JP2006235484A - Method for manufacturing electrochemical display device, and electrochemical display apparatus using the display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reflective electrochemical display device having visibility and texture extremely similar to those of paper and less display speckles. <P>SOLUTION: The method for manufacturing an electrochemical display device having an ionic conductor held between two electrode plates includes a step of tightly sticking the following ionic conductor to an electrode plate wetted with a liquid. The ionic conductor comprises: fine particles of at least one kind of organic polymer selected from a group consisting of polyamide, polyurethane and polyurea, the particles containing fine particles of at least one kind of inorganic compound selected from a group consisting of silica, metal oxides, metal hydroxides and metal carbonates; and an electrolyte held in the above polymer fine particles. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention provides a method for manufacturing a reflective display element that has very close visibility and texture similar to paper, and a display device using the display element.

  Various technologies have been researched and developed so far for display elements. Among them, various methods have been studied for display elements using reflected light, which are said to have high visibility and are easy on the eyes. The display element with reflected light has the greatest advantage that it can withstand long-term use because the display surface follows the ambient brightness and directional vertical light does not enter the eye. It is mentioned as. In order to make full use of this advantage, it is important how to produce natural and soft whiteness close to paper due to light scattering. For this reason, one of the biggest development goals is how to bring the visibility and texture of the display surface closer to paper.

A display device using liquid crystal, which is one of the technologies of the reflected light type display device, is the most widely used technology at present, but since this method requires a polarizer, the reflected light intensity is greatly attenuated, The whiteness of the display surface does not reach that of paper. In addition, there is a problem that viewing angle dependency occurs. As another display method, a so-called particle rotation type display is known in which display is performed by rotating particles (two-color particles) having two-color regions having different hues and charging characteristics (for example, Patent Documents). 1). Due to the structure of the two-color rotating particles, when the viewing surface side is light (for example, white), the opposite side is dark (for example, black). Even if the two-color particles are arranged densely, a gap is always generated. For this reason, when light coming from the viewing surface in bright color display enters a gap generated by the arranged two-color particles, most of the light is absorbed by the dark color surface on the opposite side. Is low and it is difficult to obtain whiteness close to that of paper.

In the case of a display element using a particle migration method, generally, white display is performed by moving pigment fine particles such as titanium oxide to the viewing surface side of the display device (for example, see Patent Document 2). However, in this method, since the mechanism for producing whiteness is fundamentally different from that of paper, natural whiteness such as that of paper cannot be produced due to a grainy feeling or the like.

On the other hand, as another display element that uses reflected light, an electrochemical display element that uses a reversible change in hue that occurs in a solid or liquid when a voltage is applied is known. With this device, it is possible to perform excellent display with clear hue and no viewing angle dependency during colored display. An electrochromic having a polymer material layer discolored by electrochemical oxidation and reduction existing on a transparent electrode, and a polymer solid electrolyte layer containing a colorant such as titanium oxide in contact with the polymer material layer A type display element is known (see, for example, Patent Document 3). The patent document also describes an electrodeposition type display element in which a polymer solid electrolyte layer containing a colorant such as titanium oxide and a metal ion as a color former is sandwiched between electrodes. In addition, a white semiconductor or insulator powder such as titanium oxide or magnesium oxide is dispersed in an electrolytic solution in which a silver salt (color former) and a supporting electrolyte are dissolved in a solvent, and this liquid is sandwiched between transparent electrodes. An electrodeposition type display device is described (for example, Patent Document 4).

In any of the methods of Patent Documents 3 and 4, so-called white pigment is used to give whiteness to the display element, so visibility and texture are greatly different from paper in any display element. . In addition, in the electrochemical display element, it is necessary to smoothly move ions between the counter electrodes when performing display, but in the method using the polymer electrolyte disclosed in Patent Document 3, when an electrolytic solution is used. In contrast, since the ionic conductivity is low, the display response speed is slow, and the drive voltage may be increased. In addition, since the temperature dependence of the ion conductivity is greater than when a liquid electrolyte is used, stable driving in a wide temperature range, particularly at a low temperature, is difficult. On the other hand, if the electrolytic solution is used in the display element in a liquid state as in Patent Document 4, leakage or the like is liable to occur when the display element is damaged, and the white powder is unevenly distributed. There is a risk that uniform whiteness cannot be produced.

U.S. Pat. No. 4,126,854 JP-A-1-86116 Japanese Patent Laid-Open No. 14-258327 U.S. Pat.No. 4,240,716

The present inventors are selected from the group consisting of polyamide, polyurethane and polyurea containing fine particles of at least one inorganic compound selected from the group consisting of silica, metal oxide, metal hydroxide and metal carbonate. An ionic conductor (hereinafter referred to as an ionic conductor (P)) composed of at least one organic polymer fine particle and an electrolytic solution held in the polymer fine particle is sandwiched between two electrode plates. It has been found that the electrochemical display element is very close to paper in terms of visibility and texture.

Since the ionic conductor strongly holds the electrolytic solution therein, the electrolytic solution does not ooze out on the surface of the ionic conductor and is not in a wet state. Further, the surface of the ionic conductor has a strong adhesion property and is difficult to move once it is placed on a smooth electrode plate surface such as an ITO electrode.
For this reason, it is difficult to install the ion conductor (P) on the electrode plate surface or the like so that the air layer is not mixed, and the portion where the air layer is mixed does not cause an electrode reaction at all. It has been found that the problem is that obstructing decoloration is prevented.
An object of the present invention is to provide a reflective electrochemical display element and a display device that have few display spots, and have a visibility and texture that are very close to paper.

  The inventors of the present invention have an electrochemical display device in which an ionic conductor (P) is sandwiched between two electrode plates, and the visibility and texture are very close to paper, and the ionic conductor (P) is used as an electrode. When the electrode plate surface is wetted with a liquid (hereinafter referred to as “liquid (Q)”) in advance, the ion conductor is placed between the ion conductor and the electrode plate. The present inventors have found that a display element that eliminates display spots caused by an air layer (also referred to as air bubbles) that can be made and can perform efficient decoloration can be manufactured, and the present invention has been completed.

That is, the present invention
At least one organic polymer selected from the group consisting of polyamide, polyurethane and polyurea, containing fine particles of at least one inorganic compound selected from the group consisting of silica, metal oxide, metal hydroxide and metal carbonate The ionic conductor composed of the fine particles of the polymer and the electrolytic solution held in the fine particles of the polymer was brought into close contact with the electrode plate wetted with the liquid, thereby sandwiching the ionic conductor between the two electrode plates. A method for manufacturing an electrochemical display element is provided.

