JP5566109B2 - Liquid crystal display - Google Patents

Description

  The present invention relates to a liquid crystal display device.

  2. Description of the Related Art Conventionally, a vertical alignment mode liquid crystal display device in which liquid crystal having negative dielectric anisotropy is sealed in a liquid crystal cell sandwiched between a pair of opposing substrates (hereinafter sometimes abbreviated as PBT-LCD) Is known (see, for example, Patent Document 1).

  In the PBT-LCD, when no voltage is applied to the electrodes provided on the pair of substrates, the liquid crystal is arranged in a direction perpendicular to the substrate, and combined with a polarizing plate in a crossed Nicols arrangement, Very good dark display (normally black) is obtained. Further, in the PBT-LCD, when a voltage is applied to the electrodes provided on the pair of substrates, the liquid crystal is tilted and arranged in a horizontal direction with respect to the substrate, and a bright display is performed.

  In the PBT-LCD, the optical anisotropy of the vertically aligned liquid crystal can be compensated by laminating an optical compensation plate having a negative refractive index anisotropy in a direction perpendicular to the substrate. Very good viewing angle characteristics can be obtained.

  However, although the PBT-LCD has a relatively fast response in a temperature range near room temperature, it has a disadvantage that the response is remarkably slow in a low temperature range of, for example, 0 ° C. or lower. If the response is slow, an unclear portion is generated in the moving image or the previous image remains, and the display quality is significantly impaired.

  Further, the PBT-LCD has a disadvantage that it is necessary to perform temperature compensation such as changing the driving voltage according to the temperature because the threshold value and the voltage-transmittance curve change in a low temperature region around −20 ° C. .

  Incidentally, the manufacturing process of the liquid crystal display device includes a step of inspecting the display state of the liquid crystal display device. At this time, if the polarizing plate protective film is peeled off, static electricity is generated, and the liquid crystal display device malfunctions due to the static electricity. Since the malfunction does not occur on the electrode, the charge cannot escape and the display is maintained in the malfunction state for a long time. As a result, there is a problem that the inspection time is remarkably increased or the inspection itself becomes difficult.

  When the failure due to the static electricity is significant, the product may become a display failure. As countermeasures against defects due to static electricity, it is conceivable to change the liquid crystal material or the alignment film material, or to add a conductive material to the liquid crystal material or the alignment film material.

  However, the above measures have a disadvantage that the PBT-LCD characteristics such as display performance and current consumption of the PBT-LCD are adversely affected.

  Conventionally, an active drive type liquid crystal display device provided with a switching element for each pixel is known. In the active drive type liquid crystal display device, for example, a thin layer transistor (TFT) or the like is used as the switching element (see, for example, Patent Document 2).

  In a liquid crystal display device using TFT as the switching element (hereinafter sometimes abbreviated as TFT-LCD), the display quality can be improved by increasing the resistance value of the liquid crystal layer and increasing the voltage holding ratio. it can.

  In order to increase the resistance value of the liquid crystal layer, it is necessary to reduce the ion concentration of the liquid crystal material in the liquid crystal layer. For this purpose, for example, a fluorine-based liquid crystal having a low impurity ion concentration is used as the liquid crystal material, and an alignment film made of soluble polyimide is used.

  However, in the TFT-LCD, if the protective film is removed for display inspection or the user rubs the panel surface with a cloth or the like, a malfunction occurs due to static electricity, and it takes a long time to eliminate the malfunction. There is an inconvenience.

  In the TFT-LCD, it is considered that the reason why it takes a long time to eliminate the malfunction is that, since the resistance value of the liquid crystal layer is high as described above, it is difficult for static charges to escape. Examples of the method for releasing the charge include a method of providing a conductive material on the panel surface and grounding the conductive material. However, in the above method, the manufacturing process increases and the cost increases, and a sufficient effect cannot be obtained.

Further, as an antistatic method for a liquid crystal display device, there is a method of adding a conductive material (dopant) into the liquid crystal. However, this method is effective in a simple matrix type liquid crystal display device, but it cannot be applied to a TFT-LCD because the voltage holding ratio is significantly reduced.
JP 2005-234254 A JP 2007-171680 A

  The present invention eliminates such inconvenience, and is excellent in response even in a low temperature region around -20 to 0 ° C., does not need to perform temperature compensation by changing the driving voltage according to the temperature, and adversely affects the device characteristics. It is an object of the present invention to provide a liquid crystal display device that can eliminate defects caused by static electricity.

In order to achieve this object, the liquid crystal display device of the present invention includes a Group 3 or Group 13 metal, at least one metal other than the Group 3 or Group 13 metal, and at least one liquid crystal molecule. A Group 3 or Group 13 metal liquid crystal compatible particle-added liquid crystal prepared by adding a Group 3 or Group 13 metal liquid crystal compatible particle to a mixed liquid crystal material obtained by mixing a plurality of types of liquid crystal molecules is used. It is characterized by that.

The Group 3 metal liquid crystal compatible particle-added liquid crystal is a Group 3 metal liquid crystal compatible particle containing a Group 3 metal, at least one metal other than the Group 3 metal, and at least one liquid crystal molecule. These are added to a mixed liquid crystal material obtained by mixing a plurality of types of liquid crystal molecules.

The Group 13 metal liquid crystal compatible particle-added liquid crystal is a Group 13 metal liquid crystal compatible material containing a Group 13 metal , at least one metal other than the Group 13 metal, and at least one liquid crystal molecule. The particles are added to a mixed liquid crystal material obtained by mixing a plurality of types of liquid crystal molecules.

  In the liquid crystal display device of the present invention, since the Group 3 or Group 13 metal liquid crystal compatible particle-added liquid crystal is enclosed in a liquid crystal cell, the response in a low temperature region of 0 ° C. or lower can be accelerated. Therefore, according to the liquid crystal display device of the present invention, it is possible to prevent an unclear portion in a moving image or a previous image from remaining even in a low temperature region of 0 ° C. or lower, thereby obtaining excellent display quality. The effect that it is possible can be produced.

  Further, according to the liquid crystal display device of the present invention, the liquid crystal compatible particle-containing liquid crystal contains the Group 3 or Group 13 metal liquid crystal compatible particles, so that the frequency can be reduced even in a low temperature region around -20 to 0 ° C. The threshold dependence due to the difference in the size is reduced. Therefore, according to the liquid crystal display device of the present invention, there is an effect that it is not necessary to perform temperature compensation by changing the driving voltage according to the temperature even in a low temperature region around −20 to 0 ° C.

  Furthermore, according to the liquid crystal display device of the present invention, the liquid crystal compatible particle-containing liquid crystal contains the group 3 or group 13 metal liquid crystal compatible particles, thereby preventing malfunction due to static electricity without increasing current consumption. Can be eliminated.

  The Group 3 metal liquid crystal compatible particles may contain one or more Group 3 metals, and may contain one or more Group 3 metals and other than Group 3 metals. It may contain at least one metal. In addition, the Group 13 metal liquid crystal compatible particles may contain one or more Group 13 metals, and together with one or more Group 13 metals, the Group 13 metals. It may contain at least one kind of metal other than. When the liquid crystal compatible particles include a plurality of kinds of metals, the plurality of kinds of metal particles may have a random alloy structure in which they are randomly distributed. You may have a core-shell structure which uses the particle | grains of a seed metal as a core.

  On the other hand, it is preferable that the mixed liquid crystal material to which the Group 3 metal liquid crystal compatible particles or the Group 13 metal liquid crystal compatible particles are added has a negative dielectric anisotropy in order to achieve the above effect.

  In addition, the Group 3 metal liquid crystal compatible particles or the Group 13 metal liquid crystal compatible particles may be the Group 3 metal ions or the Group 13 metal ions alone, or the Group 3 metal ions or the Group 13 metals. It is preferably composed of nanoparticles formed by reacting a mixture of ions and at least one metal ion other than the Group 3 ions or the Group 13 ions with the mixed liquid crystal material.

  The “reaction” referred to in the present invention means that the metal ions and other substances contained in the reaction system interact physically, chemically or electrically, and liquid crystal molecules gather around the metal ions. This means that nano-sized particles centered on the metal ions are formed.

  In this case, the nanoparticles are 0.02 to 0.2% by weight with respect to the total amount of liquid crystal contained in the Group 3 metal liquid crystal compatible particle-added liquid crystal or the Group 13 metal liquid crystal compatible particle-added liquid crystal. It is preferable to be included in the range.

  Even if the content of the nanoparticles exceeds 0.2% by weight with respect to the total amount of liquid crystal contained in the Group 3 metal liquid crystal compatible particle-added liquid crystal or Group 13 metal liquid crystal compatible particle-added liquid crystal, There is a problem that the effect on the particle is not improved (saturates, and even if added more, there is no difference in the effect), and the particles tend to aggregate. When the particles are aggregated, they are not only recognized as point defects in the display, but there are cases where the specific resistance of the liquid crystal is remarkably lowered due to the aggregation and the voltage holding ratio is lowered.

  In the liquid crystal display device of the present invention, the Group 3 metal liquid crystal compatible particle-added liquid crystal or the Group 13 metal liquid crystal compatible particle-added liquid crystal is aligned in a direction perpendicular to the substrate in order to achieve the above effect. It is preferable.

  In the liquid crystal display device of the present invention, the Group 3 metal is preferably at least one metal selected from the group consisting of scandium, yttrium, terbium, gadolinium, neodymium, and cerium. The metal is preferably at least one metal selected from the group consisting of thallium, indium and gallium.

  Further, the liquid crystal display device of the present invention can be a liquid crystal display device using static drive or DUTY drive. In this case, the liquid crystal display device of the present invention may be any one display panel selected from the group consisting of a character display panel, a dot matrix display panel, and a character / dot matrix mixed display panel.

  When the liquid crystal display device of the present invention is a liquid crystal display device using static drive or DUTY drive, the Group 3 metal is any one of scandium and yttrium, and the Group 13 metal is thallium or It is particularly preferable that any one metal of gallium is used.

  The liquid crystal display device of the present invention may be a liquid crystal display device using active driving. In this case, the liquid crystal display device of the present invention can eliminate malfunction due to static electricity in a very short time because the Group 3 or Group 13 metal liquid crystal compatible particle-added liquid crystal is sealed in a liquid crystal cell. An excellent display quality can be obtained by increasing the voltage holding ratio.

  When the liquid crystal display device of the present invention is a liquid crystal display device using active driving, the mixed liquid crystal material preferably has a resistivity of at least 1E + 13 Ωcm.

  When the liquid crystal display device of the present invention is a liquid crystal display device using active driving, the Group 3 metal is at least one metal selected from the group consisting of scandium, terbium, gadolinium, neodymium, and cerium. The group 13 metal is particularly preferably at least one metal selected from the group consisting of thallium, indium and gallium.

  Next, embodiments of the present invention will be described in more detail with reference to the accompanying drawings.

  As shown in FIG. 1, the liquid crystal display device of the first embodiment of the present invention is a PBT-LCD (vertical alignment liquid crystal display device) 1, which is a pair of parallel and transparent glass substrates 2a and 2b, glass Transparent electrode films 3a and 3b provided in a predetermined pattern on the inner surfaces facing each other of the substrates 2a and 2b, and insulating films 4a and 4b provided on the display portions on the inner surfaces facing each other of the transparent electrode films 3a and 3b. And vertical alignment films 5a and 5b provided in substantially the same pattern as the transparent electrode films 3a and 3b on the opposing inner surfaces of the insulating films 4a and 4b. 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 vertical alignment film 5a, and the glass substrate 2b, the transparent electrode film 3b, the insulating film 4b, and the vertical alignment film 5b. Thus, the lower substrate 6b is formed. A liquid crystal L containing liquid crystal compatible particles L is sealed in a liquid crystal cell 7 formed by being sandwiched between the upper and lower substrates 6a and 6b so as to be aligned in a direction perpendicular to the upper and lower substrates 6a and 6b.

