WO2007058046A1

WO2007058046A1 - Solid electrolyte and display element using the same

Info

Publication number: WO2007058046A1
Application number: PCT/JP2006/320832
Authority: WO
Inventors: Noriyuki Kokeguchi
Original assignee: Konica Minolta Holdings, Inc.
Priority date: 2005-11-18
Filing date: 2006-10-19
Publication date: 2007-05-24
Also published as: JP5136061B2; JPWO2007058046A1

Abstract

This invention provides a solid electrolyte and a display element using the solid electrolyte between counter electrodes. In recent years, for example, an improvement in operating speed of a personal computer and spreading of a network infrastructure have lead to an increase in the opportunity for inspecting electronic data information. A display method utilizing dissolution precipitation of a metal salt such as a silver salt in an electrolyte between counter electrodes in the display element is known as means for inspecting such electronic data information. In the prior art, the electrolyte between the counter electrodes in the display element contains an organic solvent, and, thus, the prior art is disadvantageous in that storage for a long period of time under a high temperature environment causes penetration of the organic solvent into a sealing agent in the display element and volatilization of the organic solvent, which cause a change in the composition of the electrolyte, resulting in problems such as a variation in display function. The above problems could have been solved, for example, by using, as the electrolyte between the counter electrodes in the display element, a solid electrolyte comprising a room-temperature molten salt of a silver salt, filler particles and a water-soluble polymer compound substantially without containing an organic solvent.

Description

Specification

Solid electrolyte and display element using the same

Technical field

[0001] The present invention relates to a novel silver salt room temperature molten salt and an electrochemical display element using the same and utilizing silver dissolution and precipitation.

Background art

[0002] In recent years, with the increase in the operating speed of personal computers, the spread of network infrastructure, the increase in capacity and low cost of data storage, information such as documents and images that have been provided on printed paper has been Opportunities to obtain and browse electronic information as simpler electronic information are increasing.

[0003] As a means of browsing such electronic information, conventional liquid crystal displays and CRTs, and in recent years, light-emitting types such as organic EL displays are mainly used. Especially when electronic information is document information, It is necessary to keep an eye on the browsing means for a relatively long time, and these actions are not necessarily human-friendly means. Generally, the disadvantage of the light-emitting display is that the eyes are fatigued by flickering and inconvenient to carry. It is known that the reading posture is limited, it is necessary to adjust the line of sight to the still screen, and the power consumption increases when reading for a long time.

[0004] As a display means to compensate for these drawbacks, V, a (memory type) reflective display that uses external light and does not consume power for image retention is known! It is hard to say that it has sufficient performance.

[0005] That is, the method using a polarizing plate such as a reflective liquid crystal has a low reflectance of about 40%, making it difficult to display white, and many of the manufacturing methods used to manufacture the constituent members are not easy. In addition, the polymer dispersed liquid crystal requires a high voltage and uses the difference in refractive index between organic substances, so that the contrast of the obtained image is not sufficient. In addition, polymer network type liquid crystals have problems such as high drive voltage and the need for complex TFT circuits to improve memory performance. In addition, a display element based on electrophoresis requires a high voltage of 10 V or more, and there is a concern about durability due to aggregation of electrophoretic particles. Also, the elect mouth The chromic display element can be driven at a low voltage of 3V or less, but the color quality of black or color (yellow, magenta, cyan, blue, green, red, etc.) is insufficient, and it is displayed to ensure memory performance. There is a concern that the cell requires a complicated film structure such as a deposited film.

[0006] As a display method for eliminating the drawbacks of each of the above-described methods, an electrodeposition (hereinafter abbreviated as ED) method using dissolution or precipitation of a metal or a metal salt is known. The ED method can be driven at a low voltage of 3 V or less, and has advantages such as a simple cell configuration, excellent black-to-white contrast and black quality, and various methods have been disclosed (for example, patent documents). See 1-3.)

[0007] As a result of detailed examination of the technique disclosed in the above-mentioned patent document, the present inventor displays an organic solvent in the electrolyte and displays it when stored in a high temperature environment for a long period of time. There is a problem that the sealing performance of the element is broken and liquid spills out, contaminates the surroundings, and the composition of the electrolyte changes due to the permeation and volatilization of the organic solvent into the sealant, resulting in fluctuations in display performance. It has been found.

Patent Document 1: U.S. Pat.No. 4,240,716

Patent Document 2: Japanese Patent No. 3428603

Patent Document 3: Japanese Patent Laid-Open No. 2003-241227

Disclosure of the invention

Problems to be solved by the invention

[0008] The present invention has been made in view of the above problems, and an object thereof is a solid electrolyte substantially free of an organic solvent and having excellent stability, and durability in a high-temperature environment using the same. It is to provide a display element with improved performance.

Means for solving the problem

The above object of the present invention is achieved by the following configurations.

[0010] 1. A solid electrolyte characterized by being substantially free of an organic solvent and formed from a silver salt room temperature molten salt, filler particles, and a water-soluble high molecular compound.

[0011] 2. The solid electrolyte as described in 1 above, wherein the silver salt room temperature molten salt is formed from a silver salt and a compound represented by the following general formula (I) or (II). [0012] [Chemical formula 1] General formula (1)

MS Ν '(R

[Wherein, M represents a hydrogen atom, a metal atom or a quaternary ammonium. Z represents a nitrogen-containing heterocyclic ring excluding the imidazole ring. n represents an integer of 0 to 5, and R ¹ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, or an alkoxy group. , Aryloxy group, alkylthio group, allylthio group, alkyl strength rubamoyl group, aryl carbamoyl group, strength rubamoyl group, alkyl sulfamoyl group, aryl sulfamoyl group, sulfamoyl group, cyano group, alkyl sulfol group, aryl sulfo -Alkyl group, alkoxycarbonyl group, arylcarbonyl group, alkylcarbonyl group, aryl group, carbonyl group, acyloxy group, carboxyl group, carbonyl group, sulfol group, amino group, hydroxy group Or a heterocyclic group, and when n is 2 or more, each R ¹ is the same. They may be connected to each other or may be connected to each other to form a condensed ring. ]

General formula (Π)

R ² -S-R ³

[Wherein R ² and R ³ each represents a substituted or unsubstituted hydrocarbon group. However, when a ring containing an S atom is formed, an aromatic group is not taken. In addition, no SS-bond is formed in the molecular structure. ]

3. The solid electrolyte according to 1 or 2 above, wherein the water-soluble polymer compound is a compound represented by the following general formula (III) having an average molecular weight of 100,000 or more and 2 million or less

[0014] General formula (III)

H (OR) OH

[Wherein, R represents an alkylene group having 2 to 4 carbon atoms, and n represents an integer. ] 4. When the molar concentration of halogen ion or halogen atom is [X] (mol Zkg) and the total molar concentration of silver in the compound containing silver or silver in the chemical structure is [Ag] (mol Zkg), 4. The solid electrolyte according to any one of 1 to 3, wherein the condition defined by the following formula (1) is satisfied.