  In addition, an electrochemical display device using the electrochemical display element manufactured by the method is provided.

  INDUSTRIAL APPLICABILITY According to the present invention, a method for manufacturing a reflective electrochemical display element that has very close visibility and texture, is close to paper, has excellent adhesion between an ionic conductor and an electrode, has few display spots, and is capable of efficient decolorization. In addition, a display device using the display element manufactured by the method can be provided.

Hereinafter, an electrochemical display device manufactured according to the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of an electrochemical display device of the present invention. One embodiment of the electrochemical display device of the present invention holds an electrolytic solution (1) containing a decoloring agent (hereinafter referred to as a decoloring agent) that decolorizes by electrochemical oxidation and reduction. A display element having an ionic conductor (P). In FIG. 1, the electrochemical display element includes a transparent substrate 1, a transparent electrode 3 provided thereon, an ion conductor (P) 5 provided on the transparent electrode 3, a counter substrate 2, The counter electrode 4 and the sealing material 7 provided on the top are schematically configured.

  FIG. 2 differs from FIG. 1 in that it has a decoloring material layer 6 provided on the transparent electrode 3 instead of having a decoloring agent in the ion conductor (P). In the case of a display element having such a configuration, the liquid-decoloring material layer 6 is wetted with a liquid, which is also referred to as an electrode plate in the present invention.

(Electrode plate)
The electrode plate used in the present invention may have a structure in which an electrode is formed on a substrate as described above, or it may be a metal plate that itself functions as an electrode and a substrate.

(substrate)
The substrate used in the present embodiment is not particularly limited as long as the material of the substrate 1 used on the viewing surface side is a surface having a smooth surface, a high light transmittance, and an electrode. Specific examples include plastic sheets such as polyethylene terephthalate, polyester, and polycarbonate, glass plates, and the like. In the case of the counter substrate 2 used on the opposite side of the viewing surface, the light transmittance need not be high, and the same material as that of the substrate 2 may be used.

(electrode)
As an electrode used in the present embodiment, the electrode 3 positioned on the viewing surface side needs to be transparent. As such an electrode 3, in addition to ITO (indium tin oxide) currently used most widely, ATO (antimony tin oxide), TO (tin oxide), ZO (zinc oxide), IZO (indium) -Zinc oxide), FTO (fluorine / tin oxide), etc. can be illustrated. On the other hand, the electrode 4 facing the transparent electrode is not necessarily transparent. Therefore, in addition to the above metal oxides, electrochemically stable metals such as platinum, gold, silver, cobalt, palladium, copper, bismuth and the like, plating layers thereof, and carbon materials can also be used.

(Encapsulant)
The sealing material 7 has a role of holding the gap between the electrodes 3 and 4 and preventing the moisture, oxygen, and carbon dioxide in the air from being mixed into the ion conductor (P) 5. For example, a resin such as an epoxy resin or an acrylic resin that can be pressure-cured and cured by heat or ultraviolet rays and has a gas barrier property can be used.

(Ion conductor (P))
The ionic conductor (P) according to the present embodiment includes polyamide, polyurethane, and polysiloxane containing fine particles of at least one inorganic compound selected from the group consisting of silica, metal oxide, metal hydroxide, and metal carbonate. An ionic conductor comprising fine particles of at least one organic polymer selected from the group consisting of urea and an electrolytic solution held in the fine particles of the polymer. An organic solution (A) in which organic polymer fine particles containing fine particles of an inorganic compound are dissolved in an organic solvent at least one compound selected from the group consisting of dicarboxylic acid halides, dichloroformate compounds and phosgene compounds, At least one metal compound selected from the group consisting of metal oxides, metal hydroxides and metal carbonates, having an alkali silicate and / or two or more metal elements, and one of the metal elements is an alkali metal; It is preferably organic polymer fine particles containing fine particles of an inorganic compound obtained by mixing and stirring a basic aqueous solution (B) containing diamine and causing a polycondensation reaction.

The organic polymer fine particles containing inorganic compound fine particles produced by this production method are different from the structure in which organic polymer and inorganic compound are simply mixed, and the inorganic compound fine particles of submicron to nanometer order are matrix. Organic polymer fine particles (hereinafter referred to as organic-inorganic composite) containing fine particles of an inorganic compound having a structure finely dispersed in the organic polymer.

Since the surface area of the fine particles of the inorganic compound is extremely large and the content of the inorganic compound is larger than that of the organic-inorganic composite, the organic-inorganic composite holds an electrolyte having a mass of 4 to 25 times its own weight. be able to. For this reason, the ionic conductor (P) using this organic-inorganic composite has ionic conductivity close to that of the liquid in which the supporting electrolyte is dissolved, while maintaining electronic insulation. In order to obtain an electrochemical display element having higher contrast by good color development, the ionic conductor (P) preferably holds an electrolyte having a mass 5 to 20 times that of the organic-inorganic composite.

  Moreover, it is preferable that the thickness of this ion conductor (P) is 100-1500 micrometers. If the thickness is less than 100 μm, there is a problem that the concealability and whiteness of the display element are insufficient, and if it is thicker than 1500 μm, the ion moving distance becomes long or the internal resistance of the element becomes high, resulting in responsiveness. May get worse.

(Organic inorganic composite)
The organic-inorganic composite used for the ionic conductor (P) in the present invention preferably has no conjugated structure, does not absorb visible light, has high whiteness, and does not have electronic conductivity. Is preferable from the viewpoint of being able to function as an interelectrode separator. Examples of the organic polymer used in such an organic-inorganic composite include at least one selected from the group consisting of polyamide, polyurethane, and polyurea, and preferably an aliphatic monomer. Among these, aliphatic polyamide is particularly preferable.

  Moreover, as an inorganic compound, a silica or a metal oxide is mentioned as a preferable aspect. Such a metal oxide is preferably at least one compound selected from the group consisting of aluminum oxide, zirconium oxide, zinc oxide, and tin oxide.

  The inorganic compound preferably has an average particle size of 1 μm or less and a content of the inorganic compound with respect to 100% by mass of the organic-inorganic composite is 20 to 80% by mass. By setting the average particle size of the inorganic compound to 1 μm or less, the interface area between the organic polymer fine particles and the inorganic compound fine particles becomes relatively wide, light scattering occurs favorably, and high whiteness is imparted to the organic-inorganic composite. Can do. From the viewpoint of electrolytic solution retention properties, the average particle size of the inorganic compound is preferably 500 nm or less, and more preferably 100 nm or less.