  The vertical alignment films 5a and 5b are processed so that liquid crystal molecules sealed in the liquid crystal cell 7 are aligned uniaxially and the alignment state between the upper and lower substrates 6a and 6b is in an antiparallel (antiparallel) state. The liquid crystal cell 7 is sealed with a sealing agent layer 8, and a conductive material pattern 9 is formed on the outer surface of the sealing agent layer 8. Further, polarizing plates 10a and 10b are attached to the outer surfaces of the glass substrates 2a and 2b so as to have a predetermined pattern, for example, a crossed Nicol arrangement.

  The liquid crystal display device 1 can be manufactured as follows, for example.

  First, an ITO film is formed as a transparent electrode on the glass substrates 2a, 2b by vapor deposition, sputtering, or the like, and a transparent electrode film 3a, 3b is 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, and may be formed by vapor deposition using a metal mask, sputtering, or the like.

  Next, vertical alignment films (for example, product name: SE-1211 manufactured by Nissan Chemical Industries, Ltd.) 5a and 5b having substantially the same pattern are formed on the insulating films 4a and 4b. As a method for obtaining uniform monodomain alignment, a method known per se can be employed (see, for example, Patent Document 1).

  Next, a rubbing process is performed on the vertical alignment films 5a and 5b. The rubbing treatment can be performed by rotating a cylindrical roll wound with a cloth at high speed and rubbing the vertical 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 uniaxially oriented so that the alignment state between the upper and lower substrates 6a and 6b is in an antiparallel (antiparallel) state.

  As a method for performing the alignment treatment on the vertical alignment films 5a and 5b, a photo-alignment method, an ion beam alignment method, a plasma beam alignment method, an oblique deposition method, or the like may be used instead of the rubbing treatment.

  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 a gap is formed on the inner surface of the other substrate 6b or the substrate 6a. Spray the control agent 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 cure the sealant, thereby forming the sealant layer 8.

  As the sealing agent, for example, a thermosetting sealing agent (for example, trade name: ES-7500, manufactured by Mitsui Chemicals, Inc.) can be used. The thermosetting sealant contains several weight percent of glass fibers having a size of 3.9 μm. In place of the thermosetting sealant, a photocurable sealant or a combined light / heat type sealant may be used.

  The sealing agent can be printed by, for example, a screen printing method, but may be performed using a dispenser or the like. A printing pattern of the sealant is a pattern having an injection port when the liquid crystal compatible particle-containing liquid crystal L is injected into the liquid crystal cell 7 formed between the upper and lower substrates 6a and 6b. In the case of, a closed pattern without an inlet is used. For example, a plastic ball having a diameter of 4 μm can be used as the gap control agent, but a silica ball may be used.

  Next, a conductive material is printed at a predetermined position on the outer surface of the sealant layer 8 to form a conductive material pattern 9. As the conductive material, for example, a material containing several weight percent of an Au ball having a diameter of 4.5 μm or the like in the thermosetting sealant can be used. The conductive material can be printed by, for example, screen printing.

  Next, the glass substrates 2a and 2b are scratched by a scriber device, and divided into predetermined sizes and shapes by breaking to form cells, and liquid crystal L containing liquid crystal compatible particles is injected into the cells. The liquid crystal L containing liquid crystal compatible particles can be injected by, for example, a vacuum injection method. In this case, the injection port is sealed with an end sealant.

  Thereafter, chamfering and cleaning are performed, and the polarizing plates 10a and 10b are attached to the outer surfaces of the glass substrates 2a and 2b so as to have a predetermined pattern, for example, a crossed Nicol arrangement having an angle of 45 ° with respect to rubbing. Thus, a normally black PBT-LCD 1 having the configuration shown in FIG. 1 can be obtained.

  Note that the PBT-LCD 1 may include viewing angle (optical) compensators on the polarizing plates 10a and 10b.

  In the PBT-LCD 1 of the present embodiment, the liquid crystal compatible particle-containing liquid crystal L enclosed in the liquid crystal cell 7 is a Group 3 metal liquid crystal compatible particle or Group 13 metal liquid crystal compatible particle, and a plurality of types of liquid crystal molecules. It is added to a mixed liquid crystal material obtained by mixing. The Group 3 metal liquid crystal compatible particles may contain one or more Group 3 metals, and may contain one or more Group 3 metals and other than Group 3 metals. It may contain at least one metal. In addition, the Group 13 metal liquid crystal compatible particles may contain one or more Group 13 metals, and together with one or more Group 13 metals, the Group 13 metals. It may contain at least one kind of metal other than.

  The liquid crystal compatible particles include at least one liquid crystal molecule, an organic solvent, a Group 3 metal salt or a Group 13 metal salt, a Group 3 metal salt or a Group 13 metal salt, and one other type or It can be obtained by mixing a plurality of kinds of metal salts and reacting the resulting mixed solution under heating to reflux to produce nanoparticles. In the present embodiment, the “reaction” means that the metal ion and other substances contained in the reaction system interact physically, chemically or electrically, and liquid crystal molecules are formed around the metal ion. By gathering, it means forming nano-sized particles centered on the metal ions.

  Examples of the liquid crystal molecules used to obtain the liquid crystal compatible particles include cyanobiphenyls such as 4′-n-pentyl-4-cyanobiphenyl and 4′-n-hexyloxy-4-cyanobiphenyl; cyclohexylbenzonitriles such as-(trans-4-n-pentylcyclohexyl) benzonitrile; 4'-n-pentyl-4-ethoxy-2,3-difluorobiphenyl, 1-ethoxy-2,3-difluoro-4- fluorobenzenes such as (trans-4-n-pentylcyclohexyl) benzene; phenyl esters such as 4-butylbenzoic acid (4-cyanophenyl) and 4-heptylbenzoic acid (4-cyanophenyl); 4-carboxyphenyl Carbonates such as ethyl carbonate and 4-carboxyphenyl-n-butyl carbonate; phenyls such as 4- (4-n-pentylphenylethynyl) cyanobenzene and 4- (4-n-pentylphenylethynyl) fluorobenzene Ruacetylenes; phenyl pyrimidines such as 2- (4-cyanophenyl) -5-n-pentylpyrimidine and 2- (4-cyanophenyl) -5-n-octylpyrimidine; 4,4′-bis (ethoxycarbonyl) ) Azobenzenes such as azobenzene; azoxybenzenes such as 4,4′-azoxyanisole, 4,4′-dihexylazoxybenzene; N- (4-methoxybenzylidene) -4-n-butylaniline, N— Schiff bases such as (4-ethoxybenzylidene) -4-n-butylaniline; benzidines such as N, N′-bisbenzylidenebenzidine; cholesteryl esters such as cholesteryl acetate and cholesteryl benzoate; poly (4-phenylene terephthalamide) ) And the like. These liquid crystal molecules may be used alone or in combination of two or more. 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.

  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, alcohols such as methanol, ethanol, isopropyl alcohol; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Ketones; esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate; amides such as N, N′-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; N, N′— Ureas such as dimethyl imidazolidinone; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Nitriles such as acetonitrile and propionitrile; Ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane; Hexa Aliphatic hydrocarbons such as heptane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene can be mentioned, preferably nitriles, ethers and aromatic hydrocarbons can be mentioned, More preferred are ethers. In addition, as for the said organic solvent, any 1 type of the said organic solvent may be used independently, and 2 or more types may be mixed and used for it.

  The amount of the organic solvent used is preferably in the range of 10 to 500 ml with respect to 1 g of the liquid crystal molecules.

  Examples of the Group 3 metal include at least one metal selected from the group consisting of scandium, yttrium, terbium, gadolinium, neodymium, and cerium. The group 13 metal may include at least one metal selected from the group consisting of thallium, indium, and gallium.

Examples of metals other than Group 3 metals or Group 13 metals include transition metals. The transition metal preferably has Rb ⁺ , Cs ⁺ , Sr ²⁺ , Ba ²⁺ , La ³⁺ , Sm ³⁺ , Eu ²⁺ , Eu ³⁺ , Yb ³⁺ , Ti ⁺ , Ti ²⁺ , Ti ³⁺ , Ti ⁴⁺ , ^{Zr 4+, V 3+, V 4+} , Nb 3+, Nb 4+, Nb 5+, Mo 3+, Mo 5+, Mo 6+, W 4+, W 6+, Mn 2+, Mn 3+, Mn 4+, Au +, Au 3+, Ag + ^{, Cu +, Cu 2+, Ru} 2+, Ru 3+, Ru 4+, Rh +, Rh 2+, Rh 3+, Pd 2+, Pd 4+, Os 4+, Ir +, Ir 3+, Ir 4+, Pt 2+, Pt 4+, Fe There may be mentioned at least one selected from the group consisting of ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , Ni ²⁺ , Zn ²⁺ , Al ³⁺ and Bi ³⁺ .

  Examples of the counter ion forming the metal salt include hydride ion, halogen ion, halogenate ion, perhalogenate ion, optionally substituted carboxylate ion, acetylacetonate ion, carbonate ion, sulfate ion, Examples thereof include nitrate ion, tetrafluoroborate ion, hexafluorophosphate ion and the like. The metal salt may be coordinated with a neutral ligand such as carbon monoxide, triphenylphosphine, or p-cymene.

  Group 3 metal salt or Group 13 metal salt, or Group 3 metal salt or Group 13 metal salt and at least one metal salt other than Group 3 metal salt or Group 13 metal salt are organic solvents. It is preferable to use it as a solution dissolved in. As an organic solvent which melt | dissolves the said metal salt, the said organic solvent used in order to obtain the said liquid crystal compatible particle can be mentioned, for example. The amount of the organic solvent used is not particularly limited as long as it can dissolve the metal salt completely.

  The reflux temperature (reaction temperature) at the time of heating and refluxing the mixed solution is not particularly limited, but is preferably a temperature in the range of 40 to 100 ° C. Further, the reaction pressure at the time of heating and refluxing the mixed solution may be any of pressurization, normal pressure, and reduced pressure.

  Liquid crystal compatible particle-containing liquid crystal L is prepared by adding the liquid crystal compatible particles obtained as described above to the mixed liquid crystal material obtained by mixing a plurality of types of liquid crystal molecules, and stirring the resulting mixture. It can be obtained by concentrating under reduced pressure and further vacuum drying. The liquid crystal L containing liquid crystal compatible particles obtained as described above may contain a chiral agent in order to adjust the twist angle.

  The PBT-LCD 1 of the present embodiment having the above configuration can be preferably a liquid crystal display device using static drive or DUTY drive. In this case, the PBT-LCD 1 of this embodiment may be any one display panel selected from the group consisting of a character display panel, a dot matrix display panel, and a character / dot matrix mixed display panel.

  When the PBT-LCD 1 of this embodiment is a liquid crystal display device using static drive or DUTY drive, the Group 3 metal is any one of scandium or yttrium, and the Group 13 metal is thallium. It is particularly preferable that any one metal of gallium is used.

