JP2016156930A - Electrochromic display element, display device, information appliance, manufacturing method for electrochromic display element, and electrochromic light control lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrochromic display element with the excellent transparency, capable of emitting light with clear color.SOLUTION: The electrochromic display device comprises: a display substrate 21, display electrodes (22, 25, 28), electrochromic layers (23, 26, 29) provided in contact with the display electrodes, a counter substrate 35 provided opposite to the display substrate, a counter electrode 33, a charge holding layer 32 provided in contact with the counter electrode, and an electrolyte layer 30 provided between the display substrate and the counter substrate. The electrochromic layer includes at least a particle including an insulating material, titanium oxide, and an electrochromic compound. The electrochromic layer includes at least a particle including an insulating material, and an electrochromic compound. The particle including the insulating material has its surface coated with titanium oxide.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an electrochromic display element, a display device, an information device, a method for manufacturing an electrochromic display element, and an electrochromic light control lens.

  In recent years, so-called electronic paper has been actively developed as an information medium replacing paper. As a display element used for electronic paper, a display element using a reflective liquid crystal, a display element using electrophoresis, a display element using toner migration, a display element using an electrochromic compound (electrochromic display element), Etc.

  The electrochromic display element is a promising candidate for the next generation display element because of its memory effect and being able to be driven at a low voltage. Currently, from electrochromic display element to material design to device design. A wide range of research and development is underway.

  The electrochromism phenomenon is a reversible phenomenon in which, when a voltage is applied to an electrochromic compound, the compound causes a redox reaction to develop or decolor. The electrochromic display element can develop various kinds of colors by changing the structure of the compound and utilizing the electrochromism phenomenon.

For this reason, the electrochromic display element is also expected as a display element capable of multicolor display. For example, the following Patent Documents 1 to 4 are disclosed.
Patent Document 1 discloses an electrochromic element having an organic electrochromic layer in which a plurality of polymer fine particle layers are laminated.
Patent Document 2 discloses a multicolor display element having a display layer formed by laminating or mixing a plurality of electrochromic compositions that develop different colors.
Patent Document 3 discloses an electrochromic display device in which a plurality of electrochromic layers are provided corresponding to a plurality of display electrodes.
Patent Document 4 discloses that a thin film transistor (TFT) is used as a drive element to realize practical electronic paper using an electrochromic display element, and a pixel electrode (counter electrode) on which a plurality of TFTs are separately formed is provided. It is disclosed that the charge retention layer (high resistance layer) is formed as a continuous layer (solid film). Thus, an electrochromic display device having excellent display quality and excellent durability without color bleeding, image blur, and the like is disclosed.

  In addition to the above-mentioned electronic paper, electrochromic display elements are also being considered for application to light control elements such as light control lenses, light control windows, and antiglare mirrors. For example, Patent Document 5 proposes an electrochromic dimming lens that is thin and lightweight, has a thin film dimming function formed on a single lens, and is low in cost and excellent in productivity.

  By the way, in a transmissive light control element such as a light control lens, high transparency as an element is an indispensable and important element for obtaining high display quality. In addition, in a reflective display element such as electronic paper, it is important for obtaining high display quality as an element that the constituent elements excluding the reflective layer have high transparency. And as a component which influences the transparency of this electrochromic display element, the support | carrier particle | grains of an electrochromic compound are mentioned.

  Conventionally, in an electrochromic display element, titanium oxide has been preferably used as the support particles for the electrochromic compound. The reason is that the electrochromic compound is easily adsorbed and supported by the chemical structure, that is, a structure having an OH group, and the electrochromic compound is extinguished while being interposed between the device electrode and the electrochromic compound. It has sufficient electroconductivity which enables transfer of the electric charge required for a color.

  However, although it is titanium oxide suitably used as electrochromic compound support particles, it has a problem that it is difficult to ensure sufficient transparency as a support particle film. In order to suppress light scattering and ensure transparency, a film is usually formed using particles having a small particle size (100 nm or less), but it is still difficult to obtain good transparency in the case of titanium oxide. This is because the rate is relatively large.

