JP2009053497A - Electrochromic display element and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide the manufacturing method of a low cost electrochromic display element whose productivity is high and which has high performance. <P>SOLUTION: The manufacturing method of the electrochromic display element provided with an electrochromic layer 107 and an electrolyte layer 106 between first and second electrodes 102 and 104 includes: a process for forming the electrochromic layer 107 on the first electrode 107 by an electro-spinning method; and a process for forming the electrolyte layer 106 coming in contact with the electrochromic layer 107. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an electrochromic display element and a manufacturing method thereof, and more particularly to an electrochromic display element using an electrospinning method and a manufacturing method thereof.

  In recent years, with the spread of computers, the role of paper used for storing and transmitting documents has decreased, but when browsing digital information, the tendency to print and read on paper is still strong. For this reason, the amount of paper discarded only for temporary use tends to increase. Considering books, magazines, and newspapers, the amount of paper consumed every day is a very serious problem from the viewpoint of resources and the environment.

  On the other hand, considering human information recognition methods and thinking methods, the superiority of paper over displays typified by cathode ray tubes (CRTs) and transmissive liquid crystals cannot be ignored. Therefore, as an electronic medium that replaces paper, electronic paper having both the advantages of paper and the advantages of a display is expected. The characteristics required for electronic paper include a reflective display element, a high white reflectance and a high contrast ratio, a high-definition display, a memory effect in display, and a low voltage. It can be driven, it is thin and light, and it is inexpensive.

  Electronic paper display methods include a reflective liquid crystal method, an electrophoretic method, a two-color ball method, and an electrochromic method. In the reflective liquid crystal system, the display is dark because a liquid crystal having optical rotation and a polarizing plate having birefringence are used. In addition, due to the nature of the metal reflector, the white display is a glaring reflected light, so that long-time use has the disadvantage of placing a burden on the eyes.

  In the electrophoresis method, a white pigment, black toner, or the like is laminated on an electrode by the action of an electric field. The two-color ball display system is composed of spheres that are separately painted in two colors, such as white in half and black in half, and utilizes rotation by the action of an electric field. Both methods require a gap for the granular material to enter and cannot be packed most closely, making it difficult to obtain high contrast.

  The electrochromic system utilizes the fact that a reversible oxidation-reduction reaction occurs when an electric field is applied, and color development / decoloration associated therewith occurs. Since it is a reflective display element that repeats color development / decolorization electrically with respect to other display methods, it is advantageous in terms of the burden on the eyes and the contrast (see Patent Documents 1 to 4).

  Various methods are applied to the method of forming the electrochromic layer. For example, a sputtering method, an EB (Electron Beam) resistance heating vapor deposition method, a CVD (Chemical Vapor Deposition) method, or the like is applied for forming a metal thin film or an inorganic compound thin film.

  The spotting method and coating method are methods in which a thin film is formed by applying a liquid onto a substrate with a metal tip or coater that can hold the liquid in the gap with a minute gap like the tip of a fountain pen, and then drying. It is.

  The ink jet method is a method in which a thin film is formed by ejecting a solvent in which an electrochromic material is dissolved as a small droplet from a nozzle, and depositing it on a substrate and drying it.

The electrolytic polymerization method is a method in which an electrochromic material is formed on the electrode surface by immersing the electrode substrate in a solution in which a conjugated monomer is dissolved and applying a voltage.
JP 2002-287173 A JP 2006-208862 A JP 2006-058617 A JP-A-7-134317

  However, the sputtering method and the EB vapor deposition method cannot be applied to a polymer material because they are exposed to plasma and high heat under high vacuum. Further, the spotting method, the coating method, and the ink jet method require time for drying and are not suitable for a low-cost process. In addition, the material is wasted in the coating method and the landing accuracy is difficult to control in the ink jet method. Furthermore, in the electropolymerization method, since the conductive polymer is densely formed, the adhesion with the electrolyte layer is lowered and the ionic conduction is also lowered. Moreover, since it is necessary to form a film in advance, the process becomes complicated.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for producing a high-performance electrochromic display element that is low in cost and excellent in productivity.

  The method for manufacturing an electrochromic display element according to the present invention is a method for manufacturing an electrochromic display element comprising an electrochromic layer and an electrolyte layer between a first electrode and a second electrode. A step of forming an electrochromic layer on the electrode by an electrospinning method, and a step of forming an electrolyte layer in contact with the electrochromic layer.

