+ _π 3+ _π 4+ _π , 2+ _{π 1} 3+ _π , 2 + _π , 4+ „4+ _τ + _τ 3+ _π , 2 + u, Cu, Ru, Ru, Ru, Rn, Rn, Pd, Pd, Os, Ir, Ir, Pt

, Pt ⁴⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ can be cited as at least one metal ion selected from the group. On the other hand, the counter ions for the metal ions include, for example, hydride ions, halogen ions, halogen acid ions, perhalogenate ions, optionally substituted carboxylate ions, acetyl acetate toner ions, carbonate ions, sulfate ions. And nitrate ions, tetrafluoroborate ions, hexafluorophosphate ions, and the like. The metal salt is coordinated by a neutral ligand such as carbon monoxide, triphenylphosphine, p-cymene, etc. [0054] Examples of the organic solvent used for dissolving the metal ions include the organic solvent used for obtaining the liquid crystal compatible particles. The amount of the organic solvent used is not particularly limited as long as it can dissolve the metal salt completely.

 [0055] The reflux temperature (reaction temperature) when refluxing a mixed solution obtained by mixing at least one liquid crystal molecule, the secondary alcohol, and the organic solvent is not particularly limited. However, the temperature is preferably in the range of 40 to; 100 ° C., and the reaction pressure may be pressurized, normal pressure, or reduced pressure. In addition, when a plurality of types of metal ion solutions are added to the mixed solution, the addition method is not particularly limited. For example, a method of separately adding one type of metal ion solution separately (simultaneous addition or Divided addition), and a method of preparing and adding one kind of metal ion solution containing a plurality of kinds of metal ions in advance.

 [0056] According to the reaction, the metal ions can be reduced to obtain metal nanoparticles, and the liquid crystal molecules can be obtained by bonding the liquid crystal molecules with the obtained metal nanoparticles as nuclei. . Since the liquid crystal compatible particles are dispersed in the organic solvent to form a dispersion, it is possible to obtain a uniform liquid crystal compatible particle paste by concentrating the dispersion. The method for concentrating the dispersion is not particularly limited, but it is preferably performed at a temperature in the range of 20 to 100 ° C. under reduced pressure. Further, by adding the liquid crystal molecules to the dispersion again to obtain a dispersion, and concentrating the dispersion by a similar method, a higher performance and uniform liquid crystal compatible particle paste can be obtained. .

 [0057] The liquid crystal-compatible particle-containing liquid crystal can be obtained, for example, by adding the liquid crystal-compatible particle paste obtained as described above to the base liquid crystal while stirring at room temperature and making it uniform. it can. In addition, a chiral agent may be added to the liquid crystal-compatible particle-containing liquid crystal in order to adjust the twist angle.

 Next, examples and comparative examples of the present invention are shown.

 Example 1

 In this example, first, liquid crystal-compatible palladium-silver binary nanoparticle-containing liquid crystal (hereinafter sometimes referred to as liquid crystal (I)) was prepared as follows.

[0060] A 500 ml internal volume equipped with a stirrer, thermometer, reflux condenser and syringe pump. 4'-n-pentyl-4-cyanobiphenyl 1.32 g (5.29 mmol), 146.8 ml of tetrahydrofuran and 40 ml of 2 propanol are added to a glass container with a bucket at room temperature to prepare a mixed solution. The solution was heated with stirring and refluxed at a temperature in the range of 65-75 ° C. Next, 2.64 ml (containing 0.0264 mmol as silver atoms) of tetrahydrofuran solution of 0. Olmol / 1 silver trifluoroacetate is slowly added dropwise to the above mixed solution and reacted at the same temperature for 15 minutes with stirring. 0. 56 ml (containing 0.1566 mmol of palladium atom) of 0. Olmol / 1 palladium acetate in tetrahydrofuran was slowly dropped and reacted at the same temperature for another 15 minutes with stirring. After completion of the reaction, the reaction solution was cooled to room temperature to obtain 200 ml of a blackish brown uniform liquid crystal compatible palladium-silver binary nanoparticle dispersion. The liquid crystal-compatible palladium-silver binary nanoparticles have palladium-silver binary nanoparticles as nuclei, and liquid crystal molecules 4'-n-pentyl-4-cyanobiphenyl are bound around the nuclei.

[0061] Next, 71 ml of the liquid crystal compatible palladium silver binary nanoparticle dispersion obtained in this example was added to a mixture of plural kinds of liquid crystal molecules (Liquid for STN manufactured by Dainippon Ink & Chemicals, Inc., LC, Δη = 0 150, Viscosity (20 ° = 23 [111? £ 1 '3]) plus 0.9% by weight of chiral agent (Merck, product name: S811) 4. Add 53g, Concentration and drying under reduced pressure gave 4.88 g of gray uniform liquid crystal (1) (total amount of metal contained; 4.88 mg). The liquid crystal (I) comprises the liquid crystal molecule mixture as a matrix liquid crystal, and the matrix liquid crystal contains the liquid crystal compatible palladium-silver binary nanoparticles, and 0.02% by weight of silver atoms with respect to the total amount of the liquid crystal (I). , and a palladium atom of 0.08 weight ^_0/0.

 Next, a liquid crystal display device (STN—LCD) 1 shown in FIG. 1 was produced using the liquid crystal (I), and the characteristics were evaluated.

 A liquid crystal display device (STN—LCD) 1 was produced as follows. First, glass substrate

 An ITO film was formed as a transparent electrode on 2a and 2b, and a transparent electrode film 3a and 3b was formed by forming a desired pattern by a photolithography process. Next, insulating films 4a and 4b were formed by flexographic printing on the display portions on the glass substrates 2a and 2b on which the transparent electrode films 3a and 3b were formed.

Next, alignment films 5a and 5b having substantially the same pattern were formed on insulating films 4a and 4b using a liquid crystal alignment material (trade name: SE-610, manufactured by Nissan Chemical Co., Ltd.). Then wrap the cloth By rotating the cylindrical roll at high speed and rubbing on the alignment films 5a and 5b, the rubbing process is performed, and the liquid crystal (I) sealed in the liquid crystal cell 7 is aligned in the negative axis, and between the upper and lower substrates 6a and 6b. The twist angle of was made to be a left twist of 240 °.

[0065] Next, a thermosetting sealant (trade name: ES-7500, manufactured by Mitsui Chemicals, Inc.) is printed on the inner surface of the upper substrate 6a in a pattern having an injection port by a screen printing method. As a gap control agent, a plastic ball having a diameter of 6 μm was sprayed on the inner surface of the lower substrate 6b by a dry spraying method. Then, the upper and lower substrates 6a and 6b were overlapped at predetermined positions to form cells, and heat treatment was performed in a pressed state to cure the sealant, thereby forming the sealant layer 8.