In contrast, examples of the material having a relatively small refractive index include alumina (Al ₂ O ₃ ) and silica (SiO ₂ ), and the supported particle film formed using these materials exhibits good transparency. Since this material is insulative, it cannot induce good color-decoloration of the electrochromic compound.
From the above, an electrochromic display element having excellent transparency and good display quality has been desired.

  In view of the above problems, an object of the present invention is to provide an electrochromic display element that is excellent in transparency and that can provide a vivid color.

  In order to solve the above-described problems, an electrochromic device of the present invention includes a display substrate, a display electrode, an electrochromic layer provided so as to be in contact with the display electrode, and a facing provided facing the display substrate. A substrate, a counter electrode, a charge retention layer provided in contact with the counter electrode, and an electrolyte layer provided between the display substrate and the counter substrate, wherein the electrochromic layer is The particles made of an insulating material and at least an electrochromic compound are characterized in that the particles made of the insulating material are covered with titanium oxide.

  ADVANTAGE OF THE INVENTION According to this invention, it is excellent in transparency and can provide the electrochromic display element from which a vivid color development is obtained.

It is a schematic diagram which shows an example of the structure of the electrochromic display element which concerns on this invention. It is a schematic diagram for demonstrating the structure of the electrochromic layer in FIG. It is a schematic diagram which shows the other example of the structure of the electrochromic display element which concerns on this invention. It is a figure explaining an example of the manufacturing method of the electrochromic display element concerning the present invention. It is a figure which shows schematic structure of an example of the information equipment which concerns on this invention. It is a schematic diagram which shows an example of the electrochromic light control lens which concerns on this invention. It is a schematic diagram which shows an example of the structure of the spectacles using the electrochromic light control lens which concerns on this invention.

  Hereinafter, an electrochromic display element, a display device, an information device, a method for manufacturing an electrochromic display element, and an electrochromic light control lens according to the present invention will be described with reference to the drawings. The present invention is not limited to the embodiments described below, and other embodiments, additions, modifications, deletions, and the like can be changed within a range that can be conceived by those skilled in the art, and any aspect is possible. As long as the functions and effects of the present invention are exhibited, the scope of the present invention is included.

  The electrochromic display element of the present invention includes a display substrate, a display electrode, an electrochromic layer provided so as to be in contact with the display electrode, a counter substrate provided to face the display substrate, a counter electrode, A charge retention layer provided in contact with the counter electrode; and an electrolyte layer provided between the display substrate and the counter substrate. The electrochromic layer includes particles made of an insulating material; The particles comprising at least the electrochromic compound and made of the insulating material have a surface coated with titanium oxide.

  According to this embodiment, it is possible to provide an electrochromic display element that is excellent in transparency and that can provide a vivid color. Further, in the present embodiment, a transmissive display and a reflective display can be provided. In the transmissive display, display characteristics with excellent transparency can be obtained, and in the reflective display, a bright and clear display characteristic can be obtained. A chromic display element can be provided.

[First Embodiment]
The electrochromic display element according to this embodiment will be described. In the present embodiment, description will be given below with reference to FIGS. In FIG. 1, a number of display electrodes and electrochromic layers are shown as a prominent electrochromic display element. However, as will be described later, the present invention is not limited to this, and there may be one display electrode and one electrochromic layer. Good. Moreover, although the white reflective layer is illustrated in FIG. 1, even if it does not have a white reflective layer, it is included in the present invention.

(Structure of electrochromic display element)
FIG. 1 shows an example of the structure of the electrochromic display element 20 according to this embodiment.
The electrochromic display element 20 includes a display substrate 21, a first display electrode 22, a first electrochromic layer 23, a first insulating layer 24, a second display electrode 25, a second electrochromic layer 26, and a second electrochromic layer 26. Insulating layer 27, third display electrode 28, third electrochromic layer 29, electrolyte layer 30, white reflective layer 31, charge holding layer 32, counter electrode 33, drive element layer 34, counter substrate 35, wall member 36. including.