  In the PBT-LCD 1 of this embodiment, by providing the liquid crystal L containing the liquid crystal compatible particles, the response in a low temperature region of, for example, 0 ° C. or less is accelerated. Therefore, according to the PBT-LCD 1 of the present embodiment, it is possible to prevent an unclear portion in a moving image or a previous image from remaining even in a low temperature region of 0 ° C. or lower, and to achieve excellent display quality. Can be obtained.

  In addition, the PBT-LCD 1 of the present embodiment includes the liquid crystal compatible particle-containing liquid crystal L so that the temperature dependence of the threshold due to the difference in frequency is reduced. Therefore, the PBT-LCD 1 of the present embodiment does not require temperature compensation of the drive circuit, can reduce the cost, and prevents the occurrence of non-uniform display due to the threshold value changing depending on the frequency in DUTY drive. can do.

  Moreover, the PBT-LCD 1 of the present embodiment can prevent the occurrence of malfunction due to static electricity in the step of inspecting the display state of the liquid crystal display device by including the liquid crystal L containing the liquid crystal compatible particles. In particular, in the case where the liquid crystal compatible particle-containing liquid crystal L includes metal particles composed of scandium alone or liquid crystal compatible particles composed of a plurality of metal particles containing at least scandium in at least one liquid crystal molecule serving as a matrix liquid crystal. The malfunction due to static electricity can be prevented from occurring even for a moment. In addition, when the liquid crystal compatible particle-containing liquid crystal L contains the metal particles made of scandium alone or the liquid crystal compatible particles made of a plurality of metal particles containing at least scandium in at least one kind of liquid crystal molecules serving as the matrix liquid crystal. Thus, an increase in current consumption can be prevented.

  Furthermore, the PBT-LCD 1 of this embodiment can obtain excellent display quality because the liquid crystal compatible particles contained in the liquid crystal compatible particle-containing liquid crystal L are nanoparticles. This is because the nanoparticles are particles smaller than the wavelength of light and do not adversely affect the optical characteristics of the PBT-LCD 1.

  The liquid crystal display device according to the second embodiment of the present invention is an active drive type liquid crystal display device (TFT-LCD) including a thin layer transistor (TFT) as a switching element. The TFT-LCD includes a configuration in which a liquid crystal cell is sandwiched between a pair of upper and lower substrates. For example, the TFT-LCD includes a common electrode on the liquid crystal cell side of the upper substrate, and each has a TFT on the liquid crystal cell side of the lower substrate. A pixel electrode is provided. Each of the common electrode and the pixel electrode includes an alignment film on the liquid crystal cell side. On the other hand, a polarizing plate is disposed on the surface of each substrate opposite to the liquid crystal cell.

  A black mask and a color filter may be formed between the upper substrate and the common electrode.

  In the TFT-LCD of this embodiment, the liquid crystal compatible particle-containing liquid crystal sealed in the liquid crystal cell is a group 3 metal liquid crystal compatible particle or a group 13 metal liquid crystal compatible particle mixed with a plurality of types of liquid crystal molecules. This is added to the mixed liquid crystal material. The Group 3 metal liquid crystal compatible particles may contain one or more Group 3 metals, and may contain one or more Group 3 metals and other than Group 3 metals. It may contain at least one metal. In addition, the Group 13 metal liquid crystal compatible particles may contain one or more Group 13 metals, and together with one or more Group 13 metals, the Group 13 metals. It may contain at least one kind of metal other than.

  The Group 3 metal liquid crystal compatible particles, Group 13 metal liquid crystal compatible particles, Group 3 metal liquid crystal compatible particle-containing liquid crystals, and Group 3 metal liquid crystal compatible particle-containing liquid crystals are all used in the first embodiment. Can be obtained exactly the same as in the case of. However, in the TFT-LCD of the present embodiment, the Group 3 metal liquid crystal compatible particle-containing liquid crystal or the mixed liquid crystal material used for the Group 3 metal liquid crystal compatible particle-containing liquid crystal has a resistivity of at least 1E + 13 Ωcm. Preferably it is.

  In the liquid crystal cell, the Group 3 metal liquid crystal compatible particle-added liquid crystal or the Group 13 metal liquid crystal compatible particle-added liquid crystal is preferably aligned perpendicular to the substrate.

  In the active drive type TFT-LCD of this embodiment, the Group 3 metal is at least one metal selected from the group consisting of scandium, terbium, gadolinium, neodymium, and cerium, and the Group 13 metal is Particularly preferred is at least one metal selected from the group consisting of thallium, indium and gallium.

  The TFT-LCD of the present embodiment having the above-described configuration can be manufactured without increasing the number of processes, can reliably eliminate malfunction due to static electricity in a short time, and can be used for liquid crystal televisions, notebook computers, mobile phones. It can be used for applications such as DSC display panels and automobile display panels.

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

  In this example, first, a liquid crystal L containing liquid crystal-compatible particles was prepared as follows.

  In a glass container having an internal volume of 500 ml equipped with a stirrer, thermometer, reflux condenser and dropping funnel, 0.800 g of a mixture of plural kinds of liquid crystal molecules (liquid crystal with negative dielectric anisotropy (Δε) manufactured by Merck) Then, 144 ml of tetrahydrofuran and 40 ml of 2-propanol were added, and then 16.0 ml of a 0.01 mol / l scandium (III) acetylacetonate tetrahydrofuran solution (containing 0.160 mmol as scandium atoms) was added under heating and reflux ( The reaction was performed at an internal temperature of 69 ° C. for 8 hours. After completion of the reaction, the reaction solution was cooled to room temperature to obtain 200 ml of a colorless and uniform liquid crystal-compatible scandium nanoparticle dispersion. As a result of analyzing the liquid crystal compatible scandium nanoparticle dispersion with a transmission electron microscope, the particle diameter of the central metal of the liquid crystal compatible scandium nanoparticles was 1 to 5 nm.

  Next, in a glass container having an internal volume of 300 ml, 4.44 g of the plurality of types of liquid crystal molecule mixture and 139 ml of the liquid crystal compatible scandium nanoparticle dispersion prepared in this example (including 5.00 mg as the total amount of metal) After stirring and concentrating, the obtained mixture was concentrated under reduced pressure and vacuum-dried to obtain 5.00 g of liquid crystal-compatible scandium nanoparticle-containing liquid crystal.

  Next, using the liquid crystal-compatible particle-containing liquid crystal (liquid crystal-compatible scandium nanoparticle-containing liquid crystal) L obtained in this example, a PBT-LCD 1 shown in FIG. 1 was prepared and the characteristics were evaluated.

  The PBT-LCD 1 was manufactured as follows. First, an ITO film was formed as a transparent electrode on the glass substrates 2a and 2b, and the transparent electrode films 3a and 3b were formed by forming a desired pattern in 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, on the insulating films 4a and 4b, vertical alignment films 5a and 5b having substantially the same pattern were formed using a liquid crystal alignment material (trade name: SE-1211 manufactured by Nissan Chemical Co., Ltd.). Next, a cylindrical roll wound with a cloth is rotated at high speed, and rubbing treatment is performed by rubbing on the vertical alignment films 5a and 5b, whereby the liquid crystal containing scandium nanoparticle-containing liquid crystal sealed in the liquid crystal cell 7 is obtained. The alignment between the upper and lower substrates 6a and 6b is anti-parallel (anti-parallel).

  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 inlet by a screen printing method, and as a gap control agent. Then, plastic balls having a diameter of 4 μm were sprayed on the inner surface of the lower substrate 6b by a dry spraying method. The thermosetting sealant contains 1 to 5% by weight of glass fiber having a size of 3.9 μm. Then, the upper and lower substrates 6a and 6b were superposed at predetermined positions to form a cell, 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 at a predetermined position on the outer surface of the sealant layer 8 by a screen printing method to form a conductive material pattern 9. As the conductive material, a material containing 1 to 5% by weight of Au balls having a diameter of 4.5 μm in the thermosetting sealant was used.

  Next, the glass substrates 2a and 2b are scratched by a scriber device, and cells are formed by breaking into predetermined sizes and shapes, and liquid crystal-compatible liquid crystals containing liquid crystal compatible particles ( Liquid crystal-compatible scandium nanoparticle-containing liquid crystal) L was injected, and the injection ports (two locations) were sealed with an end sealant.

  Thereafter, chamfering and cleaning are performed, and the polarizing plates 10a and 10b are attached to the outer surfaces of the glass substrates 2a and 2b in a predetermined pattern (crossed Nicol arrangement having an angle of 45 ° with respect to the rubbing). The PBT-LCD 1 having the configuration shown in FIG. 1 and having a cell thickness of 4 μm, anti-parallel alignment, and normally black was formed.

  Next, using an LCD evaluation apparatus (trade name: LCD-5200, manufactured by Otsuka Electronics Co., Ltd.), the voltage-transmittance characteristics (static drive, temperature dependence) of the PBT-LCD 1 manufactured in this example, and 1 The response characteristics with / 4 DUTY drive were measured at room temperature (25 ° C.), 0 ° C., −20 ° C., and −30 ° C. for each frequency of 100 Hz, 300 Hz, and 1000 Hz.

  Of the measurement results, the temperature dependence of the voltage-transmittance characteristics at each frequency is shown in FIGS. 2 shows a measurement result at a frequency of 100 Hz, FIG. 3 shows a measurement result at a frequency of 300 Hz, and FIG. 4 shows a measurement result at a frequency of 1000 Hz.

  Table 1 shows the response characteristics in 1/4 DUTY driving. In Table 1, the response characteristics indicate the response time at the optimum voltage and the response time when the rise time and the fall time are substantially aligned. In the liquid crystal display device, since the biggest problem is that the response at a low temperature is delayed, the response characteristics shown in Table 1 are measurement results in a low temperature region of −20 ° C. and −30 ° C.

  In this example, first, a liquid crystal L containing liquid crystal-compatible particles was prepared as follows.

  In a glass container having an internal volume of 500 ml equipped with a stirrer, thermometer, reflux condenser and dropping funnel, 0.800 g of a mixture of plural kinds of liquid crystal molecules (liquid crystal with negative dielectric anisotropy (Δε) manufactured by Merck) Then, 144 ml of tetrahydrofuran and 40 ml of 2-propanol were added, and then 16.0 ml of a 0.01 mol / l yttrium (III) acetylacetonate tetrahydrofuran solution (containing 0.160 mmol as an yttrium atom) was added under heating and reflux ( The reaction was performed at an internal temperature of 69 ° C. for 8 hours. After completion of the reaction, the reaction solution was cooled to room temperature to obtain 200 ml of a colorless uniform liquid crystal compatible yttrium nanoparticle dispersion. As a result of analyzing the liquid crystal-compatible scandium nanoparticle dispersion with a transmission electron microscope, the particle diameter of the central metal of the liquid crystal-compatible yttrium nanoparticles was 1 to 5 nm.

  Next, in a glass container having an internal volume of 300 ml, 4.71 g of the liquid crystal molecule mixture and 70.3 ml of the liquid crystal-compatible yttrium nanoparticle dispersion prepared in this example (with 5.00 mg as the total amount of metal). The resulting mixture was concentrated under reduced pressure and vacuum dried to obtain 5.00 g of liquid crystal-compatible yttrium nanoparticle-containing liquid crystal.

  Next, except that the liquid crystal-compatible particle-containing liquid crystal (liquid crystal-compatible yttrium nanoparticle-containing liquid crystal) L obtained in this example was used, a PBT- having the same configuration as that shown in FIG. LCD1 was produced.