 Next, a conductive material was printed by a screen printing method at a predetermined position on the outer surface of the sealant layer 8 to form a conductive material pattern 9. As the conductive material, a material containing 2-3% by weight of Au balls having a diameter of 6.5 m in the thermosetting sealant was used.

 [0067] Next, the glass substrates 2a and 2b are scratched by a scriber device, and a cell is formed by breaking into a predetermined size 'shape, and liquid crystal (I) is vacuum-injected into the cell. The injection port was sealed with an end sealant.

 [0068] Thereafter, chamfering and cleaning are performed, and polarizing plates 10a and 10b are attached to the outer surfaces of the glass substrates 2a and 2b in a predetermined pattern, whereby a liquid crystal display device (STN) having the configuration shown in FIG. — LCD) 1 formed.

 [0069] Next, the liquid crystal cell 7 does not contain any liquid crystal-compatible palladium-silver binary nanoparticles, and the liquid crystal cell 7 is processed so that the twisted angular force S between the upper and lower substrates 6a, 6b is right-twisted at 240 °! Compensation cell (not shown) exactly the same as the liquid crystal display device 1 of this example, except that a mixture of multiple types of liquid crystal molecules (Dai Nippon Ink Chemical Co., Ltd. STN liquid crystal, product name: LC3) was enclosed. And laminated on the liquid crystal display device 1 of this example. In the liquid crystal display device 1 and the compensation cell, the director directions of the liquid crystal molecules at the center of the cell are orthogonal to each other.

 [0070] Next, using a LCD evaluation device (trade name: LCD-5000, manufactured by Otsuka Electronics Co., Ltd.), the voltage-transmittance characteristics in the normally black mode of the liquid crystal display device 1 manufactured in this example (drive) Frequency dependence) was measured. The result is shown in figure 2.

Further, a wolf image was displayed using the liquid crystal display device 1 manufactured in this example. The results are shown in Fig. 3 as an external photograph. At this time, use the compensation cell (or compensation film)! /, NA! /, (V, so-called blue mode STN display).

[0072] Next, by using the LCD evaluation apparatus, the voltage contrast characteristics of the liquid crystal display device 1 manufactured in this example were measured, and the optimum voltage (voltage capable of obtaining the maximum contrast) was obtained from the voltage contrast characteristics. Measurement of voltage response characteristics (1/64 DUTY drive)

,-Performed at a temperature in the range of 35-85 ° C. The results are shown in Table 1.

[0073] Further, display switching was performed at 10 ° C using the liquid crystal display device 1 manufactured in this example, and an image immediately after the switching was evaluated. The result is shown on the right side of Fig. 4 as an external photograph immediately after switching. still

At this time, the liquid crystal display device 1 does not use the compensation cell.

Next, a micrograph of the liquid crystal cell 7 of the liquid crystal display device 1 produced in this example was taken.

. The results are shown in FIG.

[0075] [Table 1]

ί¾degree Number of runners Rise Rise: Dom m Rise Between B¾f TO rise F Time: ft Applicable m (\ iz) (ms) (ms) (ms) (V)

 1000 1 10 · 0.5 6920 1 2735 7290 28. 0: 1 ： 3 H 300 ： 9996 1 32- 1 丄 648 93 S 8 2 H.：2 '

 100 9456 7996 11 1 2 B 8.328 1 7 <2

1 000 3338 2787 43: 28 2855 ^18.2:: A: 2 Q 300 2832 2934 34 T 8: 3 Θ 1. 7 1 6. 1

 100 .32; 07 1 739; 457 '1 1; 81 1 15. 3

1 00: 0 85 427 1 358 443 ■ 14, 8

0 300 903 336 1489 34: 9 14.4 丄 ΰ 0 88.7 7 34 S- 1 394 3 β 3: 14. 2

1 000 259 125 407 129 14. 0

2 S 30 0 237 1 1 9 385 I: 2; 2 1 3. 8

 10 Q 3 1.94: 32 5 13. 8

1000 94 66 1 4 1 69 1 3. 4

50; 300 85 59 I 33 6 1 1 3. .2

 100. 55 '44 82 45 13 ;. 2 i α o Q 8-2 74 I 1 8 77: 12.4

70 300 90 59 L 31 60 12. 2

 100: 65 3 S: 92 40 1 2. 4

1 0 o Q: 86 87 1.1 6 89; 1 1. 6

80 300 b 5 82 8 S 84 1 1.6 i ・ o 70 3 86 40 12, 0 i a o o 91 90 127 92 11. 0.

85 300 92 74 128 75 1 1, 0:

I ϋ 40 49 42 50 12. 0 TO rising time ... Time from voltage switching to rising TO falling time from voltage switching to falling

 Comparative Example 1

 [0077] In this comparative example, instead of liquid crystal (I), a liquid crystal molecule mixture containing no liquid crystal compatible palladium silver binary nanoparticles (Liquid for STN manufactured by Dainippon Ink and Chemicals, Inc., trade name: LC3) was used. A liquid crystal display device (ST N—LCD) 1 shown in FIG. 1 was produced in the same manner as in Example 1 except that it was used.

 [0078] Next, a compensation cell (not shown) is formed in exactly the same manner as in the liquid crystal display device 1 of this comparative example, except that the twisting angular force between the upper and lower substrates 6a and 6b is right-twisted at 240 °. It was fabricated and laminated on the liquid crystal display device 1 of this comparative example. In the liquid crystal display device 1 and the compensation cell, the director directions of the liquid crystal molecules at the center of the cell are orthogonal to each other.

 [0079] Next, the voltage contrast characteristics of the liquid crystal display device 1 manufactured in this comparative example are measured exactly the same as in Example 1, and the optimum voltage (voltage that can obtain the maximum contrast) is obtained from the voltage contrast characteristics. The response characteristics at the optimum voltage (1/64 DUTY drive) were measured at a temperature in the range of 35 to 85 ° C. The results are shown in Table 2.

 Next, an external appearance photograph immediately after the display switching at 10 ° C. using the liquid crystal display device 1 manufactured in this comparative example is shown on the right side of FIG.

 Next, a micrograph of the liquid crystal cell 7 of the liquid crystal display device 1 produced in this comparative example is shown in FIG.

[0082] [Table 2]

Temperature Drive frequency Time of rise Fall time TO Rise time TO: During rise time ■ Optimal voltage

( ^c c) (Hz) (ms) Cms) (ms) (ms) (V)

 1: 000 1 5832. —— 1 721. 6 —— 29.

