JPS61204677A - Display material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] ri Higashijo Tachisarayu 1 The present invention relates to a display material and a method for manufacturing the same.

Conventional technologies and their problems In general, display methods include luminescent display, which displays by converting electrical energy into light, and non-luminescent display, which displays by controlling the absorption, scattering, reflection, diffraction, polarization, etc. of external light. display is known.

Requests for such a display method include the following.

(+) 11 degrees, with excellent contrast, gradation, pleochroism, etc., so that the display is easy to see and does not cause eye strain.

(11) It has a variety of configurations, can be manufactured to any thickness, is easy to control, has a fast response speed, and has a memory function, so it can be applied for many purposes.

(iii) Low cost, such as low material costs and simple display device manufacturing.

(iv) High reliability with little change over time, long life, robustness and excellent environmental resistance.

The above-mentioned light-emitting displays include those that utilize CRT, fluorescent display tubes, light-emitting diodes, electroluminescence, plasma light emission, etc., and have the advantage that the display is clear and easy to see. However, luminescent displays are harder to see in brighter surroundings, and because they use a conversion phenomenon from electricity to light, they require high voltage and ICl
There is a problem that 11i11 is not easy.

On the other hand, methods using liquid crystals, electrochromism, electrophoresis, etc. are being considered for non-luminescent displays, and since light can be controlled with little electrical energy, IC control is possible, and flexibility in the configuration of the display section is being considered. It is large, and the brighter the surrounding area, the easier it is to see. however,
There are problems in that it is difficult to produce a product with an arbitrary shape, and the production cost is high. Therefore, there is currently a demand for display materials that have better display functions and can be easily produced.

Steps for Solving the Problems In view of the problems of the prior art as described above, the inventor of the present invention
As a result of extensive research, we have found that by applying an aqueous solution, sol solution, or gel solution of an amorphous oxide containing V205 as a matrix onto a substrate with electrodes and drying it, it is possible to form a smooth and uniform surface very easily. 1ull was obtained, and when a voltage was applied to the electrodes, electrochromism occurred in this III and its color tone changed, and it was discovered that this phenomenon could be used as a display material. Furthermore, the present inventor adds at least one of an electrochromic substance, a dye, and a liquid crystal to the aqueous solution, sol solution, or gel solution,
By applying this solution on a substrate provided with an electrode and drying it, a thin film in which the additive substance is intercalated between the V2'05 layers is obtained. We have discovered that in addition to electrochromism, a variety of displays are possible through the effects of additive substances.

That is, the present invention provides the following display material and method for manufacturing the display material.

(1) A display material made of sII in which a metal oxide and/or a metalloid oxide is intercalated between layers of V2O5 having an amorphous or layered structure (hereinafter referred to as the first invention of the present application).

■ A display material consisting of a thin film in which at least one of an electrochromic substance, a dye, and a liquid crystal is intercalated between layers of V205 having an amorphous or layered structure (
(hereinafter referred to as the second invention).

(2) A method for manufacturing a display material, which comprises applying an aqueous solution, sol solution or gel solution of an amorphous oxide containing V2O5 as a matrix onto a substrate and drying the solution (hereinafter referred to as the third invention of the present application).

■ ■205 A display material characterized in that an aqueous solution, sol solution or gel solution consisting of an amorphous oxide as a matrix and at least one of an electrochromic substance, a dye and a liquid crystal is applied onto a substrate and dried. Manufacturing method (hereinafter referred to as the fourth invention).

The display material of the first invention of the present application can be obtained by applying an aqueous solution, sol solution or gel solution of an amorphous oxide onto a substrate provided with an electrode and drying it. Here, MyOz is Kim Will! It is a compound or metalloid oxide, and is 0 x x 1.

As MVOZ, various oxides can be used depending on the purpose, such as 1+ of group Ⅰ, Na.

K, oxides of Cs, Be, MQ, Ca of group Ⅰ.

5r, 3a oxide, group (■) Y oxide, group (■) Ti,
Zr oxide, V group Nb, Ta oxide, Ta group C
r, Mo, W oxide, Ta group Mn oxide, ■ group F
e, Go, Ni, Ru, Rh.

Pd, Os oxides, Ib group Cu, ACJ, AU oxides, mb group Zn, Cd, HQ oxides, mb group B
, A12. Ga, In, TQ oxides, rVb group 3i
, Ge, Sn, Pb oxides, Vb group P, As, S
b, B i oxide, (b) group Se, Te oxide, lanthanide type 1a, Ce.

Oxides of Nd, Gd, Tb, and Er can be used.

The effects of these oxides include, for example, B1°Ti,
Oxides such as Te, Ge, Cr, Fe, Ag, and W improve optical sensitivity; Cr.