  Next, the voltage-transmittance characteristics (static drive, temperature dependence) of the PBT-LCD 1 manufactured in this example, exactly the same as in Example 1, and the response characteristics in 1/4 DUTY drive are 100 Hz, Each frequency of 300 Hz and 1000 Hz was measured at room temperature (25 ° C.), 0 ° C., −20 ° C., and −30 ° C., respectively.

  Of the measurement results, the temperature dependence of the voltage-transmittance characteristics at each frequency is shown in FIGS. Here, FIG. 5 shows measurement results at a frequency of 100 Hz, FIG. 6 shows measurement results at a frequency of 300 Hz, and FIG. 7 shows measurement results at a frequency of 1000 Hz.

Table 2 shows the response characteristics in the 1/4 DUTY drive. In Table 2, the response characteristics indicate the response time at the optimum voltage and the response time when the rise time and the fall time are substantially aligned. In the liquid crystal display device, since the biggest problem is that the response at low temperature is delayed, the response characteristics shown in Table 2 are measurement results in a low temperature region of −20 ° C. and −30 ° C.
[Comparative Example 1]
In this comparative example, a plurality of types of liquid crystal molecule mixture (liquid crystal having negative dielectric anisotropy (Δε) made by Merck) containing no liquid crystal compatible particles (liquid crystal compatible scandium nanoparticles or liquid crystal compatible yttrium nanoparticles) are used. A PBT-LCD 1 having the configuration shown in FIG.

  Next, the voltage-transmittance characteristics (static drive, temperature dependence) of the PBT-LCD 1 manufactured in this comparative example, exactly the same as in Example 1, and the response characteristics in 1/4 DUTY drive are 100 Hz, Each frequency of 300 Hz and 1000 Hz was measured at room temperature (25 ° C.), 0 ° C., −20 ° C., and −30 ° C., respectively.

  Of the measurement results, the temperature dependence of the voltage-transmittance characteristics at each frequency is shown in FIGS. 8 shows a measurement result at a frequency of 100 Hz, FIG. 9 shows a measurement result at a frequency of 300 Hz, and FIG. 10 shows a measurement result at a frequency of 1000 Hz.

  Tables 1 and 2 show the response characteristics in the 1/4 duty driving. In Tables 1 and 2, the response characteristics indicate the response time at the optimum voltage and the response time when the rise time and the fall time are substantially aligned.

  2 to 7, it is clear that according to the PBT-LCD 1 of Examples 1 and 2, the voltage-transmittance characteristics are almost the same regardless of the temperature. On the other hand, it is clear from FIGS. 8 to 10 that, according to the PBT-LCD 1 of Comparative Example 1, the voltage-transmittance characteristics change with temperature. When the threshold value and sharpness change with temperature, it becomes necessary to change the drive voltage depending on the temperature, or the appearance of the display changes. However, according to the PBT-LCD 1 of the first and second embodiments, it is not necessary to change the driving voltage depending on the temperature, and the appearance of the display does not change. it is obvious.

  From Tables 1 and 2, it is clear that the rise time (Rise) and the fall time (Decay) are faster in the PBT-LCD 1 in Examples 1 and 2 than in the PBT-LCD 1 in Comparative Example 1. It is.

  In this example, first, a vertically aligned cell (empty cell) was prepared using a substrate on which an ITO electrode pattern (character type) was formed, and the liquid crystal compatible particle-containing liquid crystal (Example 1) obtained in Example 1 was used in the cell. A liquid crystal-compatible scandium nanoparticle-containing liquid crystal) L was injected, and a polarizing plate was attached to prepare an evaluation cell. Next, using an electrostatic test machine (trade name: SEE-200AX, manufactured by Noise Research Institute Co., Ltd.), the evaluation cell prepared in this example was placed on an insulating plate made of a 5 mm thick bake plate, and the evaluation was performed. The contact discharge was performed once for 1 second in the center of the display area of the cell for use. The time until the liquid crystal operated by electrostatic charging completely returned to the entire surface was measured as the return time. The results are shown in Table 3.

  Further, the current consumption (initial) of the evaluation cell produced in this example was measured. The consumption current is a current flowing through the evaluation cell and is the reciprocal of the resistance of the evaluation cell. The results are shown in Table 4.

In this example, a cell for evaluation was produced in the same manner as in Example 3 except that the liquid crystal-compatible particle-containing liquid crystal (liquid crystal-compatible yttrium nanoparticle-containing liquid crystal) L obtained in Example 2 was injected into the cell. did. Next, in exactly the same manner as in Example 3, the time until the liquid crystal operated by electrostatic charging in the evaluation cell produced in this example returned completely was measured as the return time. The results are shown in Table 3.
[Comparative Example 2]
In this comparative example, the cell has a liquid crystal molecule mixture (Merck's dielectric anisotropy (Δε)) that does not contain any liquid crystal compatible particles (liquid crystal compatible scandium nanoparticles or liquid crystal compatible yttrium nanoparticles) at all. An evaluation cell was produced in the same manner as in Example 3 except that the liquid crystal was injected. Next, in exactly the same manner as in Example 3, the time until the liquid crystal operated by electrostatic charging in the evaluation cell produced in this comparative example completely returned was measured as the return time. The results are shown in Table 3.

  Moreover, the consumption current (initial stage) of the evaluation cell produced in this comparative example was measured. The results are shown in Table 4.

  From Table 3, according to the evaluation cell of Examples 3 and 4 provided with the liquid crystal L containing liquid crystal compatible particles L, for evaluation of Comparative Example 2 provided with a mixture of plural kinds of liquid crystal molecules containing no liquid crystal compatible particles. It is clear that the return time is shorter than that of the cell, and the effect of preventing malfunction due to static electricity is obtained. In particular, according to the evaluation cell of Example 3 provided with the liquid crystal-compatible particle-containing liquid crystal (liquid crystal-compatible scandium nanoparticle-containing liquid crystal) L obtained in Example 1, even when a high voltage is applied, It is clear that the operation is not seen and the occurrence of malfunction due to static electricity can be prevented. Further, the evaluation cell of Example 4 provided with the liquid crystal-compatible particle-containing liquid crystal (liquid crystal-compatible yttrium nanoparticle-containing liquid crystal) L obtained in Example 2 can be applied to an applied voltage of +10 kV that is practically required. On the other hand, it is apparent that the required characteristic of the return time within 30 s is sufficiently satisfied.

  Next, from Table 4, according to the evaluation cell of Example 3 provided with the liquid crystal-compatible particle-containing liquid crystal (liquid crystal-compatible scandium nanoparticle-containing liquid crystal) L obtained in Example 1, the liquid crystal-compatible particles were The current consumption is the same as that of the evaluation cell of Comparative Example 2 having a plurality of liquid crystal molecule mixtures not contained at all, and it is clear that the current consumption does not increase even though the occurrence of malfunction due to static electricity can be prevented. is there.

  In this example, first, a liquid crystal L containing liquid crystal-compatible particles was prepared as follows.

  In a glass container having an internal volume of 500 ml equipped with a stirrer, thermometer, reflux condenser and dropping funnel, 0.800 g of a mixture of plural kinds of liquid crystal molecules (liquid crystal with negative dielectric anisotropy (Δε) manufactured by Merck) Then, 144 ml of tetrahydrofuran and 40 ml of 2-propanol were added, and then 16.0 ml of a 0.01 mol / l thallium (I) acetylacetonate tetrahydrofuran solution (containing 0.160 mmol as a thallium atom) was added and heated under reflux ( The reaction was performed at an internal temperature of 69 ° C. for 8 hours. After completion of the reaction, the reaction solution was cooled to room temperature to obtain 200 ml of a colorless and uniform liquid crystal-compatible thallium nanoparticle dispersion. As a result of analyzing the liquid crystal compatible thallium nanoparticle dispersion with a transmission electron microscope, the particle diameter of the central metal of the liquid crystal compatible thallium nanoparticle was 1 to 5 nm.

  Next, in a glass container having an internal volume of 100 ml, 4.87 g of the liquid crystal molecule mixture of plural types and 30.6 ml of the liquid crystal-compatible thallium nanoparticle dispersion prepared in this example (with 5.00 mg as the total amount of metal) The resulting mixture was concentrated under reduced pressure and dried under vacuum to obtain 5.00 g of liquid crystal-compatible thallium nanoparticle-containing liquid crystal.

  Next, using the liquid crystal-compatible particle-containing liquid crystal (liquid crystal-compatible thallium nanoparticle-containing liquid crystal) L obtained in this example, a PBT-LCD 1 shown in FIG. 1 was prepared, and an LCD evaluation apparatus (Otsuka Electronics Co., Ltd.) was produced. (Product name: LCD-5200), the voltage-transmittance characteristics (static drive, frequency dependence) of the PBT-LCD 1 manufactured in this example and the response characteristics in 1/4 DUTY drive are set to 100 Hz. , 300 Hz, and 1000 Hz were measured at room temperature (25 ° C.), 0 ° C., −20 ° C., and −30 ° C., respectively.

  Of the measurement results, the driving frequency dependence of the voltage-transmittance characteristics at each temperature is shown in FIGS. Here, FIG. 11 shows the measurement results at room temperature (25 ° C.), FIG. 12 shows the measurement results at 0 ° C., FIG. 13 shows the measurement results at −20 ° C., and FIG. 14 shows the measurement results at −30 ° C. In addition, Table 5 shows threshold values and frequency dependence of the threshold values and sharpness values that can be seen from FIGS.

  Next, of the measurement results, the temperature dependence of the voltage-transmittance characteristics at each frequency is shown in FIGS. Here, FIG. 15 shows the measurement result at 100 Hz, FIG. 16 shows the measurement result at 300 Hz, and FIG. 17 shows the measurement result at 1000 Hz.

Next, Table 6 shows response characteristics in 1/4 DUTY driving. In Table 6, the response characteristics indicate the response time at the optimum voltage and the response time when the rise time and the fall time are substantially aligned.
[Comparative Example 3]
In this comparative example, except that a plurality of kinds of liquid crystal molecule mixture (liquid crystal having negative dielectric anisotropy (Δε) manufactured by Merck) containing no liquid crystal compatible particles (liquid crystal compatible thallium nanoparticles) was used. A PBT-LCD 1 having the structure shown in FIG.

  Next, the voltage-transmittance characteristics (static drive, frequency dependence) of the PBT-LCD 1 manufactured in this comparative example, exactly the same as in Example 5, and the response characteristics in 1/4 DUTY drive are 100 Hz, Each frequency of 300 Hz and 1000 Hz was measured at room temperature (25 ° C.), 0 ° C., −20 ° C., and −30 ° C., respectively.

  Of the measurement results, the driving frequency dependence of the voltage-transmittance characteristics at each temperature is shown in FIGS. Here, FIG. 18 shows the measurement results at room temperature (25 ° C.), FIG. 19 shows the measurement results at 0 ° C., FIG. 20 shows the measurement results at −20 ° C., and FIG. 21 shows the measurement results at −30 ° C. In addition, Table 5 shows threshold values, frequency dependence of the threshold values, and sharpness values that can be seen from FIGS.

  Next, among the measurement results, the temperature dependence of the voltage-transmittance characteristics at each frequency is shown in FIGS. Here, FIG. 22 shows the measurement result at 100 Hz, FIG. 23 shows the measurement result at 300 Hz, and FIG. 24 shows the measurement result at 1000 Hz.