  The electrochromic material constituting the electrochromic layer may be polyacetylene, poly-p-phenylene, poly-p-phenylene oxide, poly-p-phenylene sulfide, poly-p-phenylene vinylene, polynaphthylene vinylene, polyiso Thianaphthene, polypyrrole, polythiophene, polythiophene vinylene, polyalkylthiophene, polyethylene dioxythiophene, polypropylene dioxythiophene, polyaniline, polyperiphthalene, polyoxadiazole, polythiazyl, polyacene, polyfuran, polyalkylfuran, polyselenophene, poly Tellurophene, polyaminopyrene, polyphenanthrene, polyimidazole, polyoxazole, polythiazole, polypyrazole, polyisoxazole, Liisothiazole, polybenzotriazole, polyfluorene, polymer whose main chain consists of aromatic ring or heteroaromatic ring and boron atom, polypyridine, polypyridazine, polypyrimidine, polypyrazine, polyquinoline polymer, polypyran polymer A conjugated polymer selected from the group is preferred.

  In addition, it is preferable to include a step of forming a buffer layer made of a material that increases electron or hole injection by an electrospinning method between the first electrode and the electrochromic layer.

  The electrochromic display element according to the present invention is manufactured by the above method.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the high performance electrochromic display element which is excellent in productivity at low cost can be provided.

  Embodiments of the present invention will be described below. However, the present invention is not limited to the following embodiment. In addition, for clarity of explanation, the following description and drawings are simplified as appropriate.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is a cross-sectional view schematically showing a part of an electrochromic display element manufactured by using a manufacturing method according to an embodiment of the present invention. As shown in FIG. 1, the electrochromic display element manufactured by the manufacturing method of the present invention includes a first substrate 101, a display electrode 102, a second substrate 103, a counter electrode 104, a spacer 105, an electrolyte layer 106, an electro A chromic layer 107 is provided.

  In the electrochromic display element according to this embodiment, a forward voltage and a reverse voltage are applied between the display electrode 102 formed on the first substrate 101 and the counter electrode 104 formed on the second substrate 103. As a result, ions are doped into or dedoped from the electrochromic layer 107 through the electrolyte layer 106. Thereby, the two states of color development and color erasure are repeated. Since the electrochromic material has a memory property, the coloring / decoloring state does not change even when the voltage is turned off.

  The first substrate 101 needs to be a transparent insulating substrate because an observer needs to be able to visually recognize the color developing layer. Therefore, it is desirable to have a total light transmittance of 70% or more, more preferably 80% or more. As the first substrate 101, a glass substrate such as a quartz glass substrate or a white plate glass substrate, polystyrene (PS), polymethyl methacrylate (PMMA), styrene-methyl methacrylate copolymer (MS), polycarbonate (PC), cycloolefin Examples thereof include transparent resin substrates such as polymer (COP), cycloolefin copolymer (COC), polyethylene terephthalate (PET), and polyethylene naphthalate (PEN).

  The display electrode 102 is also formed on the first substrate 101 and needs to be transparent for the same reason as the first substrate 101. Therefore, it is desirable to have a total light transmittance of 70% or more, more preferably 80% or more. Examples of the display electrode 102 include metal oxide films such as indium tin oxide (ITO), antimony-doped tin oxide (ATO), antimony-doped zinc oxide (AZO), and zinc oxide (ZnO), so-called transparent conductive films. Conductive carbides such as single wall carbon nanotubes (SWCNT) and double wall carbon nanotubes (DWCNT), conductive polymers such as poly (ethylene-3,4-dioxythiophene) (PEDOT), polyaniline derivatives, polypyrrole derivatives, etc. May be stacked on the first substrate 101 so as not to reduce the transmittance.

  Since the second substrate 103 does not need to be transparent, various insulating substrates can be used. For example, a glass substrate such as a quartz glass substrate and a white glass substrate, a ceramic substrate, a paper substrate, and a wood substrate can be used. However, the synthetic resin substrate is not limited to these, such as polyethylene naphthalate and polyethylene terephthalate. Esters, polyamides, polycarbonates, cellulose esters such as cellulose acetate, polyvinylidene fluoride, fluoropolymers such as poly (tetrafluoroethylene-co-hexafluoropropylene), polyethers such as polyoxymethylene, polyacetals, polystyrene, polyethylene, polypropylene, Examples thereof include polyolefins such as methylpentene polymer and polyimides such as polyimide-amide and polyetherimide. When these synthetic resins are used as a substrate, a rigid substrate that does not bend easily can be used, but a flexible film-like structure can also be used. Further, when the counter electrode 104 has sufficient rigidity, the second substrate 103 is not necessarily provided.