-30 3: 00 14 256 8582- 1 5848 02.8 20, 9

 1 0 G: 1 2896 665.7 14608 Ί 088 16.

1 000 636 1 221 3 6954 2354 19. 3

-20 300 505 1 I 726 5694 1 876 1. 5. 9

 100 4753 149 1 5400 1 620 I 4. 6

1 0 D 0 62 106 10, 1. 154 1 5. 4

0 3 G O 4 5: 154, 70 227: 1 5, 4

100: 3 δ 284 ∎ 52 2 S 8 15. 4

1 000 1 88 73 225 8 Q 14. 0

25 300 2: 47 62 29: 1 66 1 3 :. 6 l o o I 55 65 1 9 I 70] 3.6

1 0: 00 1 1 9 45 I S 4 79 13 :,: 4

5 Q 300 1 28 45 1 6 78 1 3. 2

 100 140 44 209 75 1 3. 0

1 00 Q. 62 42 1 1 9 75 1 3. 0

7 Q: 30 H 60 42: 1 1 8 75 12.S:

 100 54. 42 1 05 74 1 2. 7

1 000 43 4 86 81 1 3. 0

8 0 300 4 1 5 1 78 89 1 3. 0

 100 43 45 80 79 12.7

1 0.00 40 55 73 95 12. 9

85 300 40 56 73: 95 12, 7

10Ό 4 1 47 75 8 1 12, 5 TO rising time ... Time from voltage switching to rising TO falling time from voltage switching to falling

 From FIG. 2, in the liquid crystal display device 1 using the liquid crystal (I) of Example 1, the transmittance increases as the applied voltage increases, and the transmittance (display) of the liquid crystal display device 1 can be controlled by the voltage. It is the power that S is clear. In FIG. 2, the transmittance curves are shifted by changing the driving frequency and do not completely coincide with each other. However, since the shift amount is AV <0.3 V, the liquid crystal using the liquid crystal (I) of Example 1 is used. It is clear that the display device 1 can be driven by the duty.

 Regarding the DUTY driving, it is clear that the liquid crystal display device 1 using the liquid crystal (I) of Example 1 can display a display with no unevenness as shown in FIG.

 [0085] Next, from comparison between Table 1 and Table 2, the liquid crystal display device 1 using the liquid crystal (I) of Example 1 is more suitable in the region where the temperature is below freezing and the liquid crystal molecules are highly viscous. Compared with the liquid crystal display device 1 of Comparative Example 1, it is clear that the response time is shortened to 1/2 to 2/3 and the response is faster. High-speed response in the low-temperature range is extremely useful for wide operating temperature ranges such as LCDs for vehicles and LCDs for aircrafts!

Regarding the high-speed response in the low-temperature region, in the liquid crystal display device 1 of Comparative Example 1, the image (numbers / characters) before switching remains dark like the image on the left side of FIG. In the liquid crystal display device 1 of Example 1, it is clear that the image before switching is almost disappeared as in the image on the right side of FIG. 4, and the response in the low temperature region is fast.

Yes

 Further, from comparison between Table 1 and Table 2, the liquid crystal display device 1 using the liquid crystal (I) of Example 1 is more driven than the liquid crystal display device 1 of Comparative Example 1 (Table 1). It is clear that power consumption can be reduced.

Next, from FIG. 5, according to the micrograph of the liquid crystal cell 7 of the liquid crystal display device 1 using the liquid crystal (I) of Example 1, in addition to the white point indicating a gap control agent having a particle diameter of 6 m, It is clear that black spots indicating the aggregation of metal nanoparticles are observed. On the other hand, in the micrograph of the liquid crystal cell 7 of the liquid crystal display device 1 of Comparative Example 1, as shown in FIG. 6, only white spots indicating a gap control agent are observed. Black spots indicating particle aggregation are not observed. Therefore, it shows the aggregation of metal nanoparticles in the micrograph of liquid crystal cell 7 Whether or not the liquid crystal (I) of Example 1 is used can be easily determined based on the presence or absence of black spots.

 Example 2

 In this example, first, liquid crystal-compatible palladium-silver binary nanoparticle-containing liquid crystal (hereinafter referred to as liquid crystal (I)) was prepared as follows.

 [0090] In a glass container with a jacket having an internal volume of 500 ml equipped with a stirrer, thermometer, reflux condenser and syringe pump, a mixture of a plurality of liquid crystal molecules (STN manufactured by Dainippon Ink & Chemicals, Inc.) at room temperature. LC4, product name: LC4, Δη = 0.120, viscosity (20 ° C) = 19 [mPa • s]) 800 mg, tetrahydrofuran 144 ml and 2-propanol 40 ml were prepared to prepare a mixed solution, and the mixed solution was stirred Heated down and refluxed at a temperature in the range of 65-75 ° C. Next, 0.Omol / 0.1 ml of trifluoroacetic acid silver trifluoroacetate in silver (0.008 mmol as silver atoms) was slowly dropped into the mixed solution, and the mixture was reacted at the same temperature for 15 minutes with stirring. 0. Olmol / 1 solution of palladium acetate in 8 · Oml (0.080 mmol as a palladium atom) was slowly added dropwise and reacted at the same temperature for an additional 15 minutes while stirring. After completion of the reaction, the reaction solution was cooled to room temperature to obtain 200 ml of a blackish brown uniform liquid crystal compatible palladium-silver binary nanoparticle dispersion. The liquid crystal-compatible palladium-silver binary nanoparticles are composed of a rare-earth silver binary nanoparticle and a mixture of the above-mentioned various liquid crystal molecules (Dainippon Ink Chemical Co., Ltd. STN liquid crystal, product name: LC 4 ) Are combined.

 [0091] Next, a liquid crystal compatible palladium silver binary nanoparticle dispersion obtained in this example was mixed with 58.3 ml of a mixture of a plurality of liquid crystal molecules (liquid crystal for STN manufactured by Dainippon Ink and Chemicals, Inc., trade name: LC4, Δη = 0.120, viscosity (20 ° C) = 19 [mPa 's]) plus chiral agent (Merck's product name: S-811) added by 0.75 wt%) 4. 76 g was added, concentrated and dried under reduced pressure to obtain 4.76 g of gray uniform liquid crystal (1) (total amount of metal contained; 4.76 mg). The liquid crystal (I) is composed of the liquid crystal molecule mixture (Dai Nippon Ink Chemical Co., Ltd. STN liquid crystal, product name: LC4) as a matrix liquid crystal, and the matrix liquid crystal is a liquid crystal compatible paradium silver binary nanoparticle. Is included.