[0015] Equation (1)

5. A display element having an electrolyte containing silver or a compound containing silver in a chemical structure between the counter electrodes, and driving the counter electrode so as to cause dissolution and precipitation of silver. A display element characterized in that the electrolyte includes the solid electrolyte described in any one of the above 1 to 4 in force 1.

The invention's effect

[0016] According to the present invention, a solid electrolyte substantially free of an organic solvent and excellent in stability, and an electrode that can be driven at a low voltage with a simple member configuration and high display contrast using the solid electrolyte. A display element with improved durability could be provided.

Brief Description of Drawings

FIG. 1 is a schematic cross-sectional view showing a basic configuration of a display element of the present invention.

Explanation of symbols

[0018] 1 Counter electrode

2 Electrolyte

3 Power supply

4 Ground

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the best mode for carrying out the present invention will be described in detail.

[0020] As a result of intensive studies in view of the above problems, the present inventor has substantially achieved organicity by using a solid electrolyte characterized by being formed from silver salt room temperature molten salt, filler particles, and a water-soluble polymer compound. A solid electrolyte that does not contain a solvent and is excellent in stability can be obtained, and by using the solid electrolyte of the present invention, it can be driven with a simple member configuration and low voltage, It has been found that a display element with improved display resistance with high display contrast can be realized, and as soon as the present invention has been achieved.

[0021] Details of the present invention will be described below.

[0022] << Solid electrolyte >>

The solid electrolyte of the present invention refers to a solid electrolyte that exhibits ionic conductivity with substantially no fluidity. Compared to liquid electrolytes, they have easier handling, no risk of liquid leakage, and a gap between the counter electrodes of the display element can be secured without a spacer.

[0023] The solid electrolyte of the present invention is characterized in that it contains substantially no organic solvent and is formed from a silver salt room temperature molten salt, a filler particle and a water-soluble polymer compound.

[0024] These silver salt room temperature molten salt, filler particles and water-soluble polymer compound are not soluble in each other, and the matrix of water-soluble polymer compound forms a skeleton of solid electrolyte, and one filler particle is contained in the matrix. In addition, the dispersion of silver salt room temperature molten salt makes it non-fluid! / Forms a solid electrolyte! /

[0025] Although it is difficult to impart sufficient strength as a solid electrolyte only with a water-soluble polymer compound and a silver salt room temperature molten salt, a water-soluble polymer can be obtained by dispersing filler particles therein. The matrix formed by the compound can be strengthened, and the dispersed filler particles are not electrically conductive, so that the ion conduction path in the electrolyte can be averaged, It became possible to impart uniform conductivity to the electrolyte, and it was possible to form high-quality images with little bleeding and image unevenness.

[0026] Preferably, the volume content in the solid electrolyte is 30% or more and 75% or less of silver salt and room temperature molten salt, 15% or more and 40% or less of filler particles, water-soluble, from the viewpoint of surface stickiness and strength. The polymer compound is preferably 15% or more and 35% or less.

[0027] As a method for forming the solid electrolyte of the present invention, 1) A silver salt room temperature molten salt, filler particles and a water-soluble polymer compound are mixed in an aqueous solution, and an aqueous solution in which filler particles are dispersed is applied and dried. 2) A method in which filler particles and a water-soluble polymer compound are mixed in an aqueous solution, an aqueous solution in which filler particles are dispersed is applied, and a dried salt film is infiltrated with a silver salt at room temperature. [0028] The term "substantially free of organic solvent" as used in the present invention means that the content of the organic solvent in the electrolyte is

5. It means that it is 0% by mass or less, more preferably 1.0% by mass or less, and particularly preferably it does not contain any organic solvent.

[0029] Next, the details of the silver salt room temperature molten salt, filler particles, and water-soluble polymer compound constituting the solid electrolyte of the present invention will be described.

[Silver salt room temperature molten salt]

The room temperature molten salt according to the present invention is also called an ionic liquid, and is a liquid containing cations and ions of a cation, and has a melting point of 25 ° C or lower, preferably 0 ° C or lower, more preferably 10 ° C or lower. It is a general term for the molten salt.

The silver salt room temperature molten salt according to the present invention is formed from a silver salt and a compound represented by the general formula (I), or a silver salt and a compound represented by the general formula (式). I like to talk!

As the silver salt forming the silver salt room temperature molten salt according to the present invention, a known silver salt can be used, for example, silver nitrate, silver carbonate, silver acetate, p-toluenesulfonic acid silver, silver perchlorate Silver trifluorosulfate, silver citrate, silver trifluoroacetate, silver iodide, silver chloride, silver bromide, silver sulfide, silver oxide, fatty acid silver and the like.

[0033] The concentration of silver ions contained in the solid electrolyte of the present invention is preferably 0.2 mol / kg≤ [Ag] ≤2.0 mol Zkg. When the silver ion concentration is higher than 0.2 mol Zkg, the driving speed is not delayed. When the silver ion concentration is smaller than 2 mol Zkg, no precipitation occurs even at low temperature storage, which is advantageous.

[0034] Next, the compound represented by the general formula (I) for forming the silver salt room temperature molten salt according to the present invention will be described.

[0035] In the general formula (I), M represents a hydrogen atom, a metal atom or a quaternary ammonium. Z represents a nitrogen-containing heterocyclic ring excluding imidazole rings. n represents an integer of 0 to 5, and R ¹ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxyl group. Group, aryloxy group, alkylthio group, allylthio group, alkyl strength rubamoyl group, aryl power rubamoyl group, strong rubamoyl group, alkyl sulfamoyl group, aryl sulfamoyl group, sulfamoyl group, cyano group, alkylsulfol group, allylsulfur Hole group, alkoxy carbonyl group, arylcarbonyl group, alkyl carbonyl group, aryl carbonyl group, acyloxy group, carboxyl group, carbonyl group, sulfonyl group, amino group, hydroxy group Alternatively, it represents a heterocyclic group, and when n is 2 or more, each R ¹ may be the same or different and may be linked to each other to form a condensed ring.

[0036] Examples of the metal atom represented by M in the general formula (I) include Li, Na, K, Mg, Ca, Zn, Ag, and the like. Examples of the quaternary ammonia include, for example, NH, N (CH), N (CH),

4 3 4 4 9 4

N (CH) C H, N (CH) C H, N (CH) CH C H and the like can be mentioned.

3 3 12 25 3 3 16 33 3 3 2 6 5

[0037] Examples of the nitrogen-containing heterocyclic ring represented by Z in the general formula (I) include, for example, a tetrazole ring, a triazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole ring, an indole ring, an oxazole ring, and a benzoxa ring. Examples include a sol ring, a benzimidazole ring, a benzothiazole ring, a benzoselenazole ring, and a naphthoxazole ring.