  The counter electrode 104 is formed on the second substrate 103. The counter electrode 104 need not be transparent as long as it has conductivity, and various metal materials, polymer materials, ceramic materials, semiconductor materials, and the like can be used. In general, a metal material having high electrical conductivity is preferable, for example, lithium, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, silver, gold, copper, nickel, palladium, platinum, Examples thereof include, but are not limited to, chromium, molybdenum, tungsten, manganese, nickel, cobalt, and alloys containing these as main components. In particular, gold, silver, and copper are more preferable because they have high conductivity and are chemically inert. In addition, a highly reflective material may be stacked over the counter electrode 104 in order to improve visibility.

  The spacer 105 has a function of maintaining a distance between the electrodes and preventing a short circuit. Examples of the spacer 105 include a sphere made of a general resin such as an epoxy resin, an acrylic resin, a polyester resin, a polyether resin, a polyethylene resin, or a polyimide resin, an inorganic oxide, or a hybrid material thereof. Further, a fixed spacer having a surface coated with a thermoplastic resin is also preferably used. In addition, thickness is 1-200 micrometers normally, Furthermore, 5-100 micrometers is preferable.

The electrolyte layer 106 is formed between the counter electrode 104 and the electrochromic layer 107 and is in contact with the electrochromic layer 107. Moreover, the form is not specifically limited. For example, in the case of a solution, since the ionic conductivity is large, the response speed, the driving voltage / current can be reduced. Moreover, if it is a gel form and a solid form, a highly reliable element which does not leak can be provided. As a solution electrolyte, it is common to use a solution in which a lithium salt such as LiClO ₄ , LiAsF ₆ , LiPF ₆ , LiBF ₄ or the like is dissolved in an organic solvent such as acetonitrile, butyrolactone, or propylene carbonate. Some use ionic liquids for the purpose of improving efficiency and safety, and examples include compounds having tetrafluoroborate, trifluoromethylsulfonylimide, pentafluoroethylsulfonylimide, and the like as anions. As cations, there are imidazolium cations such as ethylmethylimidazolium and methylbutylimidazolium, pyrrolidinium cations such as butylmethylpyrrolidinium and butylpyridinium, ammonium cations such as butyltrimethylammonium and diethylmethoxyethylmethylammonium, etc. Compounds. As the ionic liquid, any combination of these anions and cations can be used.

As the solid electrolyte, a solid electrolyte such as Ta ₂ O ₅ or MgF ₂ is used. As the polymer solid electrolyte, a supporting electrolyte is dispersed in a matrix polymer material. As the matrix polymer, the main chain units are-(C-C-O) _n -and-(C-C, respectively. _{-N) n -, - (C} -C-S) n - polyethylene oxide represented by, polyethyleneimine, polyethylene sulfide. These may be branched with the main chain structure. Polymethyl methacrylate, polyvinylidene fluoride, polycarbonate and the like are also preferable. When forming the solid electrolyte, it is preferable to add a required plasticizer to the matrix polymer. As the preferred plasticizer, when the matrix polymer is hydrophilic, water, ethyl alcohol, isopropyl alcohol and a mixture thereof are preferable. When the matrix polymer is hydrophobic, propylene carbonate, dimethyl carbonate, ethylene carbonate, γ-butyrolactone is preferable. Acetonitrile, sulfolane, dimethoxyethane, ethyl alcohol, isopropyl alcohol, dimethylformaldehyde, dimethyl sulfoxide, dimethylacetamide, n-methylpyrrolidone and mixtures thereof are preferred. The solid polymer electrolyte is formed by dispersing a supporting electrolyte in the matrix polymer. Examples of the electrolyte include LiCl, LiBr, LiI, LiBF ₄ , LiClO ₄ , LiPF ₆ , and LiCF ₃ SO ₃ . Lithium salts such as potassium salts such as KCl, KI and KBr, sodium salts such as NaCl, NaI and NaBr, or tetraethylammonium borofluoride, tetraethylammonium perchlorate, tetrabutylammonium borofluoride, tetrabutyl perchlorate Examples thereof include tetraalkylammonium salts such as ammonium and tetrabutylammonium halide. The alkyl chain length of the quaternary ammonium salt may be uneven.