Next, a liquid crystal display device (STN—LCD) 1 shown in FIG. Sex was evaluated.

 In this embodiment, the liquid crystal display device (STN—LCD) 1 uses liquid crystal (I) and a photocurable sealant manufactured by Kyoritsu Chemical Industry Co., Ltd. as a sealant, and is sealed by a dispenser method. It was produced in the same manner as in Example 1 except that the agent layer 8 was formed.

 [0094] Next, the liquid crystal cell 7 does not contain any liquid crystal-compatible palladium-silver binary nanoparticles, and the twisting angular force S between the upper and lower substrates 6a, 6b is processed to a right twist of 240 °, and the liquid crystal cell 7 does not contain any liquid crystal compatible palladium / silver binary nanoparticles! Compensation cell (not shown) exactly the same as the liquid crystal display device 1 of this example, except that a plurality of types of liquid crystal molecule mixture (Dai Nippon Ink Chemical Co., Ltd. STN liquid crystal, product name: LC4) was enclosed. And laminated on the liquid crystal display device 1 of this example. In the liquid crystal display device 1 and the compensation cell, the director directions of the liquid crystal molecules at the center of the cell are orthogonal to each other.

 Next, the voltage-transmittance characteristics (drive frequency dependence) in the normally black mode of the liquid crystal display device 1 manufactured in this example were measured in exactly the same way as in Example 1. The results are shown in Fig. 7.

 [0096] Next, the voltage contrast characteristics of the liquid crystal display device 1 manufactured in this example were measured exactly the same as in Example 1, and the optimum voltage (the voltage at which maximum contrast was obtained) was obtained from the voltage contrast characteristics. The response characteristics at the optimum voltage (1/64 DUTY drive) were measured at a temperature in the range of 35 to 85 ° C. The results are shown in Table 3.

 Next, a photomicrograph of the liquid crystal cell 7 of the liquid crystal display device 1 produced in this example was taken. The results are shown in FIG.

[0098] [Table 3]

Temperature Drive frequency Time of rise Fall time TO Rise time TO: During rise time ■ Optimal voltage

( ^c c) (Hz) (ms) Cms) (ms) (ms) (V)

 1: 000 5255 4445 5590 46 1.0 30. 8

-30 3: 00 8328 4624 1 0476 4752 21. 6

 1 0 G: 3 1 3 43: 6: 0 1 0438 44: 9: 0 1,8, S

1 000 2372 1 73 29 G 1 829 20. 6

-20 300 241 9 I 528 3230 1 600 1.8: I

 100 1 4 () 1478 3560 1 65: 6 I 7. a.

1 0 D 0 727 233: 1 228 245 16. 6

0 3 G O 682 302: 1 0: 39 3 1 7 1 6. 4

100 8: 08 225 1380 24.0 16. 0

1 000 294 6: 8: ■ 457 72 1 5. 6

25 300 335 70:49: 5 76 15. 4 l o o 225 65 386 65] 5.2

1 0: 00 220 35 30 G 38 14. 8

5 Q 300 220 38: 2 5 4: 0 '1.6

 100 1 1 5 29 I 46 30 14. 4

1 00 Q. 5} 5 6 6 1. 4

7 Q: 30 2 2 4. 3 4 1 .'2

100 0: H 1 1 _; 1 3 _.: 8

1 000 4 4 6 5 14 '. Q

8 0 300 2 3 3 4 I 3. 6

 100 0 0 1 1 1 3. 4

1 0.00 2 1 1 9 2 3 21 9 :. 0

85 300 2 G 1 2: 1 17 8, 8:

10Ό 6 8 6 9 8,: 8 TO rising time ... Time from voltage switching to rising TO falling time from voltage switching to falling

 Comparative Example 2

 [0100] In this comparative example, instead of the liquid crystal (I), a liquid crystal molecule mixture containing no liquid crystal compatible palladium silver binary nanoparticles (Liquid for STN manufactured by Dainippon Ink and Chemicals, Inc., trade name: LC4) was used. A liquid crystal display device (ST N—LCD) 1 shown in FIG. 1 was produced in the same manner as in Example 2 except that it was used.

 [0101] Next, a compensation cell (not shown) was made exactly the same as the liquid crystal display device 1 manufactured in this comparative example, except that the twist angle between the upper and lower substrates 6a and 6b was a right twist of 240 °. Was laminated on the liquid crystal display device 1 of this comparative example. In the liquid crystal display device 1 and the compensation cell, the director directions of the liquid crystal molecules at the center of the cell are orthogonal to each other.

 [0102] Next, the voltage-contrast characteristics of the liquid crystal display device 1 fabricated in this comparative example were measured exactly the same as in Example 1, and the optimum voltage (voltage that can obtain the maximum contrast) was determined from the voltage contrast characteristics. The response characteristics at the optimum voltage (1/64 DUTY drive) were measured at temperatures in the range of 35 to 85 ° C. The results are shown in Table 4.

 [0103] Next, a micrograph of the liquid crystal cell 7 of the liquid crystal display device B produced in this comparative example was taken. The results are shown in FIG.

[0104] [Table 4]

Temperature Spiral Frequency: ¾ Rise Rise Fall ■ Time TO Rise Time T () Rise T Time Optimum 1 £ ( ^c c) (Hz): (ms) (.ms) (ms) (■ ms) · ( "

1 Q 00 1 44 ·] 2, 1.578 6 1 740: 6 2 9. 2 · ': 3 0 a 0 ί) 14044: 5216 1 7.472 5: 632 2 i.

 1: 00 I 3 76 0 34 7 8 1 7 I 7 0 3 750 1 7. 4

1 000 855 6 16 7 2 1 0 Q Ύ 8 i 909 1 9. 8

― 20 300 601 6 1 302 7384 Ί 62.1 T 6.7

 1 G O 46 84 1 20 T S 8 98 i 5 79 1 5. 6 l o o ύ 82 Q Q2 · 29 108: 3 263 15, 6

0: 3: 0: · 0 8 6 5 2 1 9 1 I 6 2 259 1 5. 0

1 00 5 1 7 24 3: 7 6 0: 33, 5 1 5, .0

1 000 5 84 3 1 9 6 T 9 849 1 4.:8

2 5 ^: 3 .0 649 298 7 5 7 326 1 4.: 2

 i 00 6: 8] ■■■ 279 7 '9': 9 306 14, D i · ο ひ · 40 7 · 7 84 1. 5 15-0

5 Q 300 3: 9 7 9 8- 4 1 50 1 .8

 1 00 4 1 1 06: 7 8 1 6 8 1: 4. 8 i ο ο α 3 a 88 72 154.1.