[0038] Examples of the halogen atom represented by R ¹ in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group include, for example, methyl, ethyl, and propynole. , I-propyl, butyl, t-butinole, pentinole, cyclopentyl, hexenole, cyclohexyl, octyl, dodecyl, hydroxyethyl, methoxyethyl, trifluoromethyl, benzyl, and the like. Examples of the aryl group include Examples of such groups include phenyl and naphthyl groups. Examples of the alkylcarbonamide group include acetylamino and propio-aminobutyrylamino. Examples of the arylcarbonamide group include benzoylamino and the like. Examples of the alkylsulfonamido group include methanes. Examples thereof include a sulfonylamino group, an ethanesulfonylamino group, and the like. Examples of the arylsulfonamide group include a benzenesulfo-lumino group and a toluenesulfo-lumino group. Examples of the aryloxy group include phenoxy and the like. Examples of the alkylthio group include methylthio, ethylthio, and butylthio groups. Examples of the arylthio group include a furthio group and a tolylthio group. Examples of the alkyl group rubamoyl group include: Examples include methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl, jetylcarbamoyl, dibutylcarbamoyl, piberidylcarbamoyl, morpholylcarbamoyl, and the like. Examples of the strong rubamoyl group include groups such as phenylcarbamoyl, methylphenolcarbamoyl, ethylphenolcarbamoyl, and benzylphenolcarbamoyl. Examples of the alkylsulfamoyl group include methylsulfamoyl, dimethylsulfamoyl, and the like. , Ethylsulfamoyl, jetylsulfamoyl, dibutylsulfamoyl, piberidylsulfamoyl, morpholylsulfamoyl, etc., and arylsulfamoyl groups include, for example, phenylsulfamoyl, Examples include methylphenol sulfamoyl, ethylphenylsulfamoyl, benzylphenolsulfamoyl, and the like. Examples of the alkylsulfol group include a methanesulfol group, an ethanesulfol group, and the like. Is, for example, Hue - Rusuruho

Groups, such as 4-l, 4-phenylsulfol, p-toluenesulfol and the like. Examples of alkoxycarbol groups include methoxycarbol, ethoxycarbol, butoxycarbonyl and the like. Examples of the arylcarbonyl group include phenoxy carbonyl, and examples of the alkyl carbo yl group include acetyl, propiool, butyroyl and the like. As the aryl group, for example, a benzoyl group, an alkyl benzoyl group and the like can be mentioned. As the asiloxy group, for example, each group such as acetyloxy, propio-loxy, butyroyloxy and the like can be mentioned. Is, for example, an oxazole ring, thiazole ring, triazole ring, selenazole ring, tetrazole ring, oxadiazole ring, Asianazole ring, thiazine ring, triazine ring, benzoxazole ring, benzthiazole ring, indolenine ring, benzselenazole ring, naphthothiazole ring, triazaindolizine ring, diazaindolizine ring, tetraazaindolizine ring Groups and the like. These substituents further include those having a substituent.

[0039] Next, preferred specific examples of the compound represented by the general formula (I) will be shown, but the present invention is not limited to these exemplified compounds.

[0040] [Chemical 2]

[ε ^] [woo]

0Zdf / :) d 6 91708S0 / .00Z OAV 1 -9 1- 10 卜 11

N H

I 1 15 1-16 Ϊ -17

[-18 1— 19

H ₃ C,

N 1 N

HS

SH

N

Among the above-exemplified compounds, Exemplified Compounds 1-12 and 1-18 are particularly preferable from the viewpoint that the object and effects of the present invention can be fully exhibited.

[0043] Next, the compound represented by the general formula (Π) that forms the silver salt room temperature molten salt according to the present invention will be described.

In the general formula (II), R ² and R ³ each represent a substituted or unsubstituted hydrocarbon group, and these include an aromatic straight chain group or a branched group. Further, these hydrocarbon groups may contain one or more nitrogen atoms, oxygen atoms, phosphorus atoms, sulfur atoms, and halogen atoms. However, when a ring containing an S atom is formed, an aromatic group is not taken.

[0045] Examples of the group that can be substituted with a hydrocarbon group include an amino group, a guazino group, a quaternary ammonium group, a hydroxyl group, a halogen compound, a carboxylic acid group, a carboxylate group, and an amide. Group, sulfinic acid group, sulfonic acid group, sulfate group, phosphonic acid group, phosphate group, Examples thereof include a nitro group and a cyano group.

[0046] Generally, in order to cause dissolution and precipitation of silver, it is necessary to dissolve silver in the electrolyte. For example, silver or a compound containing silver is soluble by coexisting with a compound containing a chemical structural species that interacts with silver, such as a coordinate bond with silver or a weak covalent bond with silver. It is common to use a means for converting into a product. In the present invention, the thioether group is also useful as a silver solvent, and has an effect on the coexisting compound, as the chemical structural species include a halogen atom, a mercapto group, a carboxyl group, and an imino group. It is characterized by high solubility in a small amount of solvent.

[0047] Specific examples of the compound represented by formula (II) according to the present invention are shown below, but the present invention is not limited to these exemplified compounds.

[0048] II 1: CH SCH CH OH

3 2 2

II 2: HOCH CH SCH CH OH

2 2 2 2

II 3: HOCH CH SCH CH SCH CH OH

2 2 2 2 2 2

II 4: HOCH CH SCH CH SCH CH SCH CH OH

2 2 2 2 2 2 2 2

II 5: HOCH CH SCH CH OCH CH OCH CH SCH CH OH

2 2 2 2 2 2 2 2 2 2

II 6: HOCH CH OCH CH SCH CH SCH CH OCH CH OH

2 2 2 2 2 2 2 2 2 2

II 7: H CSCH CH COOH

3 2 2

II 8: HOOCCH SCH COOH

twenty two

II 9: HOOCCH CH SCH CH COOH

2 2 2 2

II 10: HOOCCH SCH CH SCH COOH

2 2 2 2

II l l: HOOCCH SCH CH SCH CH SCH CH SCH COOH

2 2 2 2 2 2 2 2

II-12: HOOCCH CH SCH CH SCH CH (OH) CH SCH CH SCH CH C

2 2 2 2 2 2 2 2 2 2

OOH

II- 13: HOOCCH CH SCH CH SCH CH (OH) CH (OH) CH SCH CH SC

2 2 2 2 2 2 2 2

H CH COOH

twenty two

II 14: H CSCH CH CH NH

3 2 2 2 2

II 15: H NCH CH SCH CH NH

2 2 2 2 2 2

II 16: H NCH CH SCH CH SCH CH NH

2 2 2 2 2 2 2 2 II- 17 :: H CSCH CH CH (NH) COOH

3 2 2 2

II- 18: ： H NCH CH OCH CH SCH CH SCH CH OCH CH NH

2 2 2 2 2 2 2 2 2 2 2 2

II- 19: ： H NCH CH SCH CH OCH CH OCH CH SCH CH NH

2 2 2 2 2 2 2 2 2 2 2 2

II-20:: H NCH CH SCH CH SCH CH SCH CH SCH CH NH

2 2 2 2 2 2 2 2 2 2 2 2

II- 21:: HOOC (NH) CHCH CH SCH CH SCH CH CH (NH) COOH

2 2 2 2 2 2 2 2

II-22: ： HOOC (NH) CHCH SCH CH OCH CH OCH CH SCH CH (NH)