  Next, Table 6 shows response characteristics in 1/4 DUTY driving. In Table 6, the response characteristics indicate the response time at the optimum voltage and the response time when the rise time and the fall time are substantially aligned.

  From FIG. 11 to FIG. 14, according to the PBT-LCD 1 of Example 5, the transmittance increases with voltage application, the transmittance of the PBT-LCD 1 can be controlled by the voltage, and the drive frequency is changed. It is clear that the transmission curves are almost perfectly consistent.

  18 to 21, the PBT-LCD 1 of Comparative Example 3 also increases the transmittance with voltage application, as in Example 5, and the transmittance of the PBT-LCD 1 is controlled by the voltage. It is apparent that the transmittance curves are almost perfectly matched even when the drive frequency is changed.

  On the other hand, it is clear from Table 5 that the threshold value of the PBT-LCD 1 of Example 5 is lower than that of the PBT-LCD 1 of Comparative Example 3 at room temperature (25 ° C.), 0 ° C. and −20 ° C. Therefore, according to the PBT-LCD 1 of the fifth embodiment, the voltage can be reduced and the power can be saved.

  Here, in the case of DUTY driving, a driving voltage higher than that of static driving is required, and an expensive driving circuit (driver) is required. In addition, among the liquid crystal materials that can be used for the PBT-LCD 1, there are few liquid crystal materials having a high Δε, and a reduction in voltage is desired. Therefore, the PBT-LCD 1 of the fifth embodiment is advantageous in that it does not require an expensive driving circuit and can be substituted for a liquid crystal material having a high Δε.

  Also, from Table 5, it is clear that the PBT-LCD 1 of Example 5 is superior in sharpness at room temperature (25 ° C.) and 0 ° C. Since the PBT-LCD 1 of the fifth embodiment is excellent in sharpness, the maximum contrast is improved, and a remarkably excellent display quality can be obtained in high DUTY driving.

  Next, at −30 ° C., the PBT-LCD 1 of Comparative Example 3 has a lower threshold and excellent sharpness, and seems to have performance superior to that of the PBT-LCD 1 of Example 5. However, from a different point of view, the PBT-LCD 1 of Example 5 has almost the same threshold and sharpness regardless of temperature, whereas the PBT-LCD 1 of Comparative Example 3 has temperature dependency on the threshold and sharpness. It can also be said that excellent properties are exhibited only at −30 ° C.

  Therefore, when the temperature dependence is compared next, it is clear from FIGS. 18 to 21 that in the PBT-LCD 1 of Example 5, the voltage-transmittance characteristics are almost the same for each frequency and do not depend on the temperature. It is.

  On the other hand, from FIGS. 22 to 24, it is clear that in the PBT-LCD 1 of Comparative Example 3, the voltage-transmittance characteristics change with temperature.

  When the threshold value or sharpness changes depending on the temperature, it becomes necessary to change the drive voltage according to the temperature, or the appearance of the display changes. However, according to the PBT-LCD 1 of the fifth embodiment, since temperature dependence is hardly recognized as described above, it is not necessary to change the driving voltage according to the temperature, and excellent display quality can be obtained.

  Next, comparing the response characteristics, it is clear from Table 6 that at 25 ° C. and 0 ° C., the rise time and fall time of the PBT-LCD 1 of Comparative Example 3 are faster in response. . However, at −20 ° C., the rotation is reversed, and it is clear that the PBT-LCD 1 of Example 5 has a faster response in both the rise time and fall time.

  In the PBT-LCD 1, the biggest problem is that the response is slow in a low temperature region. Although the response of the PBT-LCD 1 of the fifth embodiment also becomes slower as the temperature becomes lower, the amount of change at which the response becomes slower is slower than that of the conventional liquid crystal display device such as the PBT-LCD 1 of the third comparative example. Therefore, according to the PBT-LCD 1 of Example 5, it is apparent that the response speed reduction in the low temperature region is improved.

  In this example, first, a liquid crystal L containing liquid crystal-compatible particles was prepared as follows.

  In a glass container having an internal volume of 100 ml equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, 0.200 g of a mixture of plural kinds of liquid crystal molecules (liquid crystal having negative dielectric anisotropy (Δε) manufactured by Merck) 36 ml of tetrahydrofuran and 10 ml of 2-propanol were added, and then 4.0 ml of 0.010 mol / l gallium (III) acetylacetonate in tetrahydrofuran (containing 0.040 mmol as gallium atoms) was added, and the temperature was 65 to 75 ° C. And stirred for 7 hours. After completion of the reaction, the reaction solution was cooled to room temperature to obtain 50 ml of a colorless and uniform liquid crystal-compatible gallium nanoparticle dispersion.

  Next, 8.64 ml of the liquid crystal-compatible gallium nanoparticle dispersion prepared in this example was added to 464 mg of the liquid crystal molecule mixture, and the resulting mixture was concentrated and dried under reduced pressure. 500 mg of liquid crystal-compatible gallium nanoparticle-containing liquid crystal was obtained.

Next, using the liquid crystal-compatible particle-containing liquid crystal (liquid crystal-compatible gallium nanoparticle-containing liquid crystal) L obtained in this example, a PBT-LCD 1 shown in FIG. 1 was prepared, and an LCD evaluation apparatus (Otsuka Electronics Co., Ltd.) was produced. (Product name: LCD-5200), and the voltage-transmittance characteristics (temperature dependence) of the PBT-LCD 1 manufactured in this example are 25 ° C. when the drive frequencies are 100 Hz, 300 Hz, and 1000 Hz, respectively. , 0 ° C., −20 ° C., and −30 ° C. The results are shown in FIGS. Here, FIG. 25 shows a measurement result at a driving frequency of 100 Hz, FIG. 26 shows a measurement result at a driving frequency of 300 Hz, and FIG. 27 shows a measurement result at a driving frequency of 1000 Hz.
[Comparative Example 4]
In this comparative example, except that a plurality of types of liquid crystal molecule mixture (liquid crystal having negative dielectric anisotropy (Δε) manufactured by Merck) containing no liquid crystal compatible particles (liquid crystal compatible gallium nanoparticles) was used, A PBT-LCD 1 having the structure shown in FIG.

  Next, the voltage-transmittance characteristics (temperature dependence) of the PBT-LCD 1 manufactured in this comparative example, exactly the same as in Example 6, are 25 ° C. for the driving frequencies of 100 Hz, 300 Hz, and 1000 Hz, respectively. It measured at 0 degreeC, -20 degreeC, and -30 degreeC. The results are shown in FIGS. Here, FIG. 28 shows a measurement result at a driving frequency of 100 Hz, FIG. 29 shows a measurement result at a driving frequency of 300 Hz, and FIG. 30 shows a measurement result at a driving frequency of 1000 Hz.

  From FIG. 25 to FIG. 27, according to the PBT-LCD 1 of Example 6, it is clear that the voltage-transmittance characteristics are almost the same regardless of the temperature. On the other hand, according to the PBT-LCD 1 of Comparative Example 4 from FIGS. 28 to 30, the voltage-transmittance characteristics change with temperature, and the threshold voltage and sharpness change with temperature. Therefore, it is necessary to change the driving voltage with temperature. It is clear that the appearance of the display changes. According to the PBT-LCD 1 of Example 6, it is clear that such a phenomenon hardly occurs and has excellent characteristics with respect to temperature.

  Next, when the voltage holding ratio of the PBT-LCD 1 of Example 6 and Comparative Example 4 was measured, the PBT-LCD 1 of Example 6 was 92.5%, and the PBT-LCD 1 of Comparative Example 4 was 97.2%. However, the voltage holding ratio is lowered by using the liquid crystal-compatible particle-containing liquid crystal (liquid crystal-compatible gallium nanoparticle-containing liquid crystal) L. However, the PBT-LCD 1 of Example 6 has no influence on the display due to the decrease in the voltage holding ratio, and even when driven at a drive frequency of 50 Hz or less, there is no particular problem such as non-uniform display. A good display state was shown.

In this example, first, a vertically aligned cell (empty cell) was prepared using a substrate on which an ITO electrode pattern (character type) was formed, and the liquid crystal compatible particle-containing liquid crystal (Example 6) obtained in Example 6 was used in the cell. A liquid crystal-compatible gallium nanoparticle-containing liquid crystal) L was injected, and a polarizing plate was attached to prepare an evaluation cell. Next, using an electrostatic test machine (trade name: SEE-200AX, manufactured by Noise Research Institute Co., Ltd.), the evaluation cell prepared in this example was placed on an insulating plate made of a 5 mm thick bake plate, and the evaluation was performed. The contact discharge was performed once for 1 second in the center of the display area of the cell for use. The time until the liquid crystal operated by electrostatic charging completely returned to the entire surface was measured as the return time. The measurement was performed at a temperature of 22 ° C., a humidity of 36%, a capacity of 150 pF, and a resistance of 330Ω. The results are shown in Table 7.
[Comparative Example 5]
In this comparative example, except that a plurality of types of liquid crystal molecule mixture (liquid crystal having negative dielectric anisotropy (Δε) manufactured by Merck) containing no liquid crystal compatible particles (liquid crystal compatible gallium nanoparticles) was used, An evaluation cell was fabricated in exactly the same manner as in Example 7. Next, the return time of the evaluation cell produced in this comparative example was measured exactly as in Example 7. The results are shown in Table 7.

  In this example, first, a liquid crystal L containing liquid crystal-compatible particles was prepared as follows.

  In a glass container with an internal volume of 500 ml equipped with a stirrer, thermometer, reflux condenser and dropping funnel, a liquid crystal molecule mixture of plural types (a liquid crystal having a negative dielectric anisotropy (Δε) manufactured by Dainippon Ink & Chemicals, Inc.) ) 0.800 g, 144 ml of tetrahydrofuran and 40.0 ml of 2-propanol were added, and then 16.0 ml of 0.0100 mol / l gallium (III) acetylacetonate in tetrahydrofuran (containing 0.160 mmol as gallium atoms) was added. And heated and stirred at 65 to 75 ° C. for 7 hours. After completion of the reaction, the reaction solution was cooled to room temperature to obtain 200 ml of a colorless and uniform liquid crystal-compatible gallium nanoparticle dispersion.

  Next, 144 ml of the liquid crystal compatible gallium nanoparticle dispersion prepared in this example was added to 7.42 g of the liquid crystal molecule mixture of plural types, and the resulting mixture was concentrated and dried under reduced pressure. 8.00 g of liquid crystal-compatible gallium nanoparticle-containing liquid crystal was obtained.

Next, a vertical alignment cell (empty cell) was prepared using a substrate on which an ITO electrode pattern (character type) was formed, and the liquid crystal compatible particle-containing liquid crystal (liquid crystal compatible gallium) obtained in this example was used in the cell. Nanoparticle-containing liquid crystal) L was injected, and a polarizing plate was attached to prepare an evaluation cell. Next, using an electrostatic test machine (trade name: SEE-200AX, manufactured by Noise Research Institute Co., Ltd.), the evaluation cell prepared in this example was placed on an insulating plate made of a 5 mm thick bake plate, and the evaluation was performed. The contact discharge was performed once for 1 second in the center of the display area of the cell for use. The time until the liquid crystal operated by electrostatic charging completely returned to the entire surface was measured as the return time. The measurement was performed at a temperature of 23 ° C., a humidity of 48%, a capacity of 150 pF, and a resistance of 330Ω. The results are shown in Table 8.
[Comparative Example 6]
In this comparative example, a liquid crystal molecule mixture containing no liquid crystal compatible particles (liquid crystal compatible gallium nanoparticles) (liquid crystal with negative dielectric anisotropy (Δε) manufactured by Dainippon Ink Industries, Ltd.) is used. An evaluation cell was produced in exactly the same manner as in Example 8 except that the above was used. Next, the return time of the evaluation cell produced in this comparative example was measured exactly as in Example 8. The results are shown in Table 8.