70 300 3: 8 9 0 72 1 5 5 1 4, 0

 1 00 4 1 6 1 T 5 1 Ό 5 1; 3, 8

1 000 3 8 6 3 7 3 1 1 9 1 3. 4

8 0 300 3 S 6 2 7 3 1 1 6: 1: 3 :. 2:

 i ο 0: 40 1 05 68: 1 S ϋ 1 3. 2

1 000 3 8 6 9 7 1 27 1 2 ■, 9

8 5 300 3 8 6.6: "T 1 120 1 2, 7

100 40 50 1: 3 sg 12 :. 5: O rising… Time from voltage switching to rising TO falling time · · · Time from voltage switching to falling

 From FIG. 7, in the liquid crystal display device 1 using the liquid crystal (I) of Example 2, the transmittance increases as the applied voltage increases, and the transmittance (display) of the liquid crystal display device 1 can be controlled by the voltage. It is the power that S is clear. In addition, in Fig. 7, the transmittance curves are shifted by changing the drive frequency and do not completely match.In particular, there is a difference in the curve between 1000 Hz and 300 Hz, but the shift amount is AV < It is clear that the liquid crystal display device 1 using the liquid crystal (I) of Example 2 that is as small as 0.05 V can be DUTY driven.

[0106] Next, from comparison between Table 3 and Table 4, the liquid crystal display device 1 using the liquid crystal (I) of Example 2 is more suitable in the region where the temperature is below freezing and the liquid crystal molecules become highly viscous. Compared with the liquid crystal display device 1 of Comparative Example 2, it is clear that the response time is shortened to 1/2 to 2/3 and the response is faster. High-speed response in the low-temperature range is extremely useful for wide operating temperature ranges such as LCDs for vehicles and LCDs for aircrafts!

[0107] Further, from comparison between Table 3 and Table 4, the liquid crystal display device 1 using the liquid crystal (I) of Example 2 is more driven than the liquid crystal display device 1 of Comparative Example 2 (Table 1). It is clear that the power consumption can be reduced.

 Next, from FIG. 8, according to the micrograph of the liquid crystal cell 7 of the liquid crystal display device 1 using the liquid crystal (I) of Example 2, in addition to the white point indicating a gap control agent having a particle diameter of 6 m, It is clear that black spots indicating the aggregation of metal nanoparticles are observed. On the other hand, in the micrograph of the liquid crystal cell 7 of the liquid crystal display device 1 of Comparative Example 2, as shown in FIG. 9, only white spots indicating the gap control agent are observed, Black spots indicating particle aggregation are not observed. Therefore, whether or not the liquid crystal (I) of Example 2 is used can be easily determined based on the presence or absence of black spots indicating aggregation of metal nanoparticles in the micrograph of the liquid crystal cell 7.

 Example 3

 In this example, first, a liquid crystal (la) was prepared in the same manner as in Example 1 except that no chiral agent was added.

[0110] Next, using the liquid crystal (la), a liquid crystal display device (TN—LCD) 11 shown in FIG. Characteristics were evaluated.

 [0111] The liquid crystal display device (TN-LCD) 11 uses liquid crystal (la) and uses a liquid crystal alignment material (trade name: SE-410, manufactured by Nissan Chemical Co., Ltd.) having a low pretilt angle as the alignment films 5a and 5b. The liquid crystal display device (STN—LCD) 1 of Example 1 was manufactured exactly the same except that it was processed so that the twist angle between the upper and lower substrates 6a and 6b was 90 °.

 [0112] Next, in the liquid crystal display device (TN—LCD) 11 fabricated in this example, the temperature dependence of the response is in the range of 20 to 25 ° C. Static drive, 1/64 DUTY drive Was measured. The results are shown in Table 5.

 [0113] Fig. 11 shows the temperature dependence of the response when 1/64 DUTY drive is performed.

 Comparative Example 3

 [0114] In this comparative example, instead of the liquid crystal (la), a liquid crystal molecule mixture containing no liquid crystal compatible palladium silver binary nanoparticles (Dainippon Ink Chemical Co., Ltd. STN liquid crystal, product name: LC3) A liquid crystal display device (TN-LCD) 11 shown in FIG. 10 was produced in the same manner as in Example 3 except that was used.

 [0115] Next, the temperature dependence of the response in the liquid crystal display device 11 produced in this comparative example was measured in exactly the same way as in Example 3. The results are shown in Table 6.

 [0116] Figure 11 shows the temperature dependence of the response when 1/64 DUTY drive is performed.

 Shown together with 3.

 [0117] [Table 5]

[0118] [Table 6] Static, Ku 1/4 DUTY drive

 Inn Rise Time Fall Time Rise Time Fall Time

 (° C) ns) vms) ns) Vtns)

 -2 0 1 0 0 2 4 3 4 4 8 4 3 9

 0 1 7. 1 1 8. 0 7 9. 2 8 0. 5

 2 5 6. 4 1 3. 2 1 5. 9 2 5. 3

From Tables 5 and 6 and FIG. 11, at 25 ° C. and 0 ° C., the liquid crystal display device 11 of Example 3 has a faster response than the liquid crystal display device 11 of Comparative Example 3, and particularly DUTY. It is clear that the difference becomes significant in driving.

 Example 4

 [0120] In this example, the total amount of liquid crystal-compatible palladium-silver binary nanoparticles-containing liquid crystal

 A liquid crystal (lb) was prepared in exactly the same manner as in Example 1, except that 0.05% by weight of silver atoms and 0.05% by weight of palladium atoms were contained.

 [0121] Next, a liquid crystal display device (STN-LCD) 1 shown in Fig. 1 was produced in the same manner as in Example 1 except that the liquid crystal (lb) was used. In addition, a compensation cell was fabricated in exactly the same manner as in Example 1, and laminated on the liquid crystal display device 1 of this example. The voltage-transmittance characteristics (drive frequency dependence) in the normally black mode of the liquid crystal display device 1 produced in this example were measured in exactly the same way as in Example 1. The results are shown in FIG.

 [0122] From FIG. 12, when the silver content is 0.05% by weight with respect to the total amount of liquid crystal-compatible palladium-silver binary nanoparticles-containing liquid crystal, the case shown in FIG. 2 (Example 1, liquid crystal compatibility) It is clear that the drive frequency dependence is low as in the case of 0.02% by weight of silver with respect to the total amount of liquid crystal containing palladium binary nanoparticles.

 Example 5

 [0123] In this example, the total amount of liquid crystal-compatible palladium-silver binary nanoparticle-containing liquid crystals was used.