2 2 2 2 2 2 2 2 2 2

COOH

II- 23: ： HOOC (NH) CHCH OCH CH SCH CH SCH CH OCH CH (NH)

2 2 2 2 2 2 2 2 2 2

COOH

II-24: ： HN (0 =) CCH SCH CH OCH CH OCH CH SCH C (= 0) NH

2 2 2 2 2 2 2 2 2 2

II-25: HN (0 =) CCH SCH CH SCH C (= 0) NH

2 2 2 2 2 2

II- 26:: H NHN (0 =) CCH SCH CH SCH C (= 0) NHNH

2 2 2 2 2 2

II- 27: ： H C (0 =) NHCH CH SCH CH SCH CH NHC (= 0) CH

3 2 2 2 2 2 2 3

II- 28: ： H NO SCH CH SCH CH SCH CH SO NH

2 2 2 2 2 2 2 2 2 2

II- 29: ： NaO SCH CH CH SCH CH SCH CH CH SO Na

3 2 2 2 2 2 2 2 2 3

II-30: H CSO NHCH CH SCH CH SCH CH NHO SCH

3 2 2 2 2 2 2 2 2 3

II- 31: ： H N (NH) CSCH CH SC (NH) NH · 2HBr

2 2 2 2

II- 32:: HN (NH) CSCH CH OCH CH OCH CH SC (NH) NH -2HC1

2 2 2 2 2 2 2 2

II- 33: ： HN (NH) CNHCH CH SCH CH SCH CH NHC (NH) NH -2HBr

2 2 2 2 2 2 2 2

II- 34:: [(CH) NCH CH SCH CH SCH CH N (CH)] ²⁺ -2Cl "

[Chemical 4]

11—35 11 -36

11

11-39 n-40

— CH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ — N

Π-41 II— 42

[0050] [Chemical 5]

II 43

11-45

HOOCCH-, SCH ₂ CH ₂ SCH _: -CH ₂ SCH ₂ CH ₂ SCH ₂ COOH

II 1 46 II 47

[0051] Among the above-exemplified compounds, Exemplified Compound II 2 is particularly preferable from the viewpoint that the object and effects of the present invention can be fully exhibited.

[0052] Examples of methods for preparing a room temperature molten salt containing a silver salt according to the present invention include 1) silver salt and general A method in which a compound represented by formula (I) or general formula (II) is mixed and heated to a temperature of about 120 ° C or higher to cool to a molten state, 2) a silver salt and general formula (I) or general formula ( Examples thereof include a method in which the compound represented by i) is dissolved and mixed in a solvent, and the solvent is evaporated and cooled.

[0053] The silver salt room temperature molten salt according to the present invention is an electrolyte solution for electrochemical elements such as display elements such as electochromic and electrodeposition, dye-sensitized solar cells, lithium ion batteries, and electric double layer capacitor fuel cells. Can be used as a reaction field for special synthesis reactions or metal fine particle electrodeposition reactions, or as a raw material prior to the fabrication of sintered bodies. It has an electrolyte containing a compound contained therein, and is applied to a display element that drives the counter electrode so as to cause dissolution and precipitation of silver.

[0054] [Fila single particle]

The filler particles used in the solid electrolyte of the present invention may be any particles as long as they are particles that are not mixed with the compound contained in the solid electrolyte. The filler particle used in the present invention may be an inorganic material, an organic material, or an organic-inorganic composite material thereof. Further, composite particles obtained by combining a pigment and a polymer resin or composite particles obtained by immersing or mordanting a dye in a polymer resin may be used. Examples of pigment components include anthraquinone pigments such as aminoanthraquinone, anthrapyrimidine, furanthrone, anthanthrone, indanthrone, pyrantron, and bilanthanum, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, and diketopyrrolo. Condensed polycyclic pigments such as pyrrole, dioxazine, benzimidazolone, and metal complexes, copper phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and sulfonated copper phthalocyanine lake, metal-free phthalocyanine pigments, acetoacetate chloride -Based, pyrazolone-based, β-naphthol-based, β-oxynaphthoic acid-based, β-oxynaphthoic acid-based azo lake pigments, insoluble azo pigments, condensed azo pigments, acid or basic dye lake pigments, nitrile Pigments, organic pigments such as nitroso pigments. Inorganic pigments include zinc white, titanium dioxide, red pepper, acid chrome, cobalt blue, iron black, alumina white, yellow iron oxide, zinc sulfide, vermilion, cadmium yellow, cadmium red, bitumen, yellow lead, zinc chromate , Molybdenum red, sodium sulfate, calcium carbonate, hydrous silicate, ultramarine, manganese violet, aluminum Examples thereof include powder, bronze powder, and zinc powder. Examples of the particles in which a pigment is combined with a polymer resin include JP 2002-311646, 2003-15352, 2002-236386, 200 2-214913, 2001-281928, 2001-249497. The particles described in No. etc. can be listed. Known dyes can be used as the dye coloring component. Specifically, dyes described in European Patent EP 549, 489A, ExF2-6 dyes described in JP-A-7-152129, JP-A-3-251840 AI-1 to: L1 dyes described on page 308: dyes of L1, dyes described in JP-A-6-3770, general formulas (1) and (1) listed on the lower left column of page 2 of JP-A-1280750 11), compounds represented by (III), exemplified compounds (1) to (45) listed in page 3, lower left column to page 5, lower left column, compounds described in JP-A-1-150132, Ga, Yoshida "Dyes and Chemicals" 9, 84 (Chemicals Industry Association), "New Edition Dye Handbook" 242 (Maruzen, 1970), R. Garner "Reports on the Progress of Appl. Chem" 56, 199 (1971), “Dyes and Chemicals” pages 19, 230 (Japan Chemical Industry Association, 1974), “Coloring Materials” pages 62, 288 (1989), “Dye Industries” pages 32, 208, etc., Research Disclosure (Hereinafter referred to as RD and Note) Compound No. 176 ItemZl7643 (December 1978) 25-26, RD Item 184 ItemZ 18431 (August 1979), RD Item 187 Item / 18716 (November 1979) 649 To 650, RD No. 308 ItemZ308119 (December 1989), page 1003. Examples of the polymer resin for mordanting the dye include, for example, US Pat. No. 4,500,626, columns 58 to 59, JP-A 61-88256, pages 32 to 41, and JP-A 62- Examples thereof include compounds described in 244043, JP-A-62-244036, and the like.