The electrochromic layer 107 is formed between the display electrode 102 and the electrolyte layer 106 and is in contact with the electrolyte layer 106. It also has electroactivity and changes color due to electrochemical oxidation / reduction. The electrochromic material constituting the electrochromic layer 107 is not particularly limited as long as it is a material exhibiting electrochromic. For example, as the _{inorganic, IrOx, NiOx, WO 3,} MoO 3, etc. TiO ₂ and the like. Further, in order to realize discoloration with a good display quality, a π-conjugated conductive polymer is suitable, for example, polyacetylene, poly-p-phenylene, poly-p-phenylene oxide, poly-p-phenylene sulfide, poly -P-phenylene vinylene, polynaphthylene vinylene, polyisothianaphthene, polypyrrole, polythiophene, polythiophene vinylene, polyalkylthiophene, polyethylene dioxythiophene, polypropylene dioxythiophene, polyaniline, polyperinaphthalene, polyoxadiazole, polythiazyl, Polyacene, polyfuran, polyalkylfuran, polyselenophene, polytellurophene, polyaminopyrene, polyphenanthrene, polyimidazole, polyoxazole, polythiazole, polypyrazole, polyi Xazole, polyisothiazole, polybenzotriazole, polyfluorene, polymer whose main chain is an aromatic ring or heteroaromatic ring and boron atom, aromatic ring represented by polypyridine, polypyridazine, polypyrimidine, polypyrazine, polyquinoline Examples include, but are not limited to, conjugated polymers such as polyquinoline polymers in which a part of carbon is substituted with nitrogen and polypyran polymers in which a part of carbon of an aromatic ring represented by polypyran is substituted with oxygen. Not.

  Next, the manufacturing method according to the embodiment of the present invention will be described. This manufacturing method includes a step of forming an electrochromic layer 107 on at least one electrode by an electrospinning method, and a step of forming an electrolyte layer 106 in contact with the electrochromic layer 107.

  A method for manufacturing the electrochromic display element shown in FIG. 1 will be described with reference to FIGS. FIG. 2A shows a structure in which a spacer 105 is formed on the display electrode 102 formed on the first substrate 101. A polyester resin solution or the like may be printed on the display electrode 102 on which a predetermined pattern is formed using a printing machine such as a roll coater, a gravure coater, or screen printing, and then dried and cured. Alternatively, the spacer 105 may be formed by patterning and developing by a photolithography process using a photocurable resin that does not affect the electrode.

  A roll coater or a gravure coater is a method for obtaining a prescribed coating thickness by transferring a coating solution, which has been weighed in a certain amount in advance, onto a substrate. Strictly speaking, since a certain amount of the coating liquid is applied to the substrate as it is, unevenness in the thickness of the substrate remains as it is after coating, but there is little loss of the coating liquid. On the other hand, since the coating liquid needs low viscosity, it is not suitable for thick film coating.

  Screen printing is a method of obtaining a film by applying a coating liquid onto a patterned mesh screen by pressurizing with a squeegee and then transferring it onto a substrate. This is a method suitable for obtaining a thick film because a film can be formed by pressurizing a squeegee even if it has a high viscosity.

  In this embodiment mode, the spacer 105 is formed directly over the display electrode 102 using a photolithography process.

  FIG. 2B shows an electrochromic layer 107 formed only on the display electrode 102 according to the present invention by using an electrospinning method. The electrospinning method is a method of forming a film by discharging a solution or dispersion of an electrochromic material using the force of voltage. When a high DC voltage is applied between the nozzle that supplies the solution or dispersion and the display electrode 102, the solution or dispersion of the electrochromic material is jetted toward the display electrode 102, and the electric field generated by the high voltage is further applied. An electrochromic material adheres on the display electrode 102.