 A liquid crystal (Ic) was prepared in exactly the same manner as in Example 1, except that 0.08% by weight of silver atoms and 0.02% by weight of palladium atoms were contained.

Next, a liquid crystal display device (STN—LCD) 1 shown in FIG. 1 was produced in the same manner as in Example 1 except that the liquid crystal (Ic) was used. Also, a compensation cell was made exactly as in Example 1. Then, it was laminated on the liquid crystal display device 1 of this example. The voltage-transmittance characteristics (drive frequency dependence) in the normally black mode of the liquid crystal display device 1 produced in this example were measured in exactly the same way as in Example 1. The results are shown in FIG.

[0125] From FIG. 13, when the silver content is 0.08% by weight with respect to the total amount of liquid crystal-compatible palladium-silver binary nanoparticle-containing liquid crystals, it depends on the driving frequency compared to the case shown in FIG. It is clear that the nature is higher.

 Example 6

 [0126] In this example, except that the liquid crystal-compatible palladium silver binary nanoparticle-containing liquid crystal contains 0.04 wt% of silver atoms and 0.16 wt% of palladium atoms. A liquid crystal (Id) was prepared exactly as in Example 1.

 Next, a liquid crystal display device (STN—LCD) 1 shown in FIG. 1 was produced in the same manner as in Example 1 except that the liquid crystal (Id) was used. In addition, a compensation cell was fabricated in exactly the same manner as in Example 1, and laminated on the liquid crystal display device 1 of this example. The voltage-transmittance characteristics (drive frequency dependence) in the normally black mode of the liquid crystal display device 1 produced in this example were measured in exactly the same way as in Example 1. The results are shown in FIG.

 In this example, the weight ratio of silver atoms to palladium atoms is 1: 4, the same as in Example 1.

 1S The absolute amount of silver and noradium atoms is increasing. However, from FIG. 14, it can be seen from this example that the silver content is 0.04 wt% with respect to the total amount of liquid crystal-compatible palladium-silver binary nanoparticle-containing liquid crystals, as in the case of FIG. It is clear that the dependency is low.

 Example 7

 [0129] In this example, except that the liquid crystal-compatible palladium silver binary nanoparticle-containing liquid crystal contains 0.08% by weight of silver atoms and 0.32% by weight of palladium atoms with respect to the total amount of liquid crystals. A liquid crystal (Ie) was prepared in exactly the same manner as in Example 1.

Next, a liquid crystal display device (STN—LCD) 1 shown in FIG. 1 was produced in the same manner as in Example 1 except that the liquid crystal (Ie) was used. In addition, a compensation cell was fabricated in exactly the same manner as in Example 1, and laminated on the liquid crystal display device 1 of this example. The voltage-transmittance characteristics (driving frequency dependence) in the normally black mode of the liquid crystal display device 1 manufactured in this example were The measurement was performed exactly as in Example 1. The results are shown in FIG.

 [0131] In this example, the weight ratio of silver atoms to palladium atoms is 1: 4, which is the same as in Example 1. The absolute amount of silver atoms and palladium atoms is further increased compared to Example 6, Liquid crystal compatible palladium The silver content is 0.08% by weight with respect to the total amount of liquid crystal containing silver binary nanoparticles. From FIG. 15, it is clear that the drive frequency dependency is higher in the case of the present embodiment than in the case shown in FIGS.

 [0132] According to Examples 4 to 7, in order to lower the driving frequency dependency of the liquid crystal-compatible palladium-silver binary nanoparticle-containing liquid crystal, the total amount of liquid crystal-compatible palladium-silver binary nanoparticle-containing liquid crystal is It is apparent that the silver content is preferably 0.05% by weight or less.

 Reference example

 In this reference example, first, a liquid crystal containing a liquid crystal-compatible palladium / silver binary nanoparticle (hereinafter referred to as liquid crystal (III)) was prepared as follows.

 [0134] To a Schlenk tube made of quartz, 0.33 g (l. 32 mmol) of 4, 1 n pentyl-4-cyanobiphenyl, 36.7 ml of tetrahydrofuran and 10 ml of 2 propanol were added, and stirring force at room temperature S et al., 0. Olmmol / 1 tetrahydrofuran solution of silver perchlorate 0.66 ml (0.0065 mmol as silver atom) and 0. Olmmol / 1 tetrahydrofuran solution of palladium acetate 2.64 ml (0.0264 mmol as palladium atom) were added in order, and the mixed solution was Prepared and freeze degassed the mixed solution. Next, the atmosphere inside the reaction system was set to an argon atmosphere, and the operation of irradiating with ultraviolet light for 2 hours was repeated twice using a 500 W ultra-high pressure mercury lamp (product name: UI 502Q). 100 ml of a uniform liquid crystal-compatible palladium-silver binary nanoparticle dispersion was obtained. Next, 34.53g of liquid crystal molecule mixture (liquid crystal for STN manufactured by Dainippon Ink & Chemicals, Inc., trade name: LC3) was added to 71ml of the liquid crystal compatible palladium-silver binary nanoparticle dispersion. The solution was concentrated and dried under reduced pressure to obtain 4.88 g of gray uniform liquid crystal (III) (total amount of metal contained; 4.88 mg).

 Next, a liquid crystal display device (STN LCD) 1 shown in FIG. 1 was prepared using liquid crystal (III), and the characteristics were evaluated.

[0136] In this reference example, the liquid crystal display device (STN LCD) 1 was actually used except that the liquid crystal (III) was used. It was made exactly the same as Example 1.

 [0137] Next, the liquid crystal cell 7 does not contain any liquid crystal-compatible palladium-silver binary nanoparticles in addition to being processed so as to be right-twisted with a twist angle force of 240 ° between the upper and lower substrates 6a and 6b! A compensation cell (not shown) was prepared in exactly the same way as the liquid crystal display device 1 of this example, except that the liquid crystal molecule mixture (Dai Nippon Ink Chemical Co., Ltd. STN liquid crystal, product name: LC3) was sealed. Then, it was laminated on the liquid crystal display device 1 of this example. In the liquid crystal display device 1 and the compensation cell, the director directions of the liquid crystal molecules at the center of the cell are orthogonal to each other.

 [0138] Next, the voltage-transmittance characteristics (drive frequency dependence) in the normally black mode of the liquid crystal display device 1 produced in this reference example were measured in exactly the same manner as in Example 1. The results are shown in Figure 16.

 [0139] Further, using the liquid crystal display device 1 produced in the present reference example, a wolf image was displayed.