  Moreover, when the content of the inorganic compound is 20 to 80% by mass, a large amount of inorganic compound fine particles having an average particle size of 1 μm or less and a very large surface area are present in the organic-inorganic composite. Thus, the organic-inorganic composite can hold a large amount of electrolyte. Further, if the content of the inorganic compound is less than 20% by mass, the function inherent to the inorganic compound provided by the inorganic compound to the organic-inorganic composite becomes unpreferable, whereas if it exceeds 80% by mass, the organic compound is too organic. Deterioration of the function of the organic polymer as a matrix given to the inorganic composite causes an adverse effect of poor workability, which is not preferable.

  The shape of the organic-inorganic composite according to this embodiment is not particularly limited, but is preferably a pulp (bent microfiber) shape having a fiber diameter of 20 μm or less and an aspect ratio of 10 or more. By making the organic-inorganic composite into a pulp shape, papermaking becomes possible, and a thin sheet-like wet cake having an appearance almost equal to that of paper can be obtained without using a binder or the like. Moreover, a large amount of electrolyte solution can be hold | maintained between fibers by making an organic inorganic composite body into a pulp shape.

(Synthesis of organic-inorganic composites)
This organic-inorganic composite includes an organic solution (A) obtained by dissolving at least one compound selected from the group consisting of a dicarboxylic acid halide, a dichloroformate compound, and a phosgene compound in an organic solvent, an alkali silicate, and / or Or at least one metal compound selected from the group consisting of metal oxides, metal hydroxides, and metal carbonates, having two or more metal elements and one of the metal elements is an alkali metal; It can be obtained by mixing and stirring a basic aqueous solution (B) containing diamine, followed by polymerization reaction.

  In this polymerization reaction, the monomer in the organic solution (A) and the diamine in the aqueous solution (B) react rapidly by stirring for about 10 seconds to several minutes at room temperature and normal pressure. And the said organic polymer is obtained with a sufficient yield. At that time, the alkali metal in the alkali silicate and / or the metal compound acts as a removing agent for the hydrogen halide generated during the polymerization, thereby promoting the polymerization reaction of the organic polymer. At the same time, the inorganic compound having a metal element other than the alkali metal element in the alkali silicate and / or metal compound is converted into a solid. At that time, not only one of the polymerization reaction of the organic polymer and the conversion of the inorganic compound to a solid occurs, but both occur in parallel, so that the fine particles of the inorganic compound are finely dispersed in the organic polymer. An organic-inorganic composite according to this embodiment having a structure can be obtained.

(Organic solution (A))
As the organic solution (A), a solution in which at least one compound selected from the group consisting of a dicarboxylic acid halide, a dichloroformate compound, and a phosgene compound is dissolved in an organic solvent is used. Examples of such dicarboxylic acid halides include acid halides of aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, and sebacic acid, and acid halides of aromatic dicarboxylic acids such as isophthalic acid and terephthalic acid. Or an acid halide of an aromatic dicarboxylic acid obtained by substituting hydrogen of these aromatic rings with a halogen atom, a nitro group, an alkyl group or the like. These can be used alone or in combination of two or more. Among them, when an acid halide of an aliphatic dicarboxylic acid such as adipoyl chloride, azela oil chloride, sebacoyl chloride is used, a fibrous organic-inorganic composite can be easily obtained. Can be processed into a wet cake sheet and the like, and since it does not have a conjugated structure, its whiteness is high, which is particularly preferable.

  Examples of the dichloroformate compound include aliphatic diols such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,8-octanediol. Or resorcinol (1,3-dihydroxybenzene), hydroquinone (1,4-dihydroxybenzene), 1,6-dihydroxynaphthalene, 2,2′- having two hydroxyl groups on one or more aromatic rings Examples thereof include all the hydroxyl groups of dihydric phenols such as biphenol, bisphenol S, bisphenol A, and tetramethylbiphenol that have been chloroformated by phosgenation. These can be used alone or in combination of two or more.

  Examples of the phosgene compound include phosgene, diphosgene, and triphosgene. These can be used alone or in combination of two or more.

  By selecting the monomer used for the organic solution (A) from the above, the organic polymer contained in the organic-inorganic composite can be made as described above. Specifically, when a dicarboxylic acid halide is used as a monomer, polyamide is used as an organic polymer, when a dichloroformate compound is used as a monomer, polyurethane is used as an organic polymer, and when a phosgene compound is used as a monomer, it is organic. Polyurea can be obtained as a polymer by reaction with an aqueous solution (B).

  The organic solvent used in the organic solution (A) is not particularly limited as long as it does not react with the various monomers and diamines in the organic solution (A) and dissolves the various monomers in the organic solution (A). Can be used. For example, the organic solvent incompatible with water includes aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as n-hexane, halogenated hydrocarbons such as chloroform and methylene chloride, cyclohexane and the like. An alicyclic hydrocarbon can be mentioned.

  Moreover, as an organic solvent compatible with water, ethers, such as tetrahydrofuran, ketones, such as methyl ketone and methyl ethyl ketone, can be mentioned as a typical example.

  When an organic solvent incompatible with water is used as the organic solvent used in the organic solution (A), the polymerization reaction is an interfacial polymerization reaction that occurs only at the interface between the organic solution (A) and the aqueous solution (B). Use of an organic solvent that is incompatible with water is preferable because the molecular weight of the organic polymer to be produced can be easily increased and a fiber-shaped organic-inorganic composite can be obtained. In addition, a long-strength organic-inorganic composite having high strength can be obtained by spinning the film-like organic-inorganic composite produced at the interface between the organic solution (A) and the aqueous solution (B) while pulling up.

On the other hand, when an organic solvent that is compatible with water is used as the organic solvent, the polymerization reaction proceeds in a state where the organic solvent and water are emulsified, so that a powder-shaped organic-inorganic composite is obtained.
The organic-inorganic composite obtained by using any organic solvent is in a fiber shape or a powder shape, and has a larger outer surface area than the bulk shape. Therefore, the electrolytic solution can be efficiently brought into contact with the composite without performing a treatment such as pulverization, so that the electrolytic solution can be easily held.

(Aqueous solution (B))
As aqueous solution (B), it is from the group which consists of a metal oxide, a metal hydroxide, and a metal carbonate which has an alkali silicate and / or 2 or more types of metal elements, and 1 type of this metal element is an alkali metal. A basic aqueous solution containing at least one selected metal compound and diamine is preferred.