In this example, the liquid crystal-compatible particle-containing liquid crystal (liquid crystal-compatible gallium nanoparticle-containing liquid crystal) L obtained in this example was injected into an actual product PBT-LCD to produce an evaluation cell. Next, the return time of the PBT-LCD was measured in the same manner as in Example 8 except that the polarizing plate protective film was peeled off instead of the contact discharge in Example 8. The results are shown in Table 9.
[Comparative Example 7]
In this comparative example, an actual PBT-LCD contains a plurality of types of liquid crystal molecule mixtures containing no liquid crystal compatible particles (liquid crystal compatible gallium nanoparticles) (dielectric anisotropy (Δε) manufactured by Dainippon Ink & Chemicals, Inc.). Was injected to prepare an evaluation cell. Next, the return time of the PBT-LCD was measured in the same manner as in Example 8 except that the polarizing plate protective film was peeled off instead of the contact discharge in Example 8. The results are shown in Table 9.

  From Tables 8 and 9, the PBT-LCDs of Examples 8 and 9 using liquid crystal-compatible particle-containing liquid crystal (liquid crystal-compatible gallium nanoparticle-containing liquid crystal) L are liquid crystal-compatible particles (liquid crystal-compatible gallium nanoparticles). It is clear that the return time is shorter than the PBT-LCDs of Comparative Examples 6 and 7 using a plurality of kinds of liquid crystal molecule mixtures which are not contained at all, and the liquid crystal compatible gallium nanoparticles are effective for countermeasures against static electricity.

  In Example 9 and Comparative Example 7, when the polarizing plate protective film was peeled off, the first return time was long when the protective film was peeled from the polarizing plate for the first time. This is thought to be due to the high level of static electricity. In cell inspection in the production of PBT-LCD as a real product, it is often performed after several steps of peeling off the protective film before inspection. Therefore, the measurement result after the second time can be regarded as the actual return time. In fact, it is apparent that the effect of shortening the return time in the inspection process of the PBT-LCD using the liquid crystal compatible gallium nanoparticle-containing liquid crystal is about 10 times or more that when the liquid crystal compatible gallium nanoparticle-containing liquid crystal is not used. is there.

  In addition, PBT-LCD using liquid crystal compatible gallium nanoparticles-containing liquid crystal is expected to have the same effect on the return time of display malfunction when the PBT-LCD screen is wiped with nylon cloth etc. in the actual product. Can do. In particular, it is clear from Table 8 that PBT-LCD using liquid crystal-compatible gallium nanoparticle-containing liquid crystal does not malfunction for static electricity up to an applied voltage of +8 kV, and has a great effect on actual products. It is clear.

  Next, the voltage holding ratios of the PBT-LCDs of Example 9 and Comparative Example 7 were measured 2 to 8 times at room temperature. The results are shown in Table 10.

  From Table 10, it is clear that PBT-LCD using liquid crystal-compatible gallium nanoparticle-containing liquid crystal has a slightly lower voltage holding ratio than the case where liquid crystal-compatible gallium nanoparticle-containing liquid crystal is not used. However, the PBT-LCD using the liquid crystal containing liquid crystal compatible gallium nanoparticles has no influence on the display due to the decrease in the voltage holding ratio, and the display becomes non-uniform even when driven at a driving frequency of 50 Hz or less. The defect was not particularly observed and showed a good display state.

  In this example, first, a liquid crystal-compatible particle-containing liquid crystal was prepared as follows.

  In a glass container having an internal volume of 500 ml equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, 1.2 g of a mixture of plural kinds of liquid crystal molecules (Merck, trade name: M6), 240 ml of tetrahydrofuran and 2-propanol 60 ml was added. The plurality of kinds of liquid crystal molecule mixture (trade name: M6, manufactured by Merck & Co.) have Δn: about 0.157, Δε: about −3.0, and resistivity: about 5E + 13 Ωcm.

  Next, 72.0 ml of a 0.01 mol / l thallium (I) acetylacetonate tetrahydrofuran solution (0.240 mmol as thallium atoms) was mixed into the glass container, and the resulting mixture was heated to a temperature of 60 ° C. For 7 hours with stirring. After completion of the reaction, the reaction solution was cooled to room temperature in 1 hour to obtain a liquid crystal-compatible thallium nanoparticle dispersion liquid in which liquid crystal-compatible thallium nanoparticles as Group 13 metal liquid crystal compatible particles were dispersed.

  Next, in a glass container with an internal volume of 1000 ml, 38.98 g of the liquid crystal molecule mixture (trade name: M6, manufactured by Merck & Co.) and 245 ml of the liquid crystal-compatible thallium nanoparticle dispersion prepared in this example. And stirred. Then, after concentrating under reduced pressure, it dried with the vacuum pump and obtained liquid crystal compatible thallium nanoparticle containing liquid crystal 40.03g as a group 13 metal liquid crystal compatible particle addition liquid crystal.

  Next, using the liquid crystal-compatible thallium nanoparticle-containing liquid crystal prepared in this example, a TFT-LCD was manufactured as follows.

  First, a transparent film made of indium tin oxide (ITO) was formed as a common electrode on the surface of a non-alkali glass (white plate glass) substrate serving as an upper substrate. The transparent film can be formed by CVD, vapor deposition, sputtering, or the like. At this time, the transparent film may be formed only at a predetermined position using a metal mask made of stainless steel or the like.

  In this embodiment, in order to set the MVA (Multi-domain Vertical Alignment) mode, a transparent film made of ITO having a width of about 5 to 20 μm is formed at a predetermined position of the common electrode by patterning using photolithography. Line-shaped slits that were not formed were provided.

For the patterning, first, using a roll coater or a slit coater, a photoresist material (for example, a positive resist manufactured by Tokyo Ohka Kogyo Co., Ltd., trade name: OFPR-800) is applied to a thickness of several μm on the transparent film. did. Next, the photoresist material is pre-baked for 3 minutes at a temperature of 110 ° C. using a hot plate, and then is irradiated with ultraviolet rays of 100 mJ / mm using an exposure machine using a photomask having a predetermined pattern. Irradiated with an intensity of cm ² . Next, development was performed using an alkaline solution (for example, 1 wt% -potassium hydroxide aqueous solution), and post-baking treatment was performed at a temperature of 130 ° C. for 3 minutes using a hot plate. Next, an etchant for ITO (for example, an ITO series manufactured by Kanto Chemical Co., Ltd. (trade names: ITO-02, ITO-06N, ITO-07N), etc., nitric acid / hydrochloric acid system, ferric chloride (FeCl ₃ ) system, etc.) After the transparent film was etched by wet etching, the photoresist material was removed using a strong alkali solution (for example, 3 wt% potassium hydroxide aqueous solution).

  By the patterning described above, the slits arranged so as to correlate with pixel electrodes described later were formed. In this case, for example, only one slit may be provided at a position facing the center of the pixel electrode, or a plurality of slits may be provided at a position facing the pixel electrode. The upper substrate obtained by the above procedure is hereinafter referred to as a common electrode substrate.

  In addition, in order to set it as the said MVA mode, the structure which equips the transparent electrode with the said slit is well-known (for example, refer Unexamined-Japanese-Patent No. 7-234414). Moreover, in order to set it as the said MVA mode, a projection part may be provided in a transparent electrode and the structure provided with this protrusion is also well-known (for example, refer Unexamined-Japanese-Patent No. 10-186330).

  Next, a TFT was formed on the non-alkali glass (white plate glass) substrate serving as the lower substrate as follows.

  First, a metal film was formed on the glass substrate as a gate electrode material. The metal film is made of Mo, Ta, Al, Cr, or the like, and can be formed by sputtering, vacuum deposition, or the like.

  Next, a gate electrode and a gate line were formed by patterning the metal film using photolithography. Etching of the metal film can be performed by wet etching. As the etchant, KSMF-100 (trade name), KSMF-200 (trade name) series, mixed acid, etc. manufactured by Kanto Chemical Co., Inc. can be used.

Next, a gate insulating film was formed on the alkali-free glass substrate so as to cover the gate electrode and the gate line. The gate insulating film is made of SiN _x , SiO ₂ , TaO _x or the like, and can be formed by plasma CVD, anodic oxidation, sputtering, or the like.

Next, an amorphous Si film and an n ⁺ : amorphous Si film were formed on the gate insulating film. The amorphous Si film and the n ⁺ : amorphous Si film can be formed by plasma CVD.

Next, patterning using photolithography is performed on the amorphous Si film and the n ⁺ : amorphous Si film to form regions where source / drain electrodes (described later) are formed on the gate electrode. A covering amorphous Si island was formed. Etching in the patterning was performed by dry etching. The dry etching can be performed using a mixed gas of CF ₄ and O ₂ , CF ₄ gas, CCl ₄ gas, SF ₆ gas, or the like. The dry etching is preferably performed by reactive ion etching (RIE) from the viewpoint of selectivity.

Next, the resist was removed by ashing using O ₂ , CF ₄ or a mixed gas thereof.

The amorphous Si film and the n ⁺ : amorphous Si film may be annealed before patterning or after patterning to be polycrystallized (polycrystal Si). The annealing can be performed by a laser, for example.

  Next, a metal film was formed as a source / drain electrode material on the gate insulating film and the amorphous Si island. The metal film is made of Mo, Ta, Al, Cr, or the like, and can be formed by sputtering, vacuum deposition, or the like.

  Next, source / drain electrodes and source lines were formed by patterning the metal film using photolithography. The source / drain electrodes are formed on the amorphous Si island, and the source line is connected to the source electrode and provided to be orthogonal to the gate line in plan view.

  Next, a transparent film made of ITO was formed as a pixel electrode material on the gate insulating film and the source / drain electrodes. The transparent film can be formed by sputtering, vacuum deposition or the like.

  Next, by patterning the transparent film using photolithography, a pixel electrode connected to the drain electrode was formed on the gate insulating film. Etching in the patterning can be performed using the same etchant as that used for forming the common electrode when wet etching is performed, and methanol vapor or the like can be used when performing dry etching.

  The pixel electrode may include a slit corresponding to the slit formed in the common electrode. The slit may be formed simultaneously with the pixel electrode by using a photomask pattern.

Next, the portion of the n ⁺ : amorphous Si film exposed to the outside between the source electrode and the drain electrode was removed by dry etching. For the dry etching, a mixed gas of CF ₄ and O ₂ , CF ₄ gas, CCl ₄ gas, SF ₆ gas, or the like can be used. Next, the resist was removed by ashing using O ₂ , CF ₄ or a mixed gas thereof.

Next, a passivation film was formed on the TFT and the pixel electrode formed by the above procedure. The passivation film is made of SiN _x , SiO ₂ or the like, and can be formed by plasma CVD, sputtering, vacuum deposition, or the like. The lower substrate obtained by the above procedure is hereinafter referred to as a TFT substrate.

  Next, vertical alignment films having substantially the same pattern were formed on the common electrode substrate and the display portion on the TFT substrate using a liquid crystal alignment material (trade name: SE-1211, manufactured by Nissan Chemical Industries, Ltd.). The vertical alignment film can be formed by flexographic printing or an inkjet method.