Mo, W, Fe, Go, Ti, Nb, Ni, Cu.

Oxides such as Ag, TQ, Pb, Bi, Nd, and V can provide optical effects.

These oxides may be used alone or in combination of two or more components depending on the purpose.

In the present invention, (V20s) +-x ・(My Oz
) An aqueous solution, sol solution or gel solution of an amorphous oxide having the composition x can be prepared, for example, by the following method.

i) (V20s)+-x ・(MyOz)x
A method of forming an amorphous oxide with the following composition and dissolving or dispersing it in a solvent. In this case, the method for producing the amorphous oxide may be a known method, such as heating and melting the raw material oxide and rapidly cooling it by blowing it out onto the surface of a high-speed rotating roll or a cooling plate, heating and melting the raw material oxide, Examples include a method of atomizing with high pressure gas and rapid cooling, and a method of evaporating, ionizing, or causing a gas phase reaction of the raw material by PVD or CVD and depositing it on a substrate.

11) A method in which the raw material oxide is heated and melted, poured into a solvent, and rapidly cooled and dissolved at the same time.

iii) Methods for preparing solutions from alcoholade of vanadium and other additives, methods for preparing solutions from vanadates.

The aqueous solution, sol solution, or gel solution of the present invention uses water as a solvent, and the concentration of oxide may be about 0.001 to 10% by weight, but in order to form a uniform thin film, the concentration of oxide is about 0.001 to 10% by weight.
The content is preferably about 5.0% by weight. The concentration is 0.
If it is less than 0.0111%, uneven coating tends to occur;
If it exceeds % by weight, it is not preferable because it tends to cause unevenness in the thickness of the coating film.

In the present invention, if the hydrophilicity of the substrate or electrode to which the solution is applied is poor, an organic solvent may be added to the solution for the purpose of improving the compatibility between the solution and the substrate or electrode. As the organic solvent, any common organic solvent may be used, and representative examples thereof include methanol, ethanol, acetone, dimethylformamide, dimethyl sulfoxide, and the like.

The amount of organic solvent added is 0.01 to 10 of the above solution amount.
It should be about twice that. Furthermore, a polymeric material may be added to the solution in order to make the viscosity of the solution uniform, form a homogeneous coating film, and improve adhesion to the substrate and electrodes. As the polymer material, for example, organic materials such as polyvinyl alcohol, polyacrylamide, polyacrylic acid, and polyethylene glycol, and inorganic materials such as polyphosphoric acid and water glass can be used. Furthermore, polymethyl methacrylate, polyethylene, polycarbonate, polyester, etc. can also be used in combination with an organic solvent. The amount of the polymer material added may be approximately 0.01 to 10% relative to the solution. In the present invention, stabilizers, pH adjusters, emulsifiers, and the like may be added to these solutions to improve the stability of the solutions.

In the present invention, a solution prepared by the method described above is applied onto a substrate provided with electrodes. The substrate is not particularly limited and may be made of glass, metal, synthetic resin, etc. depending on the purpose. As the electrode, a transparent electrode or its counter electrode is installed. There are no particular restrictions on the transparent electrode that can be used, such as ITO, SnO2, I
Examples include noa, 5b2o3, etc., and can be placed on the substrate according to a conventional method. There are no particular restrictions on what can be used as the counter electrode; for example, metals such as aluminum, gold, copper, indium, and tin, and oxides such as tin oxide, indium oxide, and ITO may be used depending on the purpose. For example, it can be formed on a substrate by a method such as vapor deposition, sputtering, or plating.

The solution may be applied by any conventional method, such as a spray method, a coater method, a dip coating method, a spinner method, or a dipping method.

After coating, heat treatment is performed at a temperature from room temperature to about 500°C. The heat treatment removes moisture and stabilizes the molecular structure of the oxide, resulting in a smooth and uniform film. Film thickness is 0
．． The thickness may be approximately 0.05 to 10 μm. The specific heat treatment temperature is determined depending on the type of (V20s) +-x (MVOz)x, and is set to be lower than the crystallization temperature.

According to X-ray diffraction, in the thin film obtained by heat treatment, when the heat treatment temperature is between room temperature and the glass transition point, the V2O5 lattice planes are aligned in the C-axis direction, and very random in the a- and b-axis directions. It has an amorphous structure.

Further, when the heat treatment temperature is between the glass transition point and the crystallization temperature, the lattices in the a-axis and b-axis directions are aligned and stabilized, forming a layered structure. The oxide constituting the amorphous structure or layered structure is V2O5, and MVOZ exists between the layers of V205, and if there is water that remains without being removed, it exists between the eyebrows of V2O5 together with the water.