(Alkali silicate)
An organic-inorganic composite composed of the organic polymer and silica can be obtained by performing a polymerization reaction in the aqueous solution (B) in the presence of an alkali silicate. As this silicate alkali, for example, it is represented by a composition formula of A ₂ O.nSiO ₂ such as water glass No. 1, No. 2, No. 3, etc. described in JIS K 1408, A is an alkali metal, and the average value of n is The thing of 1.8-4 is mentioned. Moreover, the liquid which melt | dissolved the powder of the alkali metal silicate (for example, sodium metasilicate 1 type, 2 types) whose average value of n is 0.8-1.1 in water is used similarly to the said water glass. be able to. The alkali metal compound contained in the alkali silicate promotes the polymerization reaction by acting as a removing agent for the hydrogen halide generated during the polymerization.

(Metal oxide, metal hydroxide, metal carbonate)
Moreover, as a metal compound used for aqueous solution (B), the group which consists of a metal oxide, a metal hydroxide, and a metal carbonate which has 2 or more types of metal elements and 1 type of this metal element is an alkali metal At least one metal compound selected from is preferred. Here, A is an alkali metal element, M is a transition metal element of Groups 3 to 12 of the periodic table, and a typical metal element of Groups 13 to 16 of the periodic table. The transition metal element mentioned here means a transition metal element in a broad sense including Group 11 and Group 12 of the periodic table including copper and zinc.
Specifically, the transition metal elements belonging to Group 3 to Group 12 of the periodic table referred to in the present invention are ²¹ Sc to ³⁰ Zn, ³⁹ Y to ⁴⁸ Cd, ⁵⁷ La to ⁸⁰ Hg in the periodic table. , ⁸⁹ Ac means a metal element.

Further, typical metal elements of Groups 13 to 16 of the periodic table are ¹³ Al, ³¹ Ga, ³² Ge, ⁴⁹ In, ⁵⁰ Sn, ⁵¹ Sb, ⁸¹ Tl, ⁸² Pb, ⁸³ Bi, and ⁸⁴ Po in the periodic table. means. Among these metal elements, particularly preferably, at least one metal element selected from the group consisting of aluminum, zirconium, zinc, and tin, and B is at least one selected from the group consisting of O, CO ₃ , and OH. More than a species, preferably O, and x, y, and z are numbers that allow the combination of A, M, and B.

The compound represented by the general formula A _x M _y B _z is preferably completely or partially dissolved in water and exhibits basicity. In addition, since the alkali metal A in the compound acts as a removing agent for the hydrogen halide generated during the polymerization and becomes a halogenated salt and is removed from the compound, the metal element M in the remaining compound is an inorganic compound. Convert to. From the viewpoint of efficiently complexing the inorganic compound with the organic polymer, the inorganic compound having the metal element M is preferably one that hardly or not dissolves in water.

Among the metal compounds A _x M _y B _z , the compound in which B is O includes sodium zincate, sodium aluminate, sodium molybdate, sodium stannate, sodium tantalate, sodium tungstate, sodium zirconate, and the like. Complex oxides, potassium zincate, potassium aluminate, potassium molybdate, potassium stannate, potassium tantalate, potassium tungstate, potassium goldate, potassium silverate, potassium zirconate, potassium tellurate, potassium antimonate, etc. In addition to lithium composite oxides such as potassium composite oxide, lithium aluminate, lithium molybdate, lithium stannate, lithium tungstate, lithium zincate, and lithium zirconate, rubidium composite oxide and cesium composite oxide are preferably used. Can.

  Among them, sodium composite oxides such as sodium aluminate, sodium zirconate, sodium zincate, and sodium stannate, and potassium composite oxides such as potassium aluminate, potassium zirconate, potassium zincate, and potassium stannate are available. Is preferable because it is easy and water-soluble.

Examples of the metal compound in which B contains one or both of CO ₃ and OH include zinc carbonate potassium, nickel carbonate potassium, zirconium carbonate potassium, cobalt carbonate potassium, tin carbonate potassium, and hydrates thereof. it can.

  Since these metal compounds are dissolved in water and used, they may be hydrates. Moreover, these can be used individually or in combination of 2 or more types.

(Diamine)
Moreover, as diamine used for aqueous solution (B), if it reacts with each monomer in organic solution (A) and produces | generates the said organic polymer, it can use without a restriction | limiting especially. For example, aliphatic diamines such as 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, m-xylylenediamine, p- Aromatic diamines such as xylylenediamine, m-phenylenediamine, p-phenylenediamine, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene and 2,3-diaminonaphthalene, or hydrogen of these aromatic rings as halogen atoms, An aromatic diamine substituted with a nitro group or an alkyl group is exemplified. You may use these individually or in combination of 2 or more types. Among them, when an aliphatic diamine such as 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane is used, a fibrous organic-inorganic composite can be easily obtained, and a nonwoven fabric can be obtained. It is particularly preferable because it can be processed into a similar shape.

(Synthesis operation of organic-inorganic composite)
The monomer concentration in the organic solution (A) and the aqueous solution (B) in this embodiment is not particularly limited as long as the polymerization reaction proceeds sufficiently, but from the viewpoint of bringing the monomers into good contact with each other, 0.01 to 3 A concentration range of mol / L is preferable, and 0.05 to 1 mol / L is particularly preferable.

  The concentration of the alkali silicate and / or metal compound in the aqueous solution (B) is determined to some extent by the monomer concentration in the organic solution (A) and the aqueous solution (B). The range of 1 to 500 g / L is preferable because it is maintained and prevents side reactions between the monomer and water in the organic solution (A) that may be generated due to excessive heat generation during polymerization.

  In this polymerization reaction, for example, the reaction proceeds sufficiently in a temperature range of about −10 to 50 ° C. near room temperature. Also, no pressurization or decompression is required. Moreover, although this polymerization reaction is based on the monomer and reaction apparatus to be used, it is usually completed in a short time of about 10 minutes.

(Electrolyte)
The electrolytic solution of the present invention is composed of a supporting electrolyte and a solvent for dissolving the supporting electrolyte. Further, the electrolytic solution preferably contains at least one material selected from the group consisting of a decoloring agent and a redox accelerator.

(solvent)
The solvent constituting the electrolytic solution may be either aqueous or non-aqueous. In addition to water, propylene carbonate, dimethyl carbonate, 2-ethoxyethanol, 2-methoxymethanol, isopropyl alcohol, N-methylpyrrolidone, dimethylacetamide, dimethyl Examples include polar solvents such as formamide, acetonitrile, butyronitrile, glutaronitrile, dimethoxyethane, γ-butyrolactone, ethylene glycol, and propylene glycol. In the case of an aqueous system, in order to prevent coagulation at 0 ° C. or lower and satisfy the operation under a low temperature condition, among the above solvents, a solvent compatible with water can be used by being dissolved.