  As shown in FIG. 1, the electrochromic display element 20 has a white reflective layer and a plurality of electrochromic layers between two opposing substrates, and the space between the substrates is filled with an electrolyte layer 30. Yes. Although not clearly shown in FIG. 1, the particles of the electrochromic compound contained in the electrochromic layer have a structure in which the surface of particles made of an insulating material is coated with titanium oxide.

  As a detailed structure on the display substrate 21 side, a first display electrode 22 is provided in contact with the display substrate 21. Further, a first electrochromic layer 23 is provided in contact with the first display electrode 22. Further, a first insulating layer 24 is provided between the first electrochromic layer 23 and the second display electrode 25. Further, a second electrochromic layer 26 is provided in contact with the second display electrode 25. Further, a second insulating layer 27 is provided between the second electrochromic layer 26 and the third display electrode 28. Further, a third electrochromic layer 29 is provided in contact with the third display electrode 28.

  On the other hand, as a detailed structure on the counter substrate 35 side, a drive element layer 34 is provided in contact with the counter substrate 35. Further, a counter electrode 33 is provided in contact with the drive element layer 34. The counter electrode 33 is provided corresponding to each drive element included in the drive element layer 34. Further, a charge retention layer 32 is provided in contact with the counter electrode 33.

The white reflective layer 31 may be formed in contact with the third electrochromic layer 29 or may be formed in contact with the charge retention layer 32. In the case of a transmissive display element, it is not necessary to provide a white reflective layer. In the present invention, a case having a white reflective layer is sometimes referred to as a reflective display element, and a case having the white reflective layer is sometimes referred to as a transmissive display element.
Details of each layer will be described below.

<Display board>
The display substrate 21 includes a first display electrode 22, a first electrochromic layer 23, a first insulating layer 24, a second display electrode 25, a second electrochromic layer 26, a second insulating layer 27, 3 is a substrate for supporting a laminated structure such as the third display electrode 28 and the third electrochromic layer 29.

  The material of the display substrate 21 is preferably a light transmissive material. For example, glass, a plastic film, etc. are mentioned.

<Display electrode>
The first display electrode 22 causes the first electrochromic layer 23 to be colored or decolored by a voltage generated between the electrode and the counter electrode 33. The second display electrode 25 causes the second electrochromic layer 26 to be colored or decolored by a voltage generated between the electrode and the counter electrode 33. The third display electrode 28 develops or decolors the third electrochromic layer 29 by a voltage generated between the electrode and the counter electrode 33. Since the color development in each electrochromic layer is determined by the magnitude of these voltages generated between the counter electrode 33 and each display electrode, the color tone of each electrochromic layer changes depending on the voltage.

The material of the first display electrode 22, the second display electrode 25, and the third display electrode is preferably a light-transmitting conductive material. Examples thereof include inorganic materials such as indium oxide doped with tin (hereinafter referred to as ITO), tin oxide doped with fluorine (hereinafter referred to as FTO), and tin oxide doped with antimony (hereinafter referred to as ATO). In addition, it is particularly preferable to use InSnO, GaZnO, SnO, In ₂ O ₃ , ZnO, or the like.

<Electrochromic layer>
Next, FIG. 2 shows a schematic diagram for explaining the electrochromic layer, which will be described below.
The first electrochromic layer 23 includes particles 23b of an insulating material having a structure supporting the electrochromic compound 23a and the electrochromic compound 23a and having a surface covered with titanium oxide 23c. As shown in FIG. 2, an insulating material having a structure in which the surface is coated with titanium oxide 23c by adsorbing a single molecule of the electrochromic compound 23a to particles 23b of the insulating material having a structure coated with titanium oxide 23c. Electrons can be efficiently injected into the electrochromic compound 23a using the large surface area of the particles 23b. Therefore, the color density of the electrochromic compound 23a during color development can be increased, and the switching speed between color development and decoloration can be increased.