After forming IIS by the above method, a transparent electrode or its counter electrode is formed on the thin film. That is, when a transparent electrode is provided on a substrate, a counter electrode may be formed, and when a counter electrode is provided on a substrate, a transparent electrode may be formed on a thin film.

*mi obtained by the above method, the number of charges on the vanadium atoms changes by applying a voltage between the transparent electrode and the counter electrode, and the color tone changes accordingly.
By utilizing this property, it can be used as a display material. Furthermore, depending on the type of MVOZ intercalated between the eyebrows, it is possible to impart various effects such as optically improving sensitivity and imparting optical effects.

The display material of the second invention of the present application is (V205) +-x・
At least one of an electrochromic substance, a dye, and a liquid crystal is added to an aqueous solution, sol solution, or gel solution of an amorphous oxide represented by (MvOz)x, and this solution is applied onto a substrate provided with an electrode and dried. □ Obtained by letting.

The aqueous solution, sol solution, or gel solution of (V205) +−x·(MV 02 ) x is prepared in the same manner as in the case of producing the display material of the first invention of the present application. However, O≦
Let x<1. In the present invention, various types of electrochromic substances can be used, representative examples of which include:
Viologen compounds such as heptyl viologen and cyanophenyl viologen; pyridyl metal complexes such as cobalt bilisyl complexes; thiofulvalene compounds such as polymerized tetrathiofulvalene; and phthalocyanine compounds such as lutetium siphthalodianine and copper phthalocyanine. Various types of dyes can be used, such as azo dyes, stilbene dyes, naphthoquinone dyes, and the like. As the liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, etc. can be used, and specific examples include p-ethoxybenzylidine-p'-n-butylaniline (EBBA), p-methoxybenzylidine-p'-n-butylaniline. (MBBA), butyl-
4-41-ethoxyphenoxycarbonylphenyl carbonate (SEPCPC), N-(4-phenoxycarbonyloxybenzylidine)-4-7nizidine (PCB
A), 4-Schiff/-4'-n-pentylpiphenyl (
CPB), dicyclophenyl-18-crown-6 (
DC-1806), azobenzenefuramide crown ether, and the like.

The above-mentioned additive substances consisting of electrochromic substances, dyes and liquid crystals can be used alone or in combination,
The amount of additive material in the thin film is V20s 1) Lt vs. To, 001~1.0T:)I.

It may be done so that it is within the range of Added substance amount is 0°001
If the amount is less than 1 mol, the effect of addition will be small, while if it exceeds 1.0 mol, the smoothness of the formed film will deteriorate, which is not preferable.

In the present invention, (V20s) +-x ・(My Oz
) in a solution of x (V205) +−x” (
When MyOz ) It is believed that the interlayer expansion substance first penetrates into the colloidal particles, and then functions to facilitate the penetration of the additive substance into the colloidal particles. Examples of interlayer expansion substances include alcohols such as methanol and ethanol, ketones such as acetone, aldehydes such as acetaldehyde, amines such as methylamine and ethylamine,
Amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, nitrosos such as nitrosoaniline, ureas such as urea and thiourea, glycols such as ethylene glycol, carboxylic acids such as acetic acid, etc. can be used. Among these, organic solvents also have the function of dissolving substances that are poorly soluble in water, such as liquid crystals and oil-based solid dyes, and if necessary, these can be dissolved in an organic solvent to create a solution. It can be added to. Furthermore, it is assumed that hydrophilic solvents such as acetone and methanol also function to make the water molecules that have already entered the colloid particles and the additive substance become compatible. The amount of these interlayer expansion substances added to the solution is (
It is effective when the amount is about 0.01 mol or more per 1 mol of V20s ) t-x ・(MV OX )
When the amount exceeds 2 moles per 1 mole, the effect is no longer improved.

The display material of the second invention of the present application can be obtained by applying the solution prepared by the above method onto a substrate provided with electrodes and drying it. The coating method, drying conditions and film thickness may be the same as in the case of the first invention of the present application.