  Since the refractive index of the organic polymer in the organic-inorganic composite is around 1.5, when using an electrolytic solution having a high refractive index difference from this organic polymer, the whiteness of the organic-inorganic composite is reduced due to the immersion of the electrolytic solution. Can be minimized, and an ionic conductor (P) maintaining higher whiteness can be produced. When the organic polymer is polyamide 6.6, since the refractive index of the polymer is 1.53, a solvent having a refractive index of 1.40 or less is preferable, and a solvent of 1.38 or less is more preferably used. Examples of such a solvent include water, acetonitrile, methanol, ethanol, 2-ethoxyethanol, 2-methoxymethanol, isopropyl alcohol, and mixtures thereof.

(Supporting electrolyte)
The supporting electrolyte constituting the electrolyte includes lithium salts such as lithium chloride, lithium bromide, lithium iodide, lithium perchlorate, lithium nitrate, lithium sulfate, lithium borofluoride, sodium chloride, sodium bromide, iodine. Alkali metal halides such as sodium chloride, potassium chloride, potassium bromide, potassium iodide, tetrabutylammonium bromide, tetrabutylammonium chloride, tetraethylammonium borofluoride, tetrabutylammonium borofluoride, ammonium perchlorate, tetraethyl perchlorate Examples thereof include ammonium salts such as ammonium and tetrabutylammonium perchlorate, and acids such as sulfuric acid, borohydrofluoric acid, perchloric acid, and hydrochloric acid.

(Decolorizer)
The electrochemical display element of the present invention turns display on and off with a decoloring agent. As shown in FIG. 1, when the decoloring agent is contained in the electrolyte solution held by the ionic conductor (P), the decoloring agent is oxidized or reduced (in some cases) on the electrode by applying a voltage. And then oxidize or reduce (in some cases) to dissolve and decolorize. On the other hand, as shown in FIG. 2, when the electrochemical display element of the present invention has a decoloring agent layer having a decoloring agent, the electrolyte retained by the ion conductor (P) is not necessarily extinguished. It is not necessary to have a color former.

  When the decoloring agent is contained in the ionic conductor (P), the content of the decoloring agent in the display element can be increased, so that color development can be strengthened and metal ions or low molecules can be used. Since the organic compound instantaneously causes a chemical change accompanied with a color change, there is a feature that the response speed can be increased. Examples of the organic compound used in such a structure include organic quinones such as benzoquinone, naphthaquinone, anthraquinone, diphenoquinone, diphenylquinone, dibenzoanthraquinone, violanthrone, isoviolanthrone, and pyranthrone. These organic quinones are reduced by applying a driving voltage to the electrodes to create a colored state peculiar to each compound. When using these compounds, in order to increase the concentration in the ionic conductor (P), an electrolytic solution having a non-aqueous solvent capable of dissolving a large amount of the above-described quinone compound is preferably used.

Examples of the metal compound used as a decoloring agent include halides such as silver, bismuth, copper, iron, chromium and nickel, sulfides, nitrates, perhalogenates and the like. By dissolving these compounds in the electrolytic solution, each metal is ionized, so that the electrolytic solution can be used as a decoloring agent. For example, when an electrolytic solution in which a silver compound is dissolved is used, when a driving voltage is applied to the electrode, a reduction reaction of Ag ⁺ + e ⁻ → Ag occurs on the cathode side, and the Ag electrode deposits the cathode electrode. It turns black. Among the above metals, bismuth and silver are particularly preferably used because they are almost transparent when dissolved in an electrolytic solution, and the precipitate has a dark color and good reversible reaction of decoloration. Many of these compounds have water solubility, and in addition to non-aqueous solvents, aqueous solvents can also be suitably used as the electrolyte solvent.

(Decolorizer layer)
If it is difficult to contain the color former in the ionic conductor (P) because the decolorizer is inferior in solvent solubility, it is erased by electrochemical redox on the transparent electrode on the viewing side. An electrochemical display element can also be obtained by providing a decoloring agent layer that develops color. (Equivalent to the configuration of FIG. 2)

As such a decoloring agent layer, an organic polymer compound or a metal compound can be used. Examples of the organic compound constituting the decolorizer layer include organic polymer compounds such as polypyrrole, polyaniline, polyazulene, polythiophene, polyindole, and polycarbazole. Among these, polypyrrole and polythiophene are particularly preferable because the precipitate color is dark and the reversible reaction of decoloration is good. The inorganic compound constituting the material layer _9, illustrate _{WO 3, MoO 3, V 2} O 5, Nb 2 O 5, TiO 2, NiO, Cr 2 O 3, MnO 2, CoO, and IrO _2, etc. can do. When an organic polymer compound is used as the decoloring agent layer, the layer can be formed on the transparent electrode by electrolytic polymerization or chemical polymerization of the raw material monomer of the polymer compound. When a metal compound is used as the decolorizer layer, it can be formed by a known method such as a vacuum deposition method, an electron beam vacuum deposition method, or a sputtering method.

In addition, a colorant-containing liquid in which various materials having good solvent solubility of the decolorizer (the above-described quinone compounds, metal ions such as silver and bismuth) are mixed with various binder resins together with a supporting electrolyte and a solvent, A display element similar to that shown in FIG. 2 can also be produced by applying a gel-like material on the transparent electrode. In this case, the colored layer can be provided by a coating method, a spin coating method, or the like. In this case, it is not always necessary to include a color former in the ion conductor (P), but it is preferable to include it in order to enhance color development.

(Redox accelerator)
In order to accelerate the electrochemical redox reaction (that is, the decoloring reaction) of the decoloring agent, a redox promoter may be introduced into the electrolytic solution. A redox accelerator is a material that promotes the redox reaction of the decoloring material by performing reversible redox at a certain redox potential on the electrode opposite to the electrode where decoloring occurs. In addition to hydroquinone, catechol and derivatives thereof, 1,4-naphthalenediol, 1,5-naphthalenediol, 2,7-naphthalenediol and derivatives thereof can be exemplified. These dihydric phenols promote reversible redox by releasing or containing electrons by reversibly changing each compound to the corresponding quinone (for example, benzoquinone in the case of hydroquinone). To do. Moreover, you may use the quinone corresponding to said dihydric phenols. Further, ferrocene, ferrocyanic potassium, ferricyanic potassium, or the like may be used as a material having a similar action.