The electrochromic compound 23a generates an oxidation-reduction reaction by a voltage generated between the first display electrode 22 and the counter electrode 33, and develops or decolors (reversible reaction). The length of the single molecule of the electrochromic compound 23a is preferably 5 nm or less.
The insulating material particles 23b having a structure in which the surface is coated with titanium oxide 23c carry an electrochromic compound 23a.

  The average primary particle size (hereinafter referred to as “average primary particle size” in the case of “particle size”) of the insulating material particles 23b having a structure in which the surface is coated with titanium oxide 23c is 5 to 100 nm. Is preferable, and it is more preferable that it is 10 nm-50 nm. By setting the particle size to 5 nm to 100 nm, the first electrochromic layer 23 can be a transparent layer. Thereby, in the reflective display element, a high white reflectance can be obtained when no color is generated. In the transmissive display element, a vivid color is obtained at the time of color development, and a colorless and transparent state is obtained at the time of decoloration.

The titanium oxide 23c is formed so as to cover the surfaces of the particles 23b of the insulating material, thereby imparting good conductivity as a supported particle film.
Further, as the particle size of the titanium oxide 23c covering the surface of the particles 23b of the insulating material,
It is preferably 1 nm to 10 nm.
As a method of coating the surface of the insulating material particles with titanium oxide, a dispersion containing the insulating material particles, titanium oxide, and titanium oxide precursor is prepared, applied on a substrate, dried by heating, and further heated. The particle film (porous film) of particles having a structure in which the particle surface of the insulating material is coated with titanium oxide can be obtained by performing UV / ozone treatment or microwave treatment.

  The method for evaluating whether the surface of the particles 23b of the insulating material is coated with the titanium oxide 23c is not particularly limited. For example, the cross section (slice) of the electrochromic layer is observed with an SEM (scanning electron microscope) or TEM (transmission electron microscope), and the state of the surface of the insulating material particles 23b covered with titanium oxide 23c is observed. Then, the covering structure is confirmed.

The coating thickness of titanium oxide is preferably 1 to 10 nm. If the coating thickness is too thin, the conductivity as the supported particle film is insufficient, and the electrochromic compound is insufficiently developed and decolored. If the coating thickness is too thick, the transparency of the supported particle film is impaired.
The mixing ratio of the insulating material particles and titanium oxide when preparing the dispersion can be adjusted so that the coating thickness of titanium oxide is 1 to 10 nm, for example. Although it varies depending on the particle sizes of both the particles of the insulating material and the titanium oxide, the mixing ratio of titanium oxide is preferably 0.1 to 0.5 parts by weight with respect to 1 part by weight of the particles of the insulating material. In other words, the mixing ratio of titanium oxide is preferably 10 to 50 parts by weight with respect to 100 parts by weight of the insulating material particles.

The insulating material is not particularly limited, but is preferably alumina or silica.
As described above, since the coating thickness of the titanium oxide 23c is thin and its optical contribution is small, it cannot be a factor that impairs transparency. Transparency depends largely on the refractive index and particle size of the insulating material particles 23b. The closer the refractive index is to 1, the more advantageous in terms of transparency. Titanium oxide: 2.52 (anatase), 2.71 (rutile), alumina: 1.76 and silica: 1.45 are more transparent It is very advantageous in terms of sex. The particle diameter is preferably 5 nm to 100 nm as described above.

  In addition, when titanium oxide is used as the support particles as in the past, photodegradation caused by the photocatalytic activity of titanium oxide is inevitable, but the degree of photodegradation can be greatly reduced by using alumina or silica. In addition, by using particles made of an insulating material having a relatively low refractive index, it is possible to provide good electrochromic compound color development and to provide an electrochromic display element with excellent transparency and high display quality. it can.