When the solid electrolyte of the present invention is used for a display element, the filler particles are preferably white particles.

Examples of white particles include, for example, titanium dioxide (anatase type or rutile type), barium sulfate, calcium carbonate, acid aluminum, zinc oxide, magnesium oxide, zinc hydroxide, magnesium hydroxide. , Magnesium phosphate, magnesium hydrogen phosphate, alkaline earth metal salts, talc, kaolin, zeolite, acid clay, glass, etc., organic compounds such as polyethylene, polystyrene, acrylic resin, ionomer, ethylene vinyl acetate copolymer Fat, benzoguanamine rosin, urea formalin rosin, melamine formal A simple substance or a composite mixture such as rosin resin or polyamide resin.

[0056] In the present invention, among the white particles, titanium dioxide, zinc oxide, and zinc hydroxide are preferably used. Also, surface treatment with inorganic oxide (Al 2 O, A10 (OH), SiO, etc.)

2 3 2

In addition to these surface treatments, titanium dioxide, titanium dioxide, which has been treated with organic substances such as trimethylolethane, triethanolamine acetate, and trimethylcyclosilane can be used.

[0057] Among these white particles, it is more preferable to use acid titanium or acid zinc from the viewpoint of preventing coloring at high temperature and the reflectance of the element due to the refractive index.

[0058] As a method for incorporating the above white scattering material into the solid electrolyte, for example, together with the silver salt room temperature molten salt according to the present invention, a disperser (for example, an ultrasonic disperser, a pressure disperser, a high-speed stirrer, etc.) And dispersed as a dispersion in which white scattering material is dispersed in a silver salt room temperature molten salt.

[0059] [Water-soluble polymer compound]

The water-soluble polymer compound used in the solid electrolyte of the present invention is not particularly limited. Power Gelatin, gum arabic, poly (bulal alcohol), hydroxyethyl cellulose, hydroxypropenoresenorerose, senorelose acetate, senore Loose acetate butyrate, poly (bulylpyrrolidone), poly (alkylene glycol), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly ( Styrene (maleic anhydride), copoly (styrene monoacrylonitrile), copoly (styrene butadiene), poly (bulusetal) (eg, poly (bulformal) and poly (bulutyl)), poly (ester) s, poly (Urethane), phenoxy resin, poly (salt Polyvinyl butylene), poly (epoxide) s, poly (carbonates), poly (butylacetate), cellose esters, poly (amides), hydrophobic transparent binders such as polybutylbutyranol and senorelose acetate , Sanolose acetate butyrate, polyesterol, polycarbonate, polyacrylic acid, polyurethane and the like.

[0060] Two or more of these water-soluble polymer compounds may be used in combination. In addition, compounds described on pages 71 to 75 of JP-A No. 64-13546 can be exemplified. Among these, the compounds preferably used are compatible with various additives and the dispersion stability of the white scattering material. From the above viewpoint, they are polybulal alcohols, polybulurpyrrolidones, hydroxypropyl celluloses, and polyalkylene glycols.

[0061] The water-soluble polymer compound preferably used in the present invention is a polymer compound having an average molecular weight of 100,000 or more and 200,000 or less and represented by the general formula (III).

[0062] In the general formula (III), R represents an alkylene group having 2 to 4 carbon atoms, and n represents an integer. R includes CH 1 -CH 1, -CH 2 CH (CH 2) 1, CH 2 CH-, 1 CH

2 2 2 3 2 2 2 2

CH CH CH etc. with a block that has different types of alkylene groups

2 2 2

Even a random number may be added. R is preferably CH 1 -CH 1, -CH

twenty two

CH (CH) —. The average molecular weight is preferably 100,000 or more and 2,000,000 or less.

twenty three

If the average molecular weight is less than 100,000, the solid electrolyte membrane strength is not sufficient due to low viscosity, and if the average molecular weight exceeds 2 million, the handling is severely restricted due to high viscosity.

[0063] [[X] Z [Ag]]

In the solid electrolyte of the present invention, the molar concentration of halogen ions or halogen atoms contained in the solid electrolyte is [X] (mole Zkg), and the silver or silver contained in the solid electrolyte is contained in the chemical structure. When the total molar concentration is [Ag] (mol Zkg), it is preferable to satisfy the conditions specified by the following formula (1).

[0064] Formula (1)

The halogen atom in the present invention means an iodine atom, a chlorine atom, a bromine atom, or a fluorine atom. When [X] Z [Ag] is greater than 0.01, X— → X

2 and X is easily cross-acidified with black silver to dissolve black silver and reduce the memory performance.

2

Therefore, the molar concentration of halogen atoms is preferably as low as possible relative to the molar concentration of silver. In the present invention, 0≤ [X] / [Ag] ≤0.001 is more preferable. In the case of adding a halogen ion, with respect to the halogen species, the total molar concentration of each halogen species is preferably [I] <[Br] <[CI] <[F] from the viewpoint of improving the memory property.

[0065] << Display element >>

The display element of the present invention includes silver or a compound containing silver in a chemical structure between counter electrodes. An ED type display element having an electrolyte contained therein and driving the counter electrode so as to cause dissolution and precipitation of silver, wherein the electrolyte includes the solid electrolyte of the present invention.

[0066] In the display element of the present invention, the organic solvent conventionally contained in the electrolyte is used as much as possible by using a novel silver salt room temperature molten salt made of a silver salt and a mercapto compound or a silver salt and a thioether compound. As a result, there is a feature that the durability of the display element can be drastically improved by reducing the influence of the sealing failure caused by the organic solvent.

[0067] [Silver or a compound containing silver in the crystal structure]

The silver or the compound containing silver in the chemical structure according to the present invention is a generic term for compounds such as silver oxide, silver sulfate, metallic silver, silver colloidal particles, silver halide silver, silver complex compounds, silver ions and the like. There are no particular limitations on the state species of the phase such as the solid state, the solubilized state in the liquid, the gas state, etc., and the charged state species such as neutrality, cation, and cationicity.

[Basic cell configuration]

FIG. 1 is a schematic cross-sectional view showing the basic configuration of the display element of the present invention.

In FIG. 1, the display device of the present invention includes an electrolyte 2 contained in a solid electrolyte 2 by holding an electrolyte 2 between a pair of counter electrodes 1 and applying a voltage or current from the power source 3 to the counter electrode 1. This is a display element that causes a dissolution reaction or precipitation reaction of silver, and changes a display state by utilizing a difference in optical properties of light transmission and absorption of a compound containing silver.