  In addition, for the purpose of improving the reversibility of decoloration, a brightener, a complexing agent, a buffering agent, a pH adjusting agent and the like used as a plating agent may be added.

(Production method of ion conductor (P))
Since the organic-inorganic composite used in the present invention has extremely high electrolytic solution retention characteristics regardless of the type of electrolytic solution, the composite dispersion (slurry) obtained by dispersing the composite in the electrolytic solution is filtered, etc. It is possible to obtain an ionic conductor (P) in which 400 to 1500 parts by mass of an electrolytic solution is held with respect to 100 parts by mass of the composite only by performing the simple operation. Further, since the composite can be obtained in the form of a fiber or powder, the dispersion in the electrolytic solution can be easily performed using a general-purpose batch type stirring layer.

  In addition, since the organic-inorganic composite can have a fiber (pulp) shape depending on the synthesis conditions, for example, by filtering a dispersion obtained by dispersing the composite in an electrolytic solution by a known and conventional method, It is possible to form a sheet without using it at all. For example, a method of passing the dispersion liquid through a filter medium such as stainless steel, nylon net or fluororesin net, a method of spraying the dispersion liquid on the electrode plate by spraying, and the like can be mentioned. By this method, a large-area sheet-like ion conductor (P) can be easily obtained. At this time, if a fluororesin-based filter medium that is particularly excellent in releasability is used as the filter medium, the ion conductor (P) can be easily peeled off from the filter medium, so that a smooth ion conductor sheet with no scratches on the surface is obtained. Can be preferably used. In addition, when a material having high electron conductivity such as a metal net or a carbon fiber nonwoven fabric is used as the filter medium, the filter medium can be used as it is as a counter electrode. In this case, it is preferable to perform an operation in which only the electrode plate on the viewing surface side is wetted and the ion conductor is brought into close contact. At this time, a known and commonly used binder can be used as long as required electrolyte solution retention, whiteness, and electronic insulation are not impaired.

  In the step of holding the electrolytic solution, if the organic-inorganic composite is used after being dried to a high solid content, the composite may solidify strongly due to hydrogen bonds derived from the polar group of the organic component. is there. Once the composite is solidified, it becomes difficult to re-disperse in the electrolyte, and the amount of electrolyte retained is greatly reduced, and the remaining undispersed material in the electrolyte has a uniform ionic conductivity and appearance. The ion conductor (P) cannot be obtained. Therefore, the obtained composite is preferably subjected to an electrolyte solution holding operation in a wet cake state. Preferably, a wet cake having a solid content of 35% by mass or less, more preferably 20% by mass or less is used. By taking the impregnation step of holding the electrolytic solution in the composite having such a solid content rate, an ionic conductor (P) that holds the electrolytic solution at a high holding rate and has uniform ionic conductivity and appearance is obtained. be able to.

  Moreover, since the ionic conductor (P) obtained by the said method hold | maintains a lot of electrolyte solutions of 400-1500 mass parts with respect to 100 mass parts of composite_body | complex, the ionic conduction close | similar to the liquid which melt | dissolved the supporting electrolyte. On the other hand, the insulating property can be maintained electronically.

(Display element manufacturing method)
In order to produce a display element using the ion conductor (P) constituting the electrochemical type display element of the present invention, a step of installing the ion conductor (P) on the electrode plate is required. However, since the ion conductor (P) has strong adhesion to a solid, it is difficult to move once it is placed on a smooth electrode surface such as an ITO electrode. If the air layer is mixed when the ion conductor is placed on the electrode surface, the electrode reaction does not occur at all in the portion where the air layer is mixed. For this reason, display cannot be performed at all, and display spots are generated, and the display quality is significantly impaired. The sheet of ionic conductor (P) has a certain tensile strength, especially when using an organic-inorganic composite having a pulp shape. If the area occupied by the air layer is large, the air layer is extruded by lamination. Although it can be removed, it is extremely difficult to remove when a small air bubble having a diameter of about 1 mm enters between the ion conductor (P) and the electrode surface.

At this time, when the electrode plate is wetted with the liquid (Q) in advance, and then the ion conductor (P) is installed, the ion conductor (P) is brought into close contact with the electrode plate. By forming a liquid layer with a uniform thickness between the electrode plate and the electrode plate, it is possible to prevent bubbles from remaining with a high probability. For example, when the contact angle between the liquid (Q) and the electrode plate is high and the wettability is poor, droplets exist independently on the electrode plate. When the ion conductor (P) is installed in this state, in the step of adhering the ion conductor (P) to the electrode plate, the droplets are pushed out on the electrode plate and the bubbles are driven out toward the end surface of the ion conductor. Thus, a display element in which no bubbles remain can be easily manufactured.

On the other hand, when the contact angle between the liquid (Q) and the electrode plate is low and the wettability is good, the liquid (Q) is formed in a thin layer on the electrode plate, so that bubbles are not easily formed and there are a small amount of bubbles. In the same way as in the case where the contact angle of the liquid (Q) on the electrode plate is large, bubbles are removed to the end face of the element, and a display element in which no bubbles remain can be manufactured. In any case, since the ionic conductor (P) used in the present invention has high liquid water absorption characteristics, it swells while absorbing the liquid (Q) on the electrode plate, and thus adheres to the electrode plate. Since the liquid layer does not stay between the ionic conductor (P) and the electrode plate by being wetted, there is no possibility that the paper texture and visibility are lowered and the liquid leaks when the element is broken.

(Liquid (Q) solvent species and contained components)
The liquid (Q) is finally absorbed by the ion conductor (P) to remove bubbles on the electrode plate. Therefore, it is preferable to select a liquid that is compatible with the electrolytic solution of the ionic conductor (P), more preferably the same liquid as the solvent of the electrolytic solution of the ionic conductor (P), most preferably That is, the liquid (Q) is the same as the electrolytic solution of the ionic conductor (P). In particular, when the liquid (Q) is the same as the electrolytic solution in the ionic conductor (P) (that is, when it contains a supporting electrolyte and a decoloring agent), the ionic conductor is compared with the case where it is a simple solvent. Since the concentration of the supporting electrolyte or the like in the electrolyte solution in (P) is not lowered, the color development characteristics and response speed can be maintained, and an increase in drive voltage can be prevented. In addition, by improving the wettability on the electrode plate, a surfactant, a leveling agent, and the like are generated in the liquid crystal (Q) in the display element for the purpose of easily adhering the ionic conductor. You may add in the range which does not inhibit reaction. As described above, the ionic conductor (P) used in the present invention can be prepared by filtering a slurry in which an organic-inorganic composite is dispersed in an electrolytic solution. Q) can also be used.