  In FIG. 1, supported particles, that is, particles 23b of an insulating material whose surface is covered with titanium oxide 23c, have a structure in which one type of electrochromic compound 23a is supported. It is also possible to carry a chromic compound.

  Similarly to the first electrochromic layer 23, the second electrochromic layer 26 and the third electrochromic layer 29 are also formed so that the titanium oxide 23c covers the surfaces of the particles 23b of the insulating material. As a result, good conductivity as a supported particle film is imparted, and good transparency can be secured.

  Although FIG. 2 shows a structure in which a single molecule of the electrochromic compound 23a is adsorbed on the support particles as an ideal state, the structure is not limited thereto. Any structure may be used as long as the electrochromic compound 23a is fixed at a high density so as not to move. In addition, as long as the electrical connection between the first electrochromic layer 23 and the first display electrode 22 is ensured so as not to hinder the transfer of electrons accompanying the redox reaction of the electrochromic compound 23a. good. The electrochromic compound 23a and the support particles (23b, 23c) may be mixed to form a single layer. The same applies to the second electrochromic layer 26 and the third electrochromic layer 29.

  As a material for the electrochromic compound, either an inorganic electrochromic compound or an organic electrochromic compound may be used. Moreover, well-known electrochromic compound materials, such as a pigment system, a polymer system, a metal complex system, and a metal oxide system, can be used.

  For example, as dye-based and polymer-based electrochromic compounds, azobenzene, anthraquinone, diarylethene, dihydroprene, dipyridine, styryl, styryl spiropyran, spirooxazine, spirothiopyran, thioindigo, tetrathiafulvalene , Terephthalic acid, triphenylmethane, triphenylamine, naphthopyran, viologen, pyrazoline, phenazine, phenylenediamine, phenoxazine, phenothiazine, phthalocyanine, fluoran, fulgide, benzopyran, Examples thereof include low molecular organic electrochromic compounds such as metallocenes, and conductive polymer compounds such as polyaniline and polythiophene.

  Further, these materials include viologen compounds (see, for example, Japanese Patent No. 39555641, Japanese Patent Application Laid-Open No. 2007-171781) or dipyridine compounds (see, for example, Japanese Patent Application Laid-Open No. 2007-171781, Japanese Patent Application Laid-Open No. 2008-116718). ) Is preferably included. By including a viologen-based compound or a dipyridine-based compound, even when the voltage applied to the display electrode and the counter electrode is low, the electrochromic compound can exhibit a good color value at the time of coloring and decoloring. For example, it is preferable to include a dipyridine compound represented by the following general formula (1).

In the general formula (1), R 1 and R 2 each independently represent a C 1-8 alkyl group or aryl group which may have a substituent, and at least one of R 1 or R 2 is COOH, It has a substituent selected from PO (OH) ₂ and Si (OC _k H _{2k + 1} ) ₃ . X represents a monovalent anion. n, m, and l represent 0, 1, or 2. A, B and C each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group or a heterocyclic group which may have a substituent.

Examples of the metal oxide electrochromic compound include tungsten oxide, molybdenum oxide, iridium oxide, indium oxide, titanium oxide, nickel oxide, vanadium oxide, and Prussian blue.
The materials used for the electrochromic compound in each electrochromic layer in the electrochromic display element 20 are preferably unified so that they are all oxidation coloring materials or all reduction coloring materials. .

<Insulating layer>
The first insulating layer 24 includes a first display electrode 22 provided with the first electrochromic layer 23 and a second display electrode 25 provided with the second electrochromic layer 26 electrically. Isolate them so that they are insulated.
The second insulating layer 27 is electrically connected between the second display electrode 25 provided with the second electrochromic layer 26 and the third display electrode 28 provided with the third electrochromic layer 29. Isolate them so that they are insulated.