[0070] [Other additives]

Examples of the constituent layers of the display element of the present invention include auxiliary layers such as a protective layer, a filter layer, an antihalation layer, a crossover light cut layer, a knocking layer, and the like. Chemical sensitizers, noble metal sensitizers, photosensitive dyes, supersensitizers, couplers, high boiling solvents, anti-capri, stabilizers, development inhibitors, bleach accelerators, fixing accelerators, color mixing inhibitors, formalin Strength bender, toning agent, hardener, surfactant, thickener, plasticizer, slip agent, UV absorber, anti-irradiation dye, filter light-absorbing dye, anti-foaming agent, polymer latex, heavy metal, electrification An inhibitor, a matting agent, and the like can be contained as necessary. [0071] The above-mentioned additives are more specifically described in Research Disclosure (hereinafter abbreviated as RD) No. 176 ItemZ 17643 (December 1978), 184 ItemZ 18431 (August 1979), 187卷 ItemZ 18716 (November 1979) and 308 卷 ItemZ308119 (December 1989).

[0072] These three types of research 'disclosures' are listed below with the types of compounds and their descriptions.

[0073] Additive RD17643 RD18716 RD308119

Classification Page Classification Page Classification

Chemical sensitizer 23 III 648 Upper right 96 III

Sensitizing dye 23 IV 648-649 996-8 IV

Desensitizing dye 23 IV 998 IV

Dye 25-26 VIII 649-650 1003 VIII

Development accelerator 29 XXI 648 Upper right

Capri inhibitor / stabilizer

24 IV 649 Top right 1006-7 VI

Brightener 24 V 998 V

Hardener 26 X 651 Left 1004 ~ 5 X

Surfactant 26-7 XI 650 Right 1005-6 XI

Antistatic agent 27 XII 650 Right 1006-7 XIII

Plasticizer 27 XII 650 Right 1006 XII

Slipper 27 XII

Matting agent 28 XVI 650 Right 1008-9 XVI

Binder 26 XXII 1003〜 '4 IX

Support 28 XVII 1009 XVII

〔Layer structure〕

The constituent layers between the counter electrodes of the display element of the present invention will be further described.

As the constituent layer according to the display element of the present invention, a constituent layer containing a hole transport material can be provided. Examples of hole transport materials include aromatic amines, triphenylene derivatives, Rigothiophene compounds, polypyrroles, polyacetylene derivatives, polyphenylene vinylene derivatives, polychelene vinylene derivatives, polythiophene derivatives, polyarine derivatives, polytoluidine derivatives, Cul, CuSCN, CuInSe, Cu (ln, Ga) Se , CuGaSe,

twenty two

Cu 0, CuS ゝ CuGaS, CuInS, CuAlSe, GaP ゝ NiO, CoO, FeO, BiO, Mo

2 2 2 2 2 3

O, Cr 2 O and the like can be mentioned.

2 2 3

[0075] [Substrate]

Examples of the substrate that can be used in the present invention include polyolefins such as polyethylene and polypropylene, polycarbonates, cellulose acetate, polyethylene terephthalate, polyethylene dinaphthalene dicarboxylate, polyethylene naphthalates, polychlorinated butyl, polyimide. , Synthetic plastic films such as polybulassetals and polystyrene can also be preferably used. Syndiotactic polystyrenes are also preferred. These can be obtained, for example, by the methods described in JP-A-62-117708, JP-A-1-46912, and JP-A-1-178505. Further, a metal substrate such as stainless steel, a paper support such as a noita paper and a resin coated paper, and a support provided with a reflective layer on the plastic film, Japanese Patent Laid-Open No. 62-253195 (pages 29 to 31) It has been cited those forces ^s described as support. Those described in RD No. 17643, page 28, RD No. 18716, page 647, right column to 648 page, left column, and 307105, page 879, can be preferably used. As these supports, those subjected to curling wrinkles by performing a heat treatment of Tg or less as in US Pat. No. 4,141,735 can be used. Further, the surface of these supports may be subjected to a surface treatment for the purpose of improving the adhesion between the support and other constituent layers. In the present invention, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, and flame treatment can be used as the surface treatment. Further, the support described on pages 44 to 149 of publicly known technology No. 5 (issued by Aztec Co., Ltd. on March 22, 1991) can also be used. Furthermore, there are those listed in RD No. 308119, page 10 09, the product “licensing” index, and the “Supports” section on page 92 P108. In addition, a glass substrate or an epoxy resin kneaded with glass can be used.

[Electrode]

In the display element of the present invention, it is preferable that at least one of the counter electrodes is a metal electrode. preferable. As the metal electrode, for example, known metal species such as platinum, gold, silver, copper, aluminum, zinc, nickel, titanium, bismuth, and alloys thereof can be used. The metal electrode is advantageous for maintaining the reduced state of silver or silver, which has a silver or silver content of 80% or more, even though a metal having a work function close to the redox potential of silver in the electrolyte is preferred. It is also excellent in preventing electrode contamination. As an electrode manufacturing method, an existing method such as a vapor deposition method, a printing method, an inkjet method, a spin coating method, or a CVD method can be used.

[0077] In the display element of the present invention, it is preferable that at least one of the counter electrodes is a transparent electrode. The transparent electrode is not particularly limited as long as it is transparent and conducts electricity. For example, Indium Tin Oxide (ITO: Indium Tin Oxide), Indium Zinc Oxide (IZO: Indium Zinc Oxide), Fluorine Doped Tin Oxide (FTO), Indium Oxide, Zinc Oxide, Platinum, Gold, Silver, Rhodium Copper, chromium, carbon, aluminum, silicon, amorphous silicon, and BSO (Bismuth Silicon Oxide). In order to form the electrode in this way, for example, a mask is deposited on the substrate by mask deposition using a sputtering method or the like. After the entire ITO film is formed, patterning may be performed by photolithography. The surface resistance value is preferably 100 Ω or less, more preferably 10 Ω or less. The thickness of the transparent electrode is not particularly limited, but is generally 0.1-20 / ζ πι.

[Other components of display element]

In the display element of the present invention, a sealant, a columnar structure, and spacer particles can be used as necessary.

[0079] The sealing agent is for sealing so as not to leak outside, and is also called a sealing agent. Epoxy resin, urethane resin, acrylic resin, vinyl acetate resin, enthiol system Curing types such as thermosetting, photo-curing, moisture-curing, and anaerobic-curing can be used, such as resin, silicone-based resin, and modified polymer resin.