(Method of wetting electrode plate surface with liquid (Q))
Prior to installing the ion conductor on the electrode plate, it is necessary to wet the electrode plate surface with the liquid (Q), but this method allows the liquid (Q) to exist without being localized on the electrode plate surface. If it is, it will not specifically limit. When the contact angle with the liquid (Q) is high and the wettability is poor, if small droplets are distributed over the entire region where the ion conductor is installed, each droplet is an electrode plate when the ion conductor is installed. It is particularly preferable that the bubbles can be efficiently removed across the entire surface of the device by spreading between the ion conductor and the ion conductor. As an example in which the liquid (Q) is present on the electrode plate in such a state, there is a method of spraying the liquid (Q) on the electrode plate by spraying or the like. On the other hand, when the affinity between the liquid (Q) and the electrode plate is high and wettability is high, there are a method of immersing the electrode plate in the liquid (Q) and pulling it up, a method of dropping the liquid (Q) on the electrode plate, and the like. Can be mentioned.

(Wet electrode plate with liquid (Q))
In the present invention, since it is an object to eliminate display defects caused by bubbles in the display element, at least the electrode plate on the viewing surface side is wetted with the liquid (Q) and then the ion conductor (P). Need to be installed. However, it is more preferable that the ionic conductor (P) is completely adhered to both electrode plates by wetting both the viewing surface side electrode plate and the counter electrode plate. This is because by being in close contact with the counter electrode plate, an electrochemical reaction at the counter electrode can be sufficiently generated, and a display element that can be stably driven can be manufactured.

(Electrochemical display)
A display device can be obtained by providing the display element shown in FIGS. 1 and 2 with a power supply portion, a circuit portion, a seal layer, a housing, and the like as necessary.

  Hereinafter, the present invention will be described more specifically with reference to examples. Unless otherwise specified, “part” means “part by mass”.

(Synthesis example: synthesis of silica / polyamide composite)
9.81 parts of water glass 3 and 1.58 parts of 1,6-diaminohexane were added to 81.1 parts of ion-exchanged water and stirred at 25 ° C. for 15 minutes to obtain a homogeneous transparent aqueous solution (B).
An organic solution (A) in which 2.49 parts of adipoyl chloride was dissolved in 44.4 parts of toluene while the aqueous solution (B) was charged into a blender bottle manufactured by Osterizer at room temperature and stirred at 10,000 rpm. Was added dropwise over 20 seconds.

Next, the produced gel was crushed with a spatula and further stirred at 10,000 rpm for 40 seconds. The pulp-like product-dispersed liquid obtained by this operation was filtered under reduced pressure on a filter paper having a mesh size of 4 μm using a Nutsche having a diameter of 90 mm.
The product on Nutsche was dispersed in 100 parts of methanol, stirred for 30 minutes with a stirrer, and filtered under reduced pressure for washing treatment. Subsequently, the same washing operation was performed using 100 parts of distilled water, followed by filtration under reduced pressure to obtain a cake sheet containing pure white silica / polyamide composite water.

  The obtained silica / polyamide composite was analyzed according to the following methods (1) to (2), and an electrochemical display device was produced according to (3) to (6).

(1) Measurement of inorganic compound content (ash content) The content of the inorganic compound contained in the silica / polyamide composite obtained in the synthesis example was measured by the following method.
The composite was precisely dried and then weighed precisely to determine the mass of the complex. This was calcined in air at 600 ° C. for 3 hours to completely burn off the organic polymer component, and the mass after calcination was measured to determine the mass of ash (= Inorganic compound mass). From these values, the inorganic compound content was calculated according to the following formula.
Inorganic compound content (mass%) = (ash content / composite mass) × 100
Since only silica is contained in this composite and is not removed by baking at 600 ° C., the value obtained by this measurement is defined as the inorganic compound content. The inorganic compound content in this measurement was 60% by mass.

(2) Measurement of average particle diameter of inorganic compound in silica / polyamide composite and observation of dispersion state The silica / polyamide composite was hot-pressed under conditions of 170 ° C. and 20 MPa / cm ² for 2 hours to obtain a thickness of about 1 mm. A flake consisting of a silica / polyamide composite was obtained. This was made into an ultrathin section having a thickness of 75 nm using a microtome. The obtained sections were observed at a magnification of 100,000 with a transmission electron microscope “JEM-200CX” manufactured by JEOL Ltd. It was observed that the inorganic compound was finely dispersed in the bright organic polymer as a dark image.

  Subsequently, the particle diameter of 100 inorganic compound fine particles was measured, and the average value was defined as the inorganic compound average particle diameter. In this silica / polyamide composite, spherical silica having an average particle diameter of about 10 nm was observed to form a network, that is, to form a three-dimensional network and to be finely dispersed in the polyamide.

(3) Preparation of dispersion for preparing electrochemical display element (3-1) Cleaning of cake sheet and measurement of solid content About 10 parts of cake sheet of the obtained silica / polyamide composite was added to more than 100 parts. A washing process was performed by repeating the steps of dispersing in pure water and filtering under reduced pressure three times to obtain a cake sheet containing ultrapure water.
After measuring the mass (wet mass) of this cake sheet, it was dried at 150 ° C. for 2 hours, and the dry mass was measured. From these numerical values, when the solid content rate of the cake sheet was calculated by the following equation, the solid content rate of the obtained cake sheet was 8.5% by mass.
Solid fraction (mass%) = (dry mass / wet mass) × 100

(3-2) Preparation of dispersion in which silica / polyamide organic / inorganic composite is dispersed in electrolyte solution 669 parts of ultrapure water as a solvent, 12.8 parts of bismuth oxyperchlorate as a decoloring agent, and a supporting electrolyte 2.48 parts of a 60% by mass solution of perchloric acid and 6.93 parts of hydroquinone as a redox accelerator were dissolved by stirring at room temperature to prepare a homogeneous, colorless and transparent electrolytic solution.
A dispersion (slurry) in which the silica / polyamide organic-inorganic composite is uniformly dispersed in the electrolytic solution by adding 88.4 parts of the cake sheet obtained by the operation of (3-1) to this electrolytic solution and dispersing by stirring. )

(4) Production of ion conductor (P) (production of silica / polyamide organic-inorganic composite wet cake sheet containing electrolyte)
65 g of the dispersion used in (3-2) was set on a filter bottle with a 90 mm diameter nutchet, and poured onto the filtration surface from above a membrane filter “Durapore” manufactured by Millipore, which is a filter material made of Teflon (registered trademark). After removing the pressure at 0.03 MPa, the excess electrolyte solution is removed, and then the filter medium is peeled off, whereby the ion conductor (P) which is a 700 μm-thick organic-inorganic composite wet cake sheet holding a large amount of the electrolyte solution Got.