  Note that the first insulating layer 24 is not necessarily provided as long as the interelectrode resistance between the first display electrode 22 and the second display electrode 25 can be increased. For example, the interelectrode resistance between the first display electrode 22 and the second display electrode 25 can be increased by increasing the film thickness of the first electrochromic layer 23. Similarly, if the interelectrode resistance between the second display electrode 25 and the third display electrode 28 can be increased, the second insulating layer 27 may not be provided.

By providing these insulating layers, color development and decoloration in each electrochromic layer can be individually controlled, so that high-definition full-color display is possible.
The material of the insulating layer is not particularly limited as long as it is a porous insulator, but a material having high insulation and durability and excellent film formability is preferable. A material containing at least ZnS is preferable. This is because ZnS can be deposited at high speed by sputtering and can reduce damage to the electrochromic layer during deposition. For example, ZnS—SiO ₂ , ZnS—SiC, ZnS—Si, ZnS—Ge, or the like is preferably used.

  The film thickness of the electrochromic layer is not particularly limited and can be appropriately changed. For example, the thickness is preferably 500 nm to 3 μm.

<Counter substrate>
The counter substrate 35 is a substrate for supporting a laminated structure of the drive element layer 34, the counter electrode 33, the charge holding layer 32, and the like.
The material of the counter substrate 35 is preferably a light transmissive material. For example, glass, a plastic film, etc. are mentioned.

<Counter electrode>
The counter electrode 33 develops or decolors the first electrochromic layer 23, the second electrochromic layer 26, and the third electrochromic layer 29 based on the voltage generated between the display electrodes.
The material of the counter electrode 33 is not particularly limited as long as it is a conductive material. For example, ITO, FTO, zinc oxide, etc. are mentioned as a light-transmitting conductive material. Moreover, zinc, platinum, etc. are mentioned as an electroconductive metal material. Carbon or the like may be used.

<Drive element>
In the present embodiment, the drive element layer 34 can be provided as necessary. The drive element layer 34 includes a plurality of drive elements, and drives the drive elements according to the selected pixel. Note that the pixel density is proportional to the number of driving elements.

<Charge retention layer>
The charge retention layer 32 relaxes the transfer of charges generated by the voltage applied between each display electrode and the counter electrode 33. By providing the charge retention layer 32, it is possible to improve the repeated durability of coloring and decoloring in each electrochromic layer. By increasing the durability repeatedly, high-definition display is possible in a display device using an electrochromic display element.

As a material of the charge retention layer 32, a mixed material of a conductive fine particle material or a semiconductor fine particle material (fine particle material) and a polymer material can be used.
The polymer material is not particularly limited, and examples thereof include acrylic, alkyd, fluorine, isocyanate, urethane, amino, epoxy, and phenol.
Examples of the conductive fine particles include ITO, FTO, and ATO.
Examples of the semiconductor fine particles include oxides such as titanium, zirconium, hafnium, chromium, molybdenum, tungsten, vanadium, niobium, tantalum, silver, zinc, strontium, iron, and nickel.

  In addition, when all the materials used for the electrochromic compound in each electrochromic layer are oxidation coloring materials, it is particularly preferable to use ATO as the fine particle material mixed with the polymer material. In addition, when all the materials used for the electrochromic compound in each electrochromic layer are reduction coloring materials, it is particularly preferable to use tungsten oxide as the fine particle material mixed with the polymer material. By using ATO in the case of an oxidative coloring material and using tungsten oxide in the case of a reducing chromogenic material, the driving voltage of the electrochromic display element can be lowered, and the repeated durability can be improved.

<Wall member>
The wall member 36 surrounds each display electrode, each electrochromic layer, and the white reflective layer 31. As the material of the wall member 36, ultraviolet curable resin materials such as acrylate type (radical polymerization type) and epoxy type (cationic polymerization type), and thermosetting resin materials such as epoxy type, phenol type, and melamine type can be used.