[0080] The columnar structure imparts strong self-holding property (strength) between the substrates, and is, for example, a columnar body, a quadrangular columnar body, arranged in a predetermined pattern such as a lattice arrangement, and the like. Columnar structures such as elliptical columnar bodies and trapezoidal columnar bodies can be mentioned. Alternatively, stripes arranged at a predetermined interval may be used. These columnar structures are arranged in equal intervals rather than in a random arrangement, an arrangement in which the interval gradually changes, and a predetermined arrangement pattern is repeated at a constant cycle. It is preferable that the arrangement is such that the distance between the substrates, such as the arrangement, can be appropriately maintained and the image display is not disturbed. If the ratio of the area occupied by the columnar structure in the display area of the display element is 1 to 40%, a practically sufficient strength as a display element can be obtained.

[0081] Between the pair of substrates, a spacer may be provided for uniformly maintaining a gap between the substrates. Examples of the spacer include spheres made of resin or inorganic oxide. Further, a fixed spacer whose surface is coated with thermoplastic resin is also preferably used. In order to maintain a uniform gap between the substrates, only the columnar structures may be provided, but both the spacers and the columnar structures may be provided, or the spacers may be replaced with the spacers. Only the space holding member may be used. The diameter of the spacer is equal to or less than the height of the columnar structure, preferably equal to the height. When the columnar structure is not formed, the spacer diameter corresponds to the thickness of the cell gap.

[0082] [Screen printing]

In the present invention, a sealant, a columnar structure, an electrode pattern, and the like can be formed by a screen printing method. In the screen printing method, a screen on which a predetermined pattern is formed is placed on an electrode surface of a substrate, and a printing material (a composition for forming a columnar structure, such as a photocurable resin) is placed on the screen. Then, the squeegee is moved at a predetermined pressure, angle, and speed. Thereby, the printing material is transferred onto the substrate through the pattern of the screen. Next, the transferred material is heat-cured and dried. In the case of forming a columnar structure by the screen printing method, the resin material is not limited to a photocurable resin, for example, a thermosetting resin such as an epoxy resin or an acrylic resin, or a thermoplastic resin can be used. . Thermoplastic resins include polyvinyl chloride resin, polysalt vinylidene resin, polyvinyl acetate resin, polymethacrylate resin resin, polyacrylate resin resin, polystyrene resin, polyamide resin, polyethylene Resin, polypropylene resin, fluorine resin, polyurethane resin, polyatyl-tolyl resin, polyvinyl ether resin, polyvinyl ketone resin, polyether resin, polyvinylpyrrolidone resin, saturated polyester resin, Polycarbonate resin, chlorinated polyether resin and the like can be mentioned. It is desirable to use the resin material in a paste form by dissolving the resin in an appropriate solvent.

[0083] The display element of the present invention can be preferably produced by an On Drop Fill (ODF) method. The For example, a sealing agent in which a spacer is kneaded on one substrate is applied to the periphery of the substrate and precured by UV curing, and a solution that forms a solid electrolyte is applied to the portion surrounded by the sealing agent. Examples of the method include forming a solid electrolyte by appropriately drying and then stacking the other substrate thereon and sealing by UV curing or heating.

[Display Element Driving Method]

In the display element of the present invention, it is preferable to perform a driving operation in which black silver is deposited by applying a voltage equal to or higher than the deposition overvoltage and black silver is continuously deposited by applying a voltage equal to or lower than the deposition overvoltage. By performing this driving operation, the writing energy can be reduced, the driving circuit load can be reduced, and the writing speed as a screen can be improved. In general, it is known that overvoltage exists in electrode reactions in the field of electrochemistry. For example, overvoltage is explained in detail on page 121 of “Introduction to Chemistry and Electrochemistry of Electron Transfer” (published by Asakura Shoten in 1996). Since the display element of the present invention can also be regarded as an electrode reaction between the electrode and silver in the electrolyte, it can be easily understood that overvoltage exists even in silver dissolution precipitation. Since the magnitude of the overvoltage is governed by the exchange current density, it is possible to continue the black silver precipitation by applying a voltage below the precipitation overvoltage after the black silver is formed as in the present invention. It is estimated that the electron injection is easier with less extra electrical energy.

[0085] The driving operation of the display element of the present invention may be simple matrix driving or active matrix driving. The simple matrix drive referred to in the present invention is a drive method in which a current is sequentially applied to a circuit in which a positive line including a plurality of positive electrodes and a negative electrode line including a plurality of negative electrodes face each other in a vertical direction. Say that. The use of simple matrix drive has the advantage that the circuit configuration and drive IC can be simplified and manufactured at low cost. Active matrix driving is a method in which scanning lines, data lines, and current supply lines are formed in a grid pattern, and are driven by TFT circuits provided in each grid pattern. Since switching can be performed for each pixel, there are advantages such as gradation and memory function. For example, a circuit described in FIG. 5 of JP-A No. 2004-29327 can be used.

[0086] [Product application] The display element of the present invention can be used in an electronic book field, an ID card field, a public field, a traffic field, a broadcast field, a payment field, a distribution logistics field, and the like. Specifically, keys for doors, student ID cards, employee ID cards, various membership cards, convenience store cards, department store cards, vending machine cards, gas station cards, subway and railway cards, buses Cards, cash cards, credit cards, highway cards, driver's licenses, hospital examination cards, electronic medical records, health insurance cards, Basic Resident Registers, passports, electronic books, etc.

Example

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the examples, “part” or “%” is used as a force to indicate “part by mass” unless otherwise specified. “/” Represents “% by mass”.

[0088] Example 1

<< Production of solid electrolyte >>

(Preparation of solid electrolyte 1)

After mixing silver bromide and Exemplified Compound (1-4) in a molar ratio of 1: 3 and heating at 150 ° C for 1 hour, it was confirmed that the powder did not remain and was in a molten state When slowly cooled to 25 ° C., room temperature molten salt 1 was formed which was in a molten state even at room temperature. Aqueous solution in which the volume ratios of room temperature molten salt 1, titanium dioxide (average particle size 0.27 m), and polyethylene glycol (average molecular weight 500,000) are 68%, 10%, and 22%, respectively. (Mass ratio of polyethylene glycol is 5% with respect to water), and after dispersing titanium dioxide with an ultrasonic dispersion method, this aqueous solution was added to polyethylene terephthalate (ITO-PET with ITO film). ) Was applied to a thickness of 80 m and dried in a vacuum at 85 ° C. for 30 minutes to obtain a solid electrolyte 1.

[Fabrication of solid electrolyte 2]

In the production of the solid electrolyte 1, the solid electrolyte 2 was produced in the same manner except that the silver bromide was changed to salty silver and the exemplified compound (I 4) was changed to the exemplified compound (I 19).

[Preparation of solid electrolyte 3]

In the production of the solid electrolyte 1, silver bromide was changed to silver p-toluenesulfonate, Further, a solid electrolyte 3 was produced in the same manner except that the exemplified compound (I 4) was changed to the exemplified compound (II 3).