  Here, the solution or dispersion of the electrochromic material is ejected as fine droplets from the nozzle due to its surface tension. Charges collect on the surface of the droplets and the droplets repel each other. When the repulsive force of this charge exceeds the surface tension, the droplet breaks up and becomes a jet. Furthermore, if the solvent in the solution or dispersion of the electrochromic material volatilizes, the repulsive force of the charge increases and breaks up into finer jets. In the state where the electrochromic material is oriented in this jet, it reaches, aggregates and deposits on the display electrode 102. Thereby, the electrochromic layer 107 is formed.

  In the electrospinning method, the desired average particle diameter and average length can be selected by appropriately selecting the applied voltage, the distance between the nozzle and the display electrode 102, the nozzle outlet diameter, the composition of the electrochromic material solution or dispersion, and the like. The electrochromic layer 107 is obtained. Further, a buffer layer may be formed between the display electrode 102 and the electrochromic layer 107 by injecting a solution or dispersion of a material that increases electron or hole injection by an electrospinning method. The material for increasing the electron or hole injection forming the buffer layer is not particularly limited, but examples thereof include organic compounds doped with carbonates such as cesium carbonate and lithium carbonate, Alq3, LiF, triphenyldiamine derivatives, Although an oxadiazole derivative, a polyphylyl derivative, a stilbene derivative, etc. can be used, it is not restricted to this.

  The applied voltage in the electrospinning method is not particularly limited, but is generally about 5 kV to 30 kV. If it is less than 5 kV, the film cannot be formed sufficiently. On the other hand, if it exceeds 30 kV, a good film cannot be obtained.

  The distance between the nozzle and the substrate electrode in the electrospinning method is generally in the range of 5 to 30 cm, although it varies depending on the applied voltage and the viscosity and conductivity of the solution or dispersion of the electrochromic material. Even if the distance is less than 5 cm or more than 30 cm, a good film cannot be obtained.

  The nozzle outlet diameter in the electrospinning method is not particularly limited, but is preferably in the range of 300 to 500 μm. Even if the nozzle discharge diameter is less than 300 μm or more than 500 μm, a good film cannot be obtained.

  The concentration of the electrochromic material in the solution or dispersion of the electrochromic material is not particularly limited, but is preferably in the range of 5 to 50% by mass, more preferably 20 to 30% by mass. If the concentration of the electrochromic material in the solution or dispersion is less than 5% by mass, the viscosity of the raw material liquid is too low to make good film formation, and if it exceeds 50% by mass, the viscosity of the raw material liquid is conversely too high. Therefore, workability is poor and good film formation is difficult.

  FIG. 2 (c) shows a structure in which the electrolyte 106 is injected into the structure manufactured in FIG. 2 (b) and the counter electrode 104 is overlaid. As a method for injecting the electrolyte 106 into the structure manufactured in FIG. 2 (b), a wet coating method is preferable as long as it is in the form of a solution. Slit coat, knife coat, lip coat, die coat, dip coat, screen printing, inkjet Examples thereof include wet coating methods such as printing, flexographic printing, and gravure printing. After injecting the electrolyte, the counter electrode 104 is overlapped to form an electrochromic display element.

  Next, although the preferable Example of this invention is described with a comparative example, it is not limited to these Examples.

[Example 1]
A spacer 105 having a thickness of 40 μm was formed on the display electrode 102 made of ITO by patterning in a photolithography process using a negative resist CA3000PM (manufactured by Tokyo Ohka Kogyo Co., Ltd.). Next, as the electrochromic material dispersion, a polyaniline dispersion (polyaniline sulfonic acid 20 mass%, pure water 80 mass% dispersion: Aqua-PASS manufactured by Mitsubishi Rayon Co., Ltd.) is used, and the distance between the nozzle and the display electrode 102 is set. The electrochromic layer 107 was formed by electrospinning at a voltage of 10 kV at a distance of 15 cm. Next, an aqueous solution of ammonium hexafluorophosphate (NH ₄ —PF ₆ , manufactured by Wako Pure Chemical Industries, Ltd.) is injected onto the electrochromic layer 107 formed between the spacers 105 on the display electrode 102, and the electrolytic layer 106 is formed. Formed. Finally, the counter electrode 104 made of ITO was opposed to the display electrode 102, and the electrochromic layer 107 and the electrolytic layer 106 were sandwiched therebetween to produce an electrochromic display element.

  When the forward voltage / reverse voltage was reversed in the produced electrochromic display element, the polyaniline film showed electrochromic properties and a color change from purple to yellow to green.