  Next, a thermosetting sealant (trade name: ES-7500, manufactured by Mitsui Chemicals, Inc.) is applied to the inner surface of one of the common electrode substrate and the TFT substrate in a predetermined pattern by screen printing. Printed. As the thermosetting sealant, one containing several weight% of glass fiber having a size of 3.9 μm was used.

  The pattern is a pattern having an inlet when the vacuum injection method is used, and a closed pattern without an inlet when the ODF method is used. The printing may be performed using a dispenser or the like. In place of the thermosetting sealant, a photocurable sealant, a combined light / heat sealant, or the like may be used.

  Next, printing was performed by a screen printing method at a predetermined position on the inner surface of the substrate on which the sealing agent was printed, using the thermosetting sealing agent containing several wt% of 4.5 μm Au balls as a conductive material. The conductive material is printed to connect a part of terminals provided on the TFT substrate side and the common electrode.

  Next, silica spheres having a diameter of 4 μm were sprayed as a gap control agent on the inner surface of the common electrode substrate or the TFT substrate on which the sealant was not printed by a dry spraying method. The gap control agent may be subjected to a surface treatment so as not to disturb the alignment of the liquid crystal, or may be colored.

  Instead of the gap control agent, ribs may be formed. The rib is generally formed on the common electrode substrate side, and is formed in a dot shape at a position facing the portion other than the pixel electrode of the TFT substrate. The ribs are formed with a predetermined thickness using a photosensitive resin by spin coating, slit coating, or the like, and then patterned into a predetermined shape using photolithography.

  Next, the common electrode substrate and the TFT substrate were overlapped at predetermined positions to form a cell, and heat treatment was performed in a pressed state to cure the sealant, thereby forming a sealant layer.

  Next, the common electrode substrate and the TFT substrate were scratched with a scriber device, and cells were formed by breaking into predetermined sizes and shapes. Next, the liquid crystal-compatible thallium nanoparticle-containing liquid crystal was injected into the cell by a vacuum injection method, and the injection port was sealed with an end sealant.

  In the case where the liquid crystal compatible thallium nanoparticle-containing liquid crystal is injected by the ODF method, the liquid crystal compatible thallium nanoparticle-containing liquid crystal is placed inside the sealing agent printed in a closed pattern without an injection port. After a predetermined amount is dropped on the substrate by a dispenser or the like, the common electrode substrate and the TFT substrate are overlapped at a predetermined position in a vacuum to form a cell, and the sealant is irradiated with ultraviolet rays while being pressed at atmospheric pressure. After that, heat treatment is performed to cure the sealant to form a sealant layer. Then, the common electrode substrate and the TFT substrate are scratched by a scriber device, and divided into predetermined sizes and shapes by breaking.

  Thereafter, chamfering and cleaning are performed, and a polarizing plate is attached to the outer surface of the common electrode substrate and the TFT substrate in a predetermined pattern (a crossed Nicol arrangement having an angle of 45 ° with respect to the rubbing). A mari black vertical alignment TFT-LCD was formed. A polarizing plate with a visual (optical) compensation plate was used.

Next, using the TFT-LCD of this example, the time until the malfunction due to static electricity was eliminated was measured as the return time. The return time is measured by placing the evaluation cell on a 5 mm-thick bake plate using an electrostatic tester (trade name: SEE-200AX, manufactured by Noise Research Institute Co., Ltd.). A contact discharge of 1 second was performed once in the center of the area, and the time until the liquid crystal operated by electrostatic charging completely returned was measured. The results are shown in Table 11. Further, the voltage holding ratio at room temperature of the TFT-LCD of this example was measured by the electrostatic test machine. The results are shown in Table 12.
[Comparative Example 8]
In this comparative example, a mixture of a plurality of types of liquid crystal molecules (trade name: M6, manufactured by Merck & Co., Inc.) was used, which was exactly the same as Example 10 except that a liquid crystal compatible thallium nanoparticle was not used at all. A normally black vertical alignment TFT-LCD was manufactured. Next, the return time and the voltage holding ratio at room temperature were measured in the same manner as in Example 10 except that the TFT-LCD obtained in this comparative example was used. Table 11 shows the measurement results of the return time, and Table 12 shows the measurement results of the voltage holding ratio.

  From Table 11, according to the TFT-LCD of Example 10 provided with a liquid crystal cell comprising the liquid crystal compatible thallium nanoparticle-containing liquid crystal, the liquid crystal molecules containing no liquid crystal compatible thallium nanoparticles with respect to the elimination time of malfunction due to static electricity It is clear that the TFT-LCD of Comparative Example 8 having a liquid crystal cell made of a mixture has remarkably superior performance.

  From Table 12, the liquid crystal cell composed of the liquid crystal containing thallium nanoparticles containing liquid crystal compatible in Example 10 has a better voltage holding than the liquid crystal cell composed of a mixture of liquid crystal molecules containing no liquid crystal compatible thallium nanoparticles in Comparative Example 8. It is clear that it can be suitably used as a liquid crystal cell of a TFT-LCD.

  In this example, first, a liquid crystal-compatible particle-containing liquid crystal was prepared as follows.

  In a glass container having an internal volume of 500 ml equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, 0.800 g of a mixture of plural kinds of liquid crystal molecules (Merck, product name: M4), 144 ml of tetrahydrofuran and 2-propanol 40 ml was added.

  Next, 16.0 ml of a 0.01 mol / l thallium (I) acetylacetonate tetrahydrofuran solution (0.160 mmol as a thallium atom) was added to the glass container, and the resulting mixture was heated under reflux ( The reaction was performed at an internal temperature of 69 ° C. for 8 hours. After completion of the reaction, the reaction solution was cooled to room temperature in 1 hour to obtain 200 ml of a liquid crystal compatible thallium nanoparticle dispersion liquid in which liquid crystal compatible thallium nanoparticles as Group 13 metal liquid crystal compatible particles were dispersed. The liquid crystal-compatible thallium nanoparticle dispersion was colorless and uniform.

  Next, as a result of analyzing the liquid crystal compatible thallium nanoparticles with a transmission electron microscope, the particle diameter of the central metal of the liquid crystal compatible thallium nanoparticles was uniform within a range of 1 to 5 nm.

  Next, in a glass container with an internal volume of 1000 ml, 4.87 g of the liquid crystal molecule mixture (trade name: M4, manufactured by Merck & Co.) and the liquid crystal-compatible thallium nanoparticle dispersion 30 prepared in this example. .6 ml (5.00 mg as total metal amount) was added and stirred. Then, after concentrating under reduced pressure, it dried with the vacuum pump, and obtained liquid crystal compatible thallium nanoparticle containing liquid crystal 5.00g as a group 13 metal liquid crystal compatible particle addition liquid crystal.

  Next, a vertical alignment cell (empty cell) is prepared using a substrate on which an ITO electrode pattern (character type) is formed, and the liquid crystal containing the liquid crystal-compatible thallium nanoparticles prepared in this example is injected into the cell. An evaluation cell was prepared by attaching a polarizing plate to the outer surface of the substrate. Next, using an electrostatic test machine (trade name: SEE-200AX, manufactured by Noise Research Institute Co., Ltd.), the evaluation cell prepared in this example was placed on an insulating plate made of a 5 mm thick bake plate, and the evaluation was performed. A one-second contact discharge was performed once in the center of the display area of the cell. The time until the liquid crystal operated by electrostatic charging completely returned to the entire surface was measured as the return time. The results are shown in Table 13.

Further, the voltage holding ratio at room temperature and the power consumption of the evaluation cell produced in this example were measured by the electrostatic test machine. Table 14 shows the measurement results of the voltage holding ratio, and Table 15 shows the measurement results of the power consumption.
[Comparative Example 9]
In this comparative example, a mixture of a plurality of types of liquid crystal molecules (trade name: M6, manufactured by Merck & Co., Inc.) was used, which was exactly the same as Example 11 except that liquid crystal compatible thallium nanoparticles were not used at all. An evaluation cell was produced. Next, the return time, voltage holding ratio, and power consumption were measured in exactly the same manner as in Example 11 except that the evaluation cell obtained in this comparative example was used. Table 13 shows the return time measurement results, Table 14 shows the voltage retention measurement results, and Table 15 shows the power consumption measurement results.

  From Table 13, according to the TFT-LCD of Example 11 provided with the liquid crystal cell comprising the liquid crystal compatible thallium nanoparticle-containing liquid crystal, the liquid crystal molecules containing no liquid crystal compatible thallium nanoparticles with respect to the elimination time of malfunction due to static electricity It is clear that the TFT-LCD of Comparative Example 9 having a liquid crystal cell made of a mixture has remarkably superior performance.

  From Table 14, the liquid crystal cell composed of the liquid crystal containing thallium nanoparticles compatible with the liquid crystal of Example 11 has the same voltage holding ratio as the liquid crystal cell composed of the liquid crystal molecule mixture containing no liquid crystal compatible thallium nanoparticles of Comparative Example 9. It is clear that

  Since the TFT-LCD of Example 11 provided with a liquid crystal cell composed of the liquid crystal containing thallium nanoparticles compatible with the liquid crystal is effective in eliminating malfunction caused by static electricity as shown in Table 13, power consumption (current flowing through the cell) (Indicated by the reciprocal of cell resistance). However, from Table 15, the power consumption of the TFT-LCD of Example 11 is equivalent to that of the TFT-LCD of Comparative Example 9 having a liquid crystal cell composed of a liquid crystal molecule mixture containing no liquid crystal-compatible thallium nanoparticles. it is obvious.

  In this example, a liquid crystal compatible scandium nanoparticle-containing liquid crystal was obtained as a Group 3 metal liquid crystal compatible particle-added liquid crystal in the same manner as in Example 11 except that scandium was used instead of thallium.

  Next, a normally black vertical alignment TFT-LCD was produced in exactly the same manner as in Example 10 except that the liquid crystal-compatible scandium nanoparticle-containing liquid crystal prepared in this example was used. Next, except for using the TFT-LCD obtained in this example, the time until the malfunction due to static electricity is eliminated, the voltage holding ratio at room temperature, and the current consumption are exactly the same as in Example 11. It was measured.

  Table 16 shows the time until the malfunction due to static electricity is eliminated, and Table 17 shows the voltage holding ratio. For comparison, the results of Comparative Example 9 are shown again in Tables 16 and 17, respectively.

  In this example, liquid crystal-compatible terbium nanoparticle-containing liquid crystal was obtained in the same manner as in Example 11 except that terbium was used instead of thallium, as a liquid crystal added with a Group 3 metal liquid crystal compatible particle.

  Next, a normally black vertical alignment TFT-LCD was produced in exactly the same manner as in Example 10 except that the liquid crystal-compatible terbium nanoparticle-containing liquid crystal prepared in this example was used. Next, except for using the TFT-LCD obtained in this example, the time until the malfunction due to static electricity is eliminated, the voltage holding ratio at room temperature, and the current consumption are exactly the same as in Example 11. It was measured.

  Table 16 shows the time until the malfunction due to static electricity is eliminated, and Table 17 shows the voltage holding ratio.

  In this example, liquid crystal-compatible gadolinium nanoparticle-containing liquid crystal as a Group 3 metal liquid crystal compatible particle-added liquid crystal was obtained in the same manner as in Example 11 except that gadolinium was used instead of thallium.