 The results are shown in Fig. 17 as an appearance photograph. At this time, the liquid crystal display device 1 used a compensation film instead of the compensation cell.

 [0140] Next, the voltage contrast characteristics of the liquid crystal display device 1 fabricated in this reference example were measured exactly the same as in Example 1, and the optimum voltage (voltage that could obtain the maximum contrast) was obtained from the voltage contrast characteristics. The response characteristics at the optimum voltage (1/64 DUTY drive) were measured at a temperature in the range of 35 to 85 ° C. The results are shown in Table 7.

 [0141] Next, a microphotograph of the liquid crystal cell 7 of the liquid crystal display device 1 produced in the present reference example was taken. In the microphotograph, only white spots indicating a gap control agent were observed. No black spots indicating aggregation were observed. This is thought to be because the metal nanoparticles in the liquid crystal cell 7 of the liquid crystal display device 1 produced in this reference example are hardly aggregated and therefore cannot be observed with a microscope.

[0142] [Table 7] Temperature Drive frequency Rising time Falling time TO Rising time TO Rising]-'During time Optimal power £ h (.c) (Hz) Cms) (ma) tis) (V)

 1 000 1 3 3 7 6 6 09 6 1 764 8 6 1— 28 2 7. 0

-3 0 300 1 1 6 2 0 9 96 7 1 3 540 1 0 26 0 1 .4

 1 00 1 2 2 6 7 4 84 0 1 84 5 7 5 0 70 1 6. 8

1 000 3 2 6 3 3 25 0 44 8 9 3 32 9 1 7. 6 One 2 0 300 26 9 3 2 2 3 0 4 7 34 2 309 1 5. 4

 1 00 2 5 00 1 44 9 4 54 8 1 53 7 1 4. 9

1 000 9 8 2 2 54 1 600 26 9 1 4. 6

0 300 9 3 2 2 30 1 70 6 244 1 4. 0

1 0 0 9 1 0 258 1 744 2 79 1 3. 8

1 000 2 7 1 1 0 5 44 5 1 1 2 1 3. 8

2 5 300 2 7 9 1 0 7 4 5 8 1 1 6 1 3. 8

 1 00 2 3 5 7 5 40 7 79 1 5. 2

1 000 1 24 9] 1 9 1 9 5 1 4.0

5 0 300 1 4 8 4 7 2 1 8 5 1 1 5. 8

 1 00 8 0 3 3 1 3 2 34 2 0. 0

1 000 8 7 9 6 1 0 7 9 9 1 5. 2

7 0 300 2 1 7 3 3 2 5 6 8 5 1 .0

 1 00 5 5 1 9 7 6 20 2 5. 2

1 000 94 8 7 1 0 6 90 1 6. 0

8 0 300 1 94 3 3 2 2 3 36 2 0. 6

 1 00 5 5 1 9 6 1 20 2 8. 6

1 00 0 1 4 7 5 7 1 6 9 6 0 1 6. 0

8 5 300 1 9 7 3 6 2 2 1 38 2 1. 0

1 00 5 5 1 9 6 1 20 2 9. 6 O rising ... Time from voltage switching to rising TO falling time · · · Time from voltage switching to falling

 From FIG. 16, in the liquid crystal display device 1 using the liquid crystal (III) of the reference example, the transmittance increases as the applied voltage increases), and the transmittance (display) of the liquid crystal display device 1 can be controlled by the voltage. That power S clear power. However, in Fig. 16, it is clear that the transmittance curve is greatly shifted by changing the drive frequency, which is not suitable for DUTY drive display.

[0144] In the liquid crystal display device 1 using the liquid crystal (III) of the reference example for the DUTY drive display, display unevenness is seen as shown in FIG. In DUTY drive, the effective force and frequency change depending on the display state, so Vth changes depending on the location, and it is considered that the display unevenness occurred.

 [0145] Next, from comparison between Table 7 and Table 2, the liquid crystal display device 1 using the liquid crystal (III) of the reference example is in the region where the liquid crystal molecules are highly viscous at a low temperature below freezing point. Compared with the liquid crystal display device 1 of Comparative Example 1, it is clear that the response time is shortened to 1/2 to 2/3 and the response is faster. Further, from comparison between Table 7 and Table 2, in the low temperature range, the liquid crystal display device 1 using the liquid crystal (III) of the reference example has a driving voltage higher than that of the liquid crystal display device 1 of Comparative Example 1. It is clear that low power consumption (corresponding to the optimum voltage in the table) can be reduced. However, in the high temperature range, the driving voltage of the liquid crystal display device 1 using the liquid crystal (III) of the reference example is higher than that of the liquid crystal display device 1 of the comparative example 1.

 In each of the above embodiments, the normally black mode has been described. However, similar effects can be obtained even in the normally white mode.

 Brief Description of Drawings

 FIG. 1 is an explanatory cross-sectional view showing a configuration example of a liquid crystal display device of the present invention.

 FIG. 2 is a graph showing voltage-transmittance characteristics in the liquid crystal display device according to the first embodiment of the present invention.

 FIG. 3 is an external view photograph when an image is displayed on the liquid crystal display device of the first embodiment of the present invention.

 FIG. 4 is an appearance photograph immediately after an image is displayed on the liquid crystal display device of the first embodiment of the present invention and the image is switched at 10 ° C.

 FIG. 5 is a micrograph of a liquid crystal cell of a liquid crystal display device according to a first embodiment of the present invention.

FIG. 6 shows a liquid crystal cell microscope of a liquid crystal display device of a comparative example with respect to the first embodiment of the present invention. Photo.

 FIG. 7 is a graph showing voltage-transmittance characteristics in the liquid crystal display device according to the second embodiment of the present invention.

 FIG. 8 is a micrograph of a liquid crystal cell of a liquid crystal display device according to a second embodiment of the present invention.

 FIG. 9 is a micrograph of a liquid crystal cell of a liquid crystal display device of a comparative example with respect to the second embodiment of the present invention.

 FIG. 10 is an explanatory cross-sectional view showing another configuration example of the liquid crystal display device of the present invention.

 FIG. 11 is a graph showing the temperature dependence of responsiveness when DUTY driving is performed in the liquid crystal display device according to the third embodiment of the present invention.

 FIG. 12 is a graph showing voltage-transmittance characteristics in the liquid crystal display device according to the fourth embodiment of the present invention.

 FIG. 13 is a graph showing voltage-transmittance characteristics in the liquid crystal display device of Example 5 of the present invention.

 FIG. 14 is a graph showing voltage-transmittance characteristics in a liquid crystal display device according to a sixth embodiment of the present invention.