The display material of the second invention of the present application is a thin film in which an electrochromic substance, dye, or liquid crystal as an additive is intercalated between layers of V2O5 having an amorphous structure or a layered structure. That is, as mentioned above, when heat treatment is carried out at a temperature between room temperature and the glass transition point, there are In the case of heat treatment, a thin film is formed in which the additive substance is intercalated between the layers of V20s having a layered structure. In such a display material, when a voltage is applied between the transparent electrode and the opposite rod, in addition to a change in color tone due to a change in the number of charges of vanadium, an effect due to the additive substance occurs. That is, in a thin film intercalated with an electrochromic substance, in addition to the electrochromism of V2O5, electrochromism of the additive substance occurs, and various displays are possible. A thin film in which dyes are intercalated has effects such as pleochroism of color tone and improvement of contrast ratio. *m with intercalated liquid crystal
In this case, when a voltage is applied, the liquid crystal exhibits its display function, making it possible to display a complex display, resulting in effects such as improved color tone pleochroism, brightness, gradation sensitivity, and contrast ratio. In addition, when a thin film with intercalated liquid crystal is formed into a layered structure by heat treatment, the interlayer spacing is the minimum size of the intercalated substance, so a monomolecular layer of liquid crystal is easily formed between the layers, resulting in display effects. becomes higher. Therefore, the method according to the fourth invention of the present application is also useful as a liquid crystal containment technique.

In the present invention, the display effect can be further improved by forming a 3NWA layer having an optical absorption or reflection effect at an appropriate position of the display medium composed of the above-mentioned substrate, transparent electrode, display material, and counter electrode. can. Further, in order to improve durability, an organic or inorganic I film may be formed on the display medium. This organic or inorganic thin film may be appropriately selected from transparent or opaque depending on the display method.For example, organic resin such as polyester resin, urethane resin, acrylic resin, polyimide resin, epoxy resin, ultraviolet curable resin, etc. , 5tO2, etc. can be used.

The display materials of the first and second inventions of the present application can be used not only as a single thin film, but also can be easily laminated into multiple thin films by repeating this process after coating and drying, and electrodes can be placed between the thin films as appropriate. This allows it to be used as a multiplicity display material.

In such a case, significant effects such as improved color tone pleochroism, brightness, and gradation sensitivity can be achieved.

Various known methods can be used as display methods using the display materials of the first and second inventions of the present application, such as methods that utilize light absorption, scattering, reflection, diffraction, polarization, etc. .

1 凰oni 11 The present invention provides the following effects.

(2) Since a coating liquid of any composition can be easily obtained, display materials suitable for purposes can be easily produced with high precision.

(2) Since the display material of the present invention is produced by coating7, it can be easily produced in a large area or in a complicated shape, and can be produced on a substrate provided with arbitrary electrodes.

■ The display material is easy to produce and can be obtained at low cost. Additionally, the resulting display material has a long life.

■ The display material has a low operating voltage and a wide operating temperature range.
Moreover, the display speed is fast.

■ Brightness and contrast ratio are 1.5 to 1.5 compared to conventional display materials.
It is more than twice as large, has no visual dependence, and has a memory function.

(2) Display materials with any desired pleochroism can be made by combining additive substances.

(2) Display materials can be easily laminated and can be made into multifunctional display materials.

Example Next, the present invention will be explained in more detail by showing examples.

Examples 1 to 12 Amorphous ribbon materials were obtained using V2O3 (purity 99.9%) as a matrix by ultra-quenching with high-speed rotating rolls.

The composition and manufacturing conditions are shown in Table 1.

Each ribbon material obtained by the method described above has a particle size of 30 to 40.
Grind to μm1 thickness 5-10 μm and add 3
After adding 0.001 g of the mixture and shaking it for 30 minutes, it was allowed to stand at room temperature, and then undissolved amorphous substances were separated by filtration. Next, 100 ma of additive substances shown in Table 2 were added to each solution to prepare coating solutions.

In addition, for Example 7, the molar ratio is EBBA:MBBA-223.

Prepared using the method described above! 1! The first step is to apply the cloth solution onto the glass substrate on which the ITO electrode is installed using a spinner method.
(stage 120 rpm x 30 seconds), second stage 1200 rpm x 5 seconds) and dried to obtain a display material. The drying conditions and film thickness are shown in Table 2.

Next, on this display material, aluminum was formed as an electrode with high reflectance by sputtering to serve as a counter electrode. Table 2 shows the results of display by applying a voltage between the ITO electrode and the counter electrode. All the samples of Examples 1 to 12 had excellent brightness and contrast, and good display.

Claims (4)

[Claims] (1) A display material consisting of a thin film in which a metal oxide and/or a metalloid oxide is intercalated between layers of V_2O_5 having an amorphous or layered structure. (2) A display material comprising a thin film in which at least one of an electrochromic substance, a dye, and a liquid crystal is intercalated between layers of V_2O_5 having an amorphous or layered structure. (3) A method for producing a display material, which comprises applying an aqueous solution, sol solution or gel solution of an amorphous oxide having V_2O_5 as a matrix onto a substrate and drying it. (4) A display material characterized by applying an aqueous solution, sol solution, or gel solution comprising an amorphous oxide as a V_2O_5 matrix and at least one of an electrochromic substance, a dye, and a liquid crystal onto a substrate and drying it. manufacturing method.