[Example 2]
Instead of the polyaniline dispersion in Example 1, an electrochromic layer 107 was formed by electrospinning using a polypyrrole dispersion (SSPY: manufactured by TA Chemical). In place of the _NH 4 -PF ₆ solution in Example 1, butyl methyl imidazolium tetrafluoroborate (BMIM-BF _4, manufactured by Wako Pure Chemical) was used to form the electrolyte layer 106. Other than that, the electrochromic display element was produced by the same procedure and prescription as Example 1.

  When the forward voltage / reverse voltage was inverted in the produced electrochromic display element, the polypyrrole film exhibited electrochromic properties and a purple-yellow color change.

[Example 3]
Instead of the polyaniline dispersion in Example 1, an electrochromic layer 107 was formed by an electrospinning method using a polythiophene dispersion (Espacer 100, SD-PT: manufactured by TA Chemical). In addition, the electrolyte layer 106 was formed using BMIM-BF ₄ instead of the NH ₄ —PF ₆ aqueous solution. Other than that, the electrochromic display element was produced by the same procedure and prescription as Example 1.

  When the forward voltage / reverse voltage was reversed in the produced electrochromic display element, the polythiophene film exhibited electrochromic properties and a color change from red to dark blue.

[Comparative Example 1]
Instead of the electrospinning method in Example 1, the polyaniline dispersion was dropped on the display electrode 102, spin-coated, and dried at 80 ° C. for 30 minutes using a dryer to form the electrochromic layer 107. Other than that, the electrochromic display element was produced by the same procedure and prescription as Example 1.

  In the produced electrochromic display element, polyaniline was formed in a portion other than the electrode. Further, when the forward voltage / reverse voltage was inverted, the color change from purple to yellow to green was delayed as compared with Example 1.

  In the present invention, the electrochromic layer 107 is formed by electrospinning. Therefore, the solvent is dried simultaneously with the formation of the electrochromic layer 107, and the productivity is excellent. In addition, the electrochromic layer 107 can be multilayered. Furthermore, since the electrochromic layer 107 can be formed only in the region to be formed on the electrode, the material utilization efficiency is high. In addition, a film formed by the electrospinning method can be made porous depending on the film formation conditions, and adhesion with the electrolyte is improved. Therefore, the color can be changed over the entire electrochromic layer 107, and a high response speed can be obtained.

It is typical sectional drawing which shows a part of electrochromic display element which concerns on embodiment. It is typical sectional drawing which shows the manufacturing method of the electrochromic display element which concerns on embodiment.

Explanation of symbols

101 First substrate 102 Display electrode 103 Second substrate 104 Counter electrode 105 Spacer 106 Electrolyte layer 107 Electrochromic layer

Claims (4)

An electrochromic display element manufacturing method comprising an electrochromic layer and an electrolyte layer between a first electrode and a second electrode,
Forming an electrochromic layer on the first electrode by an electrospinning method;
Forming an electrolyte layer in contact with the electrochromic layer.   The electrochromic material constituting the electrochromic layer is polyacetylene, poly-p-phenylene, poly-p-phenylene oxide, poly-p-phenylene sulfide, poly-p-phenylene vinylene, polynaphthylene vinylene, polyisothianaphthene , Polypyrrole, polythiophene, polythiophene vinylene, polyalkylthiophene, polyethylene dioxythiophene, polypropylene dioxythiophene, polyaniline, polyperiphthalene, polyoxadiazole, polythiazyl, polyacene, polyfuran, polyalkylfuran, polyselenophene, polytellophene , Polyaminopyrene, polyphenanthrene, polyimidazole, polyoxazole, polythiazole, polypyrazole, polyisoxazole, polyi From the group consisting of thiazole, polybenzotriazole, polyfluorene, polymer whose main chain is an aromatic ring or heteroaromatic ring and a boron atom, polypyridine, polypyridazine, polypyrimidine, polypyrazine, polyquinoline polymer, polypyran polymer The method for producing an electrochromic display element according to claim 1, wherein the conjugated polymer is selected.   3. The method according to claim 1, further comprising: forming a buffer layer made of a material that increases electron or hole injection by an electrospinning method between the first electrode and the electrochromic layer. Manufacturing method of electrochromic display element.   The electrochromic display element manufactured by the method as described in any one of Claims 1-3.

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