 FIG. 15 is a graph showing voltage-transmittance characteristics in the liquid crystal display device according to the seventh embodiment of the present invention.

 FIG. 16 is a graph showing voltage-transmittance characteristics of a liquid crystal display device of a reference example according to the present invention.

 FIG. 17 is an external view photograph when an image is displayed on a liquid crystal display device of a reference example according to the present invention. Explanation of symbols

 1, 11 ··· Liquid crystal display device, 2a, 2b… Glass substrate, 3a, 3b… Transparent electrode film, 4a, 4b… Insulating film, 5a, 5b… Alignment film, 6a, 6b… Substrate, 7 ··· Liquid crystal Cell, 8 ... sealant layer, 9 ... conductive material pattern, 10a, 10b ... polarizing plate.

Claims

 The scope of the claims

While refluxing a mixed solution obtained by mixing at least one liquid crystal molecule, a secondary alcohol represented by the following general formula (1), and an organic solvent, at least one metal ion solution is added. A liquid crystal compatible particle obtained by adding and reacting, a metal nanoparticle obtained by reducing the metal ion, and binding around the metal nanoparticle with the metal nanoparticle as a nucleus. Liquid crystal compatible particle-containing liquid crystal, comprising liquid crystal compatible particles comprising the liquid crystal molecules.

(Wherein R ¹ and R ² represent a hydrocarbon group which may be the same or different, and may have a substituent. R ¹ and R ² are bonded to each other to form a ring. In the liquid crystal containing liquid crystal compatible particles according to claim 1,

 Liquid crystal compatible particle-containing liquid crystal, wherein the mixed solution is refluxed at a temperature in the range of 30 to 200 ° C.

 In the liquid crystal containing liquid crystal compatible particles according to claim 1,

 Liquid crystal compatible particle-containing liquid crystal, wherein the mixed solution is refluxed at a temperature in a range of 40 to 150 ° C.

 In the liquid crystal containing liquid crystal compatible particles according to claim 1,

The metal ions are Au ⁺ , Au ³⁺ , Ag ⁺ , Cu ⁺ , Cu ²⁺ , Ru ²⁺ , Ru ³⁺ , Ru ⁴⁺ , Rh ²⁺ , Rh ³⁺ , Pd ²⁺ , Pd ⁴⁺ , Must be at least one metal ion selected from the group consisting of Os ⁴⁺ , Ir ⁺ , Ir ³⁺ , Pt ²⁺ , Pt ⁴⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ Liquid crystal compatible particles containing liquid crystal.

 In the liquid crystal containing liquid crystal compatible particles according to claim 1,

 The liquid crystal compatible particle-containing liquid crystal characterized in that the liquid crystal compatible particle has a palladium-silver binary nanoparticle as a nucleus.

 In the liquid crystal containing the liquid crystal compatible particles according to claim 5,!

The palladium-silver binary nanoparticles are 0.0% of the total liquid crystal containing liquid crystal compatible particles. Liquid crystal-compatible particle-containing liquid crystal containing silver in an amount of 5% by weight or less.

[7] The liquid crystal containing the liquid crystal compatible particles according to claim 1! /,

 The liquid crystal containing liquid crystal compatible particles contains 0.0% of the total liquid crystal containing liquid crystal compatible particles.

A liquid crystal-compatible particle-containing liquid crystal comprising the liquid crystal-compatible particle in an amount ranging from 01 to 0.5% by weight.

 [8] The liquid crystal containing the liquid crystal compatible particles according to claim 1! /,

 The liquid crystal containing liquid crystal compatible particles contains 0.0% of the total liquid crystal containing liquid crystal compatible particles.

02- 0. A liquid crystal compatible particle-containing liquid crystal comprising the liquid crystal compatible particle in an amount in the range of 2% by weight.

[9] While refluxing a mixed solution obtained by mixing at least one liquid crystal molecule, a secondary alcohol represented by the following general formula (1), and an organic solvent, at least one metal ion Liquid crystal compatible particles obtained by adding and reacting a solution, metal nanoparticles obtained by reducing the metal ions, and the metal nanoparticles as a nucleus around the metal nanoparticles. A liquid crystal display device comprising: a liquid crystal cell in which a liquid crystal containing liquid crystal compatible particles containing liquid crystal compatible particles composed of the liquid crystal molecules bonded to each other is enclosed.

(Wherein R ¹ and R ² represent a hydrocarbon group which may be the same or different, and may have a substituent. R ¹ and R ² are bonded to each other to form a ring. ) [10] In the liquid crystal display device according to claim 9,! /,

 The liquid crystal display device, wherein the liquid crystal cell includes a chiral agent together with the liquid crystal compatible particle-containing liquid crystal.

[11] The liquid crystal display device according to claim 9,

 The liquid crystal display device, wherein the liquid crystal cell has a twist angle of the liquid crystal compatible particle-containing liquid crystal in the range of 180 to 270 °.

[12] In the liquid crystal display device according to claim 9,

The liquid crystal compatible particles are characterized by having palladium-silver binary nanoparticles as nuclei. Liquid crystal display device.

[13] The liquid crystal display device according to claim 12,

 The palladium silver binary nanoparticles contain 0.05% by weight or less of silver with respect to the whole liquid crystal compatible particle-containing liquid crystal.

[14] In the liquid crystal display device according to claim 9,! /,

 The liquid crystal containing liquid crystal compatible particles contains 0.0% of the total liquid crystal containing liquid crystal compatible particles.

01 to 0.5% by weight of the liquid crystal-compatible particles in an amount ranging from 5 to 5% by weight.

 [15] In the liquid crystal display device according to claim 9,! /,

 The liquid crystal containing liquid crystal compatible particles contains 0.0% of the total liquid crystal containing liquid crystal compatible particles.

02- 0. A liquid deficiency characterized in that it contains the liquid crystal compatible particles in an amount in the range of 2% by weight.

 [16] The liquid crystal display device according to claim 9, wherein

 A liquid crystal display device characterized by being a dot matrix panel using DUTY drive.

[17] In the liquid crystal display device according to claim 9,

 A liquid crystal display device characterized by being a liquid crystal display device selected from the group consisting of a super twist nematic LCD, a twist nematic LCD, an in-plane switching LCD, a guest host LCD, and a polymer network LCD .

[18] In the liquid crystal display device according to claim 9,! /,

 A liquid crystal display device characterized by being a simple matrix display device in a super twist nematic take mode or a twist nematic take mode.

[19] In the liquid crystal display device according to claim 9,! /,

 A liquid crystal display device characterized by being an active matrix display device using a twisted nematic mode or an in-plane switching mode.