<White reflective layer>
The white reflective layer 31 is for improving the white reflectance in the electrochromic display element 20. The white reflective layer 31 includes titanium oxide particles and a metal hydroxide dispersed inside and on the surface of the titanium oxide particles.
The particle size of the titanium oxide particles is preferably 200 nm to 3 μm, and more preferably 250 nm to 2 μm.

<Electrolyte layer>
The electrolyte layer 30 fills a space generated between the counter substrate 35 and the display substrate 21 surrounded by the wall member 36. The electrolyte layer 30 fills the space so that each electrochromic layer is included in the electrolyte layer 30. The electrolyte layer 30 moves electric charge between the first display electrode 22, the second display electrode 25, or the third display electrode 28 and the counter electrode 33, and the first electrochromic layer 23, The electrochromic layer 26 and the third electrochromic layer 29 are promoted to be colored or decolored.

As a material for the electrolyte layer 30, inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, acids, and supporting salts of alkalis can be used.
For example, LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ COO, KCl, NaCl, NaBF ₄ , NaSCN, KBF ₄ , Mg (ClO ₄ ) ₂ , Mg (BF ₄ ) _2, etc. Can be mentioned.

  Moreover, an ionic liquid can also be used as a material of the electrolyte layer 30. Since organic ionic liquid has a molecular structure showing a liquid in a wide temperature range including room temperature, it is preferable to use this.

  For example, cation components include imidazole derivatives such as N, N-dimethylimidazole salt, N, N-methylethylimidazole salt, and N, N-methylpropylimidazole salt. Further, pyridinium derivatives such as N, N-dimethylpyridinium salt, N, N-methylpropylpyridinium salt, and the like can be given. In addition, aliphatic quaternary ammonium compounds such as trimethylpropylammonium salt, trimethylhexylammonium salt, and triethylhexylammonium salt can be used.

For example, it is preferable to use a compound containing fluorine as the anion component in consideration of stability in the air. For example, BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , PF 4 ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , and the like can be given.

  That is, as the material of the electrolyte layer 30, it is preferable to use an ionic liquid in which a cation component and an anion component are arbitrarily combined. The ionic liquid may be directly dissolved in any of photopolymerizable monomers, oligomers, and liquid crystal materials. If the solubility is poor, a small amount of solvent (for example, propylene carbonate, acetonitrile, γ-butyrolactone, ethylene carbonate, sulfolane, dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,2-dimethoxyethane, 1, 2-ethoxymethoxyethane, polyethylene glycol, alcohols, etc.) and the solution may be mixed with any of photopolymerizable monomers, oligomers, and liquid crystal materials.

<Protective layer>
Further, if necessary, a protective layer may be provided so as to be in contact with the surface of each of the first electrochromic layer 23 and the second electrochromic layer 26 opposite to the display substrate 21. By providing the protective layer, adhesion to a layer adjacent to the first electrochromic layer 23 or the second electrochromic layer 26 (for example, the first insulating layer 24, the second insulating layer 27, etc.), a solvent As a result, it is possible to improve the durability of the electrochromic display element 20.

As a material for the protective layer, an organic polymer material is preferably used. For example, general resins such as polyvinyl alcohol, poly-N-vinylamide, polyester, polystyrene, and polypropylene can be used.
An inorganic protective layer may be provided between the third electrochromic layer 29 and the electrolyte layer 30. By providing the inorganic protective layer, it is possible to improve the dissolution resistance, corrosion resistance, and the like of the third electrochromic layer 29 with respect to the electrolyte layer 30 and improve the durability of the electrochromic display element 20.

(Multicolor display of electrochromic display elements)
Next, multicolor display of the electrochromic display element will be described.
The electrochromic display element 20 shown in FIG. 1 can easily perform multicolor display by having the above-described structure.
In the electrochromic display element 20, for example, the first electrochromic layer 23 develops cyan, the second electrochromic layer 26 develops magenta, and the third electrochromic layer 29 is yellow. To develop color.