[Preparation of solid electrolyte 4]

The solid electrolyte 1 was prepared in the same manner except that silver bromide was changed to silver p-toluenesulfonate and polyethylene glycol (average molecular weight 500,000) was changed to polyethylene glycol (average molecular weight 1 million). Electrolyte 4 was produced.

[Fabrication of solid electrolyte 5]

In the preparation of the solid electrolyte 1, the solid electrolyte 5 was changed in the same manner except that the silver bromide was changed to silver p-toluenesulfonate and the exemplified compound (I 4) was changed to the exemplified compound (II 4). Produced.

[Preparation of solid electrolyte 6]

A solid electrolyte 6 was prepared in the same manner as in the production of the solid electrolyte 5 except that 30% of propylene carbonate was added to the silver salt room temperature molten salt.

[Preparation of solid electrolyte 7]

A solid electrolyte 7 was produced in the same manner as in the production of the solid electrolyte 5 except that polyethylene glycol (average molecular weight 500,000) was changed to polyvinyl alcohol (saponification degree 86%, polymerization degree 3500).

[Fabrication of solid electrolyte 8]

A solid electrolyte 8 was prepared in the same manner as in the production of the solid electrolyte 5 except that polyethylene glycol (average molecular weight 500,000) was changed to gelatin.

[0096] << Evaluation of Solid Electrolyte >>

For each of the prepared solid electrolytes 1 to 8, ITO-PET was pressed so that ITO overlapped from the surface of the solid electrolyte, and heated and pressed at 80 ° C. to form an ITO-PETZ solid electrolyte ZITO-PET film. When a current value of 1.5 V DC was applied from both ITO electrodes, a current of ² mA to ²⁰ mAZcm ² was observed, confirming that the solid electrolyte membrane of the present invention functions as an electrolyte. In addition, liquid leakage due to the overlapping edge force was not observed.

[0097] << Production of Display Element >> (Production of display element 1)

(Preparation of electrolyte 1)

After adding 210 mg of potassium iodide and 300 mg of silver iodide in 2.5 g of dimethyl sulfoxide and completely dissolving it, 0.5 g of titanium oxide (average primary particle size 0.34 m) is added, and an ultrasonic dispersion device is added. Then, 150 mg of polybulurpyrrolidone (average molecular weight 15000) was added and stirred for 1 hour while heating to 120 ° C. to obtain an electrolytic solution 1.

[0098] (Preparation of transparent electrode 1)

An ITO film having a pitch of 145 μm and an electrode width of 130 μm was formed on a glass substrate having a thickness of 1.5 mm and 2 cm × 4 cm according to a known method to obtain a transparent electrode (electrode 1).

[0099] (Production of metal electrode 2)

Using a known method, a silver electrode (electrode 2) having an electrode thickness of 0.2 μm, a pitch of 145 μm, and an electrode interval of 130 μm was obtained on a glass substrate having a thickness of 1.5 mm and 2 cm × 4 cm.

[0100] (Production of display element)

Insert electrode 1 and electrode 2 through a 30-meter spacer so that the electrode surfaces face each other, and seal the area around the pattern electrode with an epoxy sealant, excluding a portion of the sealing hole. An empty cell was produced. The electrolyte solution 1 was injected into this empty cell by vacuum injection, and then the sealing port was sealed to produce a display element 1.

[0101] [Production of display element 2]

The solid electrolyte 1 is formed on the transparent electrode 1, and then the metal electrode 2 is stacked on the solid electrolyte 1 so that the electrodes face each other across the solid electrolyte, and then heated and pressed at 85 ° C. The display element 2 was produced by bonding.

[0102] [Production of display elements 3 to 9]

Display elements 3 to 9 were produced in the same manner as in the production of the display element 2 except that the solid electrolyte 1 was changed to solid electrolytes 2 to 8, respectively.

[0103] << Evaluation of display element: durability >>

Apply a voltage of ± 1.5 to each manufactured display element, and apply an application time (half time 1) that reduces the reflectance at 550 nm of the spectrocolorimeter CM-3700d manufactured by Co-Caminolta Sensing. Asked. In addition, the display element was forced for 2 weeks in a constant temperature and humidity chamber at 80 ° C and 45% relative humidity. After the deterioration treatment, a half-life time 2 was determined in the same manner as described above. Half time ratio = Half time 2

Z half time 1 was calculated and used as an evaluation value of durability.

[0104] Table 1 shows the durability results obtained as described above.

[0105] [Table 1]

As is clear from the results shown in Table 1, it is clear that the display element using the silver salt room temperature molten salt of the present invention has improved durability with a small fluctuation range of the half value after the forced deterioration treatment. Yes.

Claims

The scope of the claims

[1] A solid electrolyte characterized by being substantially free of an organic solvent and formed from a silver salt room temperature molten salt, filler particles, and a water-soluble polymer compound.

[2] The solid electrolyte according to claim 1, wherein the silver salt room temperature molten salt is formed into a compound force represented by the following general formula (I) or (II) with a silver salt: .

[Chemical 1]

[In the formula, M represents a hydrogen atom, a metal atom, or a quaternary ammonia. Z represents a nitrogen-containing heterocyclic ring excluding the imidazole ring. n represents an integer of 0 to 5, and R ¹ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, or an alkoxy group. , Aryloxy group, alkylthio group, allylthio group, alkyl strength rubamoyl group, aryl carbamoyl group, strength rubamoyl group, alkyl sulfamoyl group, aryl sulfamoyl group, sulfamoyl group, cyano group, alkyl sulfol group, aryl sulfo -Alkyl group, alkoxycarbonyl group, arylcarbonyl group, alkylcarbonyl group, aryl group, carbonyl group, acyloxy group, carboxyl group, carbonyl group, sulfol group, amino group, hydroxy group Or a heterocyclic group, and when n is 2 or more, each R ¹ is the same. They may be connected to each other or may be connected to each other to form a condensed ring. ]

General formula (Π)

R ² -S-R ³

[3] The water-soluble polymer compound has the following general formula (III 3. The solid electrolyte according to claim 1 or 2, wherein the solid electrolyte is a compound represented by the following formula:

General formula (ΠΙ)

H (OR) OH

[Wherein, R represents an alkylene group having 2 to 4 carbon atoms, and n represents an integer. ]

[4] When the molar concentration of halogen ion or halogen atom is [X] (mol Zkg) and the total molar concentration of silver of the compound containing silver or silver in the chemical structure is [Ag] (mol Zkg), The solid electrolyte according to any one of claims 1 to 3, wherein the condition defined by the formula (1) is satisfied.

Formula (1)

[5] A display element having an electrolyte containing silver or a compound containing silver in a chemical structure between counter electrodes, and driving the counter electrode so as to cause dissolution and precipitation of silver. 5. A display element, wherein the electrolyte comprises the solid electrolyte according to any one of claims 1 to 4.