  Next, a normally black vertical alignment TFT-LCD was produced in exactly the same manner as in Example 10 except that the liquid crystal-compatible gadolinium nanoparticle-containing liquid crystal prepared in this example was used. Next, except for using the TFT-LCD obtained in this example, the time until the malfunction due to static electricity is eliminated, the voltage holding ratio at room temperature, and the current consumption are exactly the same as in Example 11. It was measured.

  Table 16 shows the time until the malfunction due to static electricity is eliminated, and Table 17 shows the voltage holding ratio.

  In this example, a liquid crystal-compatible indium nanoparticle-containing liquid crystal as a Group 13 metal liquid crystal compatible particle-added liquid crystal was obtained in the same manner as in Example 11 except that indium was used instead of thallium.

  Next, a normally black vertical alignment TFT-LCD was produced in exactly the same manner as in Example 10, except that the liquid crystal-compatible indium nanoparticle-containing liquid crystal prepared in this example was used. Next, except for using the TFT-LCD obtained in this example, the time until the malfunction due to static electricity is eliminated, the voltage holding ratio at room temperature, and the current consumption are exactly the same as in Example 11. It was measured.

  Table 16 shows the time until the malfunction due to static electricity is eliminated, and Table 17 shows the voltage holding ratio.

  In this example, a liquid crystal compatible gallium nanoparticle-containing liquid crystal was obtained as a Group 13 metal liquid crystal compatible particle-added liquid crystal in the same manner as in Example 11 except that gallium was used instead of thallium.

  Next, a normally black vertical alignment TFT-LCD was produced in exactly the same manner as in Example 10 except that the liquid crystal-compatible gallium nanoparticle-containing liquid crystal prepared in this example was used. Next, except for using the TFT-LCD obtained in this example, the time until the malfunction due to static electricity is eliminated, the voltage holding ratio at room temperature, and the current consumption are exactly the same as in Example 11. It was measured.

  Table 16 shows the time until the malfunction due to static electricity is eliminated, and Table 17 shows the voltage holding ratio.

  In this example, liquid crystal-compatible neodymium nanoparticle-containing liquid crystal as a Group 3 metal liquid crystal compatible particle-added liquid crystal was obtained in the same manner as in Example 11 except that neodymium was used instead of thallium.

  Next, a normally black vertical alignment TFT-LCD was produced in exactly the same manner as in Example 10 except that the liquid crystal-compatible neodymium nanoparticle-containing liquid crystal prepared in this example was used. Next, except for using the TFT-LCD obtained in this example, the time until the malfunction due to static electricity is eliminated, the voltage holding ratio at room temperature, and the current consumption are exactly the same as in Example 11. It was measured.

  Table 16 shows the time until the malfunction due to static electricity is eliminated, and Table 17 shows the voltage holding ratio.

  In this example, a liquid crystal compatible cerium nanoparticle-containing liquid crystal as a Group 3 metal liquid crystal compatible particle-added liquid crystal was obtained in the same manner as in Example 11 except that cerium was used instead of thallium.

  Next, a normally black vertical alignment TFT-LCD was produced in exactly the same manner as in Example 10 except that the liquid crystal-compatible cerium nanoparticle-containing liquid crystal prepared in this example was used. Next, except for using the TFT-LCD obtained in this example, the time until the malfunction due to static electricity is eliminated, the voltage holding ratio at room temperature, and the current consumption are exactly the same as in Example 11. It was measured.

  Table 16 shows the time until the malfunction due to static electricity is eliminated.

  From Table 16, according to TFT-LCD of Examples 12-18 provided with the liquid crystal cell which consists of said group 3 metal liquid crystal compatible particle addition liquid crystal or group 13 metal liquid crystal compatibility particle addition liquid crystal, elimination of malfunction due to static electricity In terms of time, it was markedly superior to the TFT-LCD of Comparative Example 9 comprising a liquid crystal cell comprising a liquid crystal molecule mixture containing no Group 3 metal liquid crystal compatible particles or no Group 13 metal liquid crystal compatible particles. It is clear that it has performance.

  From Table 17, the liquid crystal cells composed of the Group 3 metal liquid crystal compatible particle-added liquid crystal or the Group 13 metal liquid crystal compatible particle-added liquid crystal of Examples 12 to 18 each have a voltage holding ratio of 90% or more. It is apparent that the voltage holding ratio is the same as that of the liquid crystal cell composed of the liquid crystal molecule mixture of Comparative Example 9 which does not contain the Group 3 metal liquid crystal compatible particles or the Group 13 metal liquid crystal compatible particles.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. The graph which shows the temperature dependence of the voltage-transmittance characteristic in the drive frequency of 100 Hz of the liquid crystal display device of the 1st Example of this invention. 3 is a graph showing temperature dependence of voltage-transmittance characteristics at a driving frequency of 300 Hz of the liquid crystal display device according to the first embodiment of the present invention. The graph which shows the temperature dependence of the voltage-transmittance characteristic in the drive frequency 1000Hz of the liquid crystal display device of the 1st Example of this invention. The graph which shows the temperature dependence of the voltage-transmittance characteristic in the drive frequency of 100 Hz of the liquid crystal display device of the 2nd Example of this invention. The graph which shows the temperature dependence of the voltage-transmittance characteristic in the drive frequency of 300 Hz of the liquid crystal display device of the 2nd Example of this invention. The graph which shows the temperature dependence of the voltage-transmittance characteristic in the drive frequency 1000Hz of the liquid crystal display device of the 2nd Example of this invention. The graph which shows the temperature dependence of the voltage-transmittance characteristic in the drive frequency of 100 Hz of the liquid crystal display device of the 1st comparative example with respect to this invention. The graph which shows the temperature dependence of the voltage-transmittance characteristic in the drive frequency of 300 Hz of the liquid crystal display device of the 1st comparative example with respect to this invention. The graph which shows the temperature dependence of the voltage-transmittance characteristic in the drive frequency 1000Hz of the liquid crystal display device of the 1st comparative example with respect to this invention. The graph which shows the drive frequency dependence of the voltage-transmittance characteristic in room temperature (25 degreeC) of the liquid crystal display device of the 5th Example of this invention. The graph which shows the drive frequency dependence of the voltage-transmittance characteristic in 0 degreeC of the liquid crystal display device of the 5th Example of this invention. The graph which shows the drive frequency dependence of the voltage-transmittance characteristic in -20 degreeC of the liquid crystal display device of the 5th Example of this invention. The graph which shows the drive frequency dependence of the voltage-transmittance characteristic in -30 degreeC of the liquid crystal display device of the 5th Example of this invention. The graph which shows the temperature dependence of the voltage-transmittance characteristic in the drive frequency of 100 Hz of the liquid crystal display device of the 5th Example of this invention. The graph which shows the temperature dependence of the voltage-transmittance characteristic in the drive frequency of 300 Hz of the liquid crystal display device of the 5th Example of this invention. The graph which shows the temperature dependence of the voltage-transmittance characteristic in the drive frequency 1000Hz of the liquid crystal display device of the 5th Example of this invention. The graph which shows the drive frequency dependence of the voltage-transmittance characteristic in room temperature (25 degreeC) of the liquid crystal display device of the 3rd comparative example with respect to this invention. The graph which shows the drive frequency dependence of the voltage-transmittance characteristic in 0 degreeC of the liquid crystal display device of the 3rd comparative example with respect to this invention. The graph which shows the drive frequency dependence of the voltage-transmittance characteristic in -20 degreeC of the liquid crystal display device of the 3rd comparative example with respect to this invention. The graph which shows the drive frequency dependence of the voltage-transmittance characteristic in -30 degreeC of the liquid crystal display device of the 3rd comparative example with respect to this invention. The graph which shows the temperature dependence of the voltage-transmittance characteristic in the drive frequency of 100 Hz of the liquid crystal display device of the 3rd comparative example with respect to this invention. The graph which shows the temperature dependence of the voltage-transmittance characteristic in the drive frequency of 300 Hz of the liquid crystal display device of the 3rd comparative example with respect to this invention. The graph which shows the temperature dependence of the voltage-transmittance characteristic in the drive frequency of 1000 Hz of the liquid crystal display device of the 3rd comparative example with respect to this invention. The graph which shows the temperature dependence of the voltage-transmittance characteristic in the drive frequency of 100 Hz of the liquid crystal display device of the 6th Example of this invention. The graph which shows the temperature dependence of the voltage-transmittance characteristic in the drive frequency of 300 Hz of the liquid crystal display device of the 6th Example of this invention. The graph which shows the temperature dependence of the voltage-transmittance characteristic in the drive frequency 1000Hz of the liquid crystal display device of the 6th Example of this invention. The graph which shows the temperature dependence of the voltage-transmittance characteristic in the drive frequency of 100 Hz of the liquid crystal display device of the 4th comparative example with respect to this invention. The graph which shows the temperature dependence of the voltage-transmittance characteristic in the drive frequency of 300 Hz of the liquid crystal display device of the 4th comparative example with respect to this invention. The graph which shows the temperature dependence of the voltage-transmittance characteristic in the drive frequency of 1000 Hz of the liquid crystal display device of the 4th comparative example with respect to this invention.

Claims (12)

Group 3 or Group 13 metal liquid crystal compatible particles comprising a Group 3 or Group 13 metal , at least one metal other than the Group 3 or Group 13 metal, and at least one liquid crystal molecule, A liquid crystal display device comprising a group 3 or group 13 metal liquid crystal compatible particle-added liquid crystal added to a mixed liquid crystal material formed by mixing a plurality of types of liquid crystal molecules.   The liquid crystal display device according to claim 1, wherein the mixed liquid crystal material has a negative dielectric anisotropy.   The liquid crystal display device according to claim 1, wherein the Group 3 or Group 13 metal liquid crystal compatible particles are nanoparticles. The Group 3 metal or Group 13 of the nanoparticles in the range of 0.02 to 1.0% by weight with respect to the total amount of liquid crystal contained in the Group 3 or Group 13 metal liquid crystal compatible particle-added liquid crystal. 4. The liquid crystal display device according to claim 3 , comprising metal liquid crystal compatible particles.   2. The liquid crystal display device according to claim 1, wherein the Group 3 or Group 13 metal liquid crystal compatible particle-added liquid crystal is aligned in a direction perpendicular to the substrate.   The Group 3 metal is at least one metal selected from the group consisting of scandium, yttrium, terbium, gadolinium, neodymium, and cerium, and the Group 13 metal is selected from the group consisting of thallium, indium, and gallium. The liquid crystal display device according to claim 1, wherein the liquid crystal display device is at least one kind of metal.   The liquid crystal display device according to claim 1, wherein the liquid crystal display device is a display panel using static drive or DUTY drive. 8. The liquid crystal display according to claim 7 , wherein the liquid crystal display device is a display panel selected from the group consisting of a character display panel, a dot matrix display panel, and a character / dot matrix mixed display panel. apparatus. 8. The liquid crystal display according to claim 7 , wherein the Group 3 metal is any one of scandium or yttrium, and the Group 13 metal is any one of thallium or gallium. apparatus.   The liquid crystal display device according to claim 1, wherein the liquid crystal display device is a display panel using active driving. The liquid crystal display device according to claim 10 , wherein the mixed liquid crystal material has a resistivity of at least 1E + 13 Ωcm. The Group 3 metal is at least one metal selected from the group consisting of scandium, terbium, gadolinium, neodymium, and cerium, and the Group 13 metal is at least selected from the group consisting of thallium, indium, and gallium. The liquid crystal display device according to claim 10 , wherein the liquid crystal display device is one kind of metal.

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