(5) Preparation of electrode plate wetting liquid (Q) An electrolyte solution was prepared in the same manner as the electrolyte solution preparation step in (3-2). This was designated as electrode plate wetting liquid (Q).

(6) Electrode plate and electrode For the display element of the present invention, a transparent electrode substrate having an ITO electrode (manufactured by Eetch Sea Co., Ltd., surface resistance 10 Ω / □) on a 700 μm thick glass substrate is cut into a 6 cm square. It was.

(Example 1: Production of display element by wetting electrode plate)
The ion conductor (P) produced in (4) was cut into 4 cm × 4 cm prior to installation on the electrode plate. Subsequently, the liquid (Q) produced in (5) was sprayed on the electrode surface side of the transparent electrode substrate (electrode plate) in (6) by small spraying. The liquid (Q) was distributed almost uniformly over the entire area of the electrode plate as a large number of droplets of about 1 mmΦ on the electrode. Thereafter, the side from which the Teflon (registered trademark) filter material was peeled was placed on the ITO electrode. At the time of installation, a small amount of air bubbles was mixed between the ion conductor (P) and the electrode surface, but when the ion conductor (P) was pressed against the electrode surface, the liquid (Q) droplet on the electrode By being sandwiched between the ion conductor (P) and the electrode, it spreads on the electrode, and by connecting adjacent droplets, the bubbles are moved to the end face side of the ion conductor and completely removed. A sheet in which the ionic conductor (P) was placed on the transparent electrode substrate (electrode plate) could be produced in the absence. Immediately after this operation, the liquid (Q) layer between the transparent electrode substrate (electrode plate) and the ionic conductor is absorbed by the ionic conductor (P) having high liquid absorption characteristics, resulting in ionic conduction. The body (P) and the transparent electrode were completely adhered.

Next, the electrode plate is wetted by spraying the liquid (Q) on the electrode surface side of the other transparent electrode substrate (electrode plate), and the ion conductor ( The sheet | seat in which P) was installed was installed from the ion conductor side. At this time, by applying pressure to the electrode plates sandwiching the ionic conductor, the bubbles were completely removed on the second surface side as well as the first surface side. Next, the periphery of the ionic conductor (P) was sealed with an epoxy resin to produce an electrochemical display element (1) having a thickness of about 700 μm. In this display element, the ion conductor (P) on the side from which the Teflon (registered trademark) filter material is peeled is used as the viewing surface side.

(Reference Example 1: Production of a display element that does not wet the electrode plate)
The ion conductor (P) produced in (4) was cut into 4 cm × 4 cm, and the side on which the Teflon (registered trademark) filter material was peeled off was not subjected to the wet operation of the electrode plate performed in Example 1. It installed on the transparent electrode of a transparent electrode substrate (electrode board). At that time, since the bubbles mixed the electrode plate between the ion conductors, the operation of pressing the ion conductor (P) against the electrode plate side to make the electrode and the ion conductor (P) closely contact each other. Since the ionic conductor (P) surface was smooth due to the side from which the (registered trademark) filter material was peeled off, most of the bubbles could be removed, but very small bubbles of 0.5 mm or less at three locations. Remained and could not be finally removed.
Subsequently, a transparent electrode used as a counter electrode was placed on the ion conductor (P) placed on the electrode plate without performing the wet treatment performed in Example 1. In addition to the fact that the electrode plate was not wetted on the side where the transparent electrode was installed afterwards, the cake surface was not smooth because it was the side without the filtering material (the free surface side). Many bubbles were mixed on the surface, and the bubbles could not be removed. This display element is referred to as an electrochemical display element (2).

  After connecting lead wires to the electrodes of the above electrochemical display elements (1) and (2), they are connected to a function generator, and a rectangular wave with a frequency of ± 1.5 V and a period of 2 seconds is applied. The element (1) has excellent display characteristics with no spots on the display and excellent paper texture due to excellent adhesion between the electrode of the electrode plate and the ion conductor (P). Had characteristics.

On the other hand, the display element (2) has poor adhesion between the electrode and the cake on the back side, so that the display surface has many display spots and good display despite the relatively good adhesion on the viewing surface side. There wasn't.

  From the above results, according to the present invention, after the electrode plate is wetted with the liquid (Q), the ion conductor (P) is placed on the electrode plate, so that the display characteristics without display spots are good. It was confirmed that a chemical display element can be manufactured.

It is a schematic diagram of an electrochemical display element in which an ion conductor is sandwiched between two electrode plates in the present invention. FIG. 3 is a schematic view of an electrochemical display element having an ionic conductor sandwiched between two electrode plates and having a decoloring layer on the viewing side electrode plate in the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Counter substrate 3 Transparent electrode 4 Counter electrode 5 Ion conductor (P)
6 Decolorizing material layer 7 Sealing material

Claims (4)

At least one organic polymer selected from the group consisting of polyamide, polyurethane and polyurea, containing fine particles of at least one inorganic compound selected from the group consisting of silica, metal oxide, metal hydroxide and metal carbonate An ion conductor composed of a fine particle and an electrolytic solution held in the polymer fine particle is brought into close contact with an electrode plate wetted with the liquid, thereby sandwiching the ion conductor between the two electrode plates. A method for producing a chemical display element. The method for producing an electrochemical display element according to claim 1, wherein the liquid for wetting the electrode plate surface is an electrolytic solution of an ionic conductor. The organic polymer fine particles include an organic solution (A) in which at least one compound selected from the group consisting of a dicarboxylic acid halide, a dichloroformate compound, and a phosgene compound is dissolved in an organic solvent, an alkali silicate, and / or two or more types. Basicity containing at least one metal compound selected from the group consisting of metal oxides, metal hydroxides and metal carbonates, wherein one of the metal elements is an alkali metal and a diamine 2. The method for producing an electrochemical display element according to claim 1, wherein the organic polymer fine particles are fine particles of an organic compound containing fine particles of an inorganic compound obtained by mixing and stirring the aqueous solution (B). The electrochemical type display apparatus using the electrochemical type display element produced with the manufacturing method in any one of Claims 1-3.

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