Since the first display electrode 22 and the second display electrode 25 are provided separately via the first insulating layer 24, the electrochromic display element 20 includes the counter electrode 33 and the first display electrode. The voltage generated between the counter electrode 33 and the second display electrode 25 can be controlled independently.
In addition, since the second display electrode 25 and the third display electrode 28 are provided separately from each other with the second insulating layer 27 interposed therebetween, the electrochromic display element 20 includes the counter electrode 33 and the second display electrode 20. The voltage generated between the display electrode 25 and the voltage generated between the counter electrode 33 and the third display electrode 28 can be controlled independently.

  That is, the electrochromic display element 20 includes a first electrochromic layer 23 provided in contact with the first display electrode 22 and a second electrochromic layer 26 provided in contact with the second display electrode 25. The third electrochromic layer 29 provided in contact with the third display electrode 28 can be colored or decolored independently.

  As a result, the electrochromic display element 20 can arbitrarily color or decolor each electrochromic layer based on the voltage applied to the counter electrode and each display electrode. For example, a multi-step color pattern such as color development of only the first electrochromic layer 23, color development of only the second electrochromic layer 26, color development of only the first electrochromic layer 23 and the third electrochromic layer 29, etc. Any color can be developed. Further, a desired multicolor display can be performed by appropriately adjusting the color, color density, brightness, and the like of each electrochromic layer based on the voltage applied to the counter electrode and each display electrode.

  In the electrochromic display element 20, the color developed by the first electrochromic layer 23 is not limited to cyan, and the color developed by the second electrochromic layer 26 is not limited to magenta. The color that the electrochromic layer 29 develops is not limited to yellow.

(Method for manufacturing electrochromic display element)
Next, the manufacturing method of the electrochromic display element of this invention is demonstrated.
The method for producing an electrochromic display element of the present invention includes a step of forming a display electrode on a display substrate, a step of forming an electrochromic layer on the display electrode, a step of forming a counter electrode on the counter substrate, The method includes a step of forming a charge retention layer on the counter electrode and a step of bonding the display substrate and the counter substrate through an electrolyte layer.

  The method of manufacturing an electrochromic display element of the present invention includes a step of forming a display electrode on a display substrate, a step of forming an electrochromic layer on the display electrode, and a white reflective layer on the electrochromic layer. A step of forming, a step of forming a drive element layer on the counter substrate, a step of forming a counter electrode on the drive element layer, a step of forming a charge retention layer on the counter electrode, and the display A step of bonding the electric substrate and the counter substrate through an electrolyte layer.

The method for manufacturing an electrochromic display element of the present invention is not limited to a case where there is one electrochromic layer, but can be applied to a case where there are a plurality of electrochromic layers.
In the present embodiment, an example of a method for manufacturing the electrochromic display element 20 will be described with reference to FIG. 4 in the case where there are a plurality of electrochromic layers.

The method for manufacturing the electrochromic display element 20 is shown in steps S11 to S23 in FIG. The outline of step S11 to step S23 is as follows.
Step S11: First display electrode forming step for forming the first display electrode 22 on the display substrate 21 Step S12: First electrochromic layer formation for forming the first electrochromic layer 23 thereon Step S13: First insulating layer forming step for forming the first insulating layer 24 thereon Step S14: Second display electrode forming step for forming the second display electrode 25 thereon Step S15 : Second electrochromic layer forming step for forming the second electrochromic layer 26 thereon Step S16: second insulating layer forming step for forming the second insulating layer 27 thereon Step S17: the step Third display electrode forming step for forming the third display electrode 28 on top thereof. Step S18: Third for forming the third electrochromic layer 29 thereon Step S19: White reflective layer forming step for forming the white reflective layer 31 thereon Step S20: Drive element layer forming step for forming the drive element layer 34 on the counter substrate 35 Step S21: Step S22: a charge holding layer forming step for forming the charge holding layer 32 thereon Step S23: a bonding step for bonding the display substrate 21 and the counter substrate 35 to each other

  Next, an example of the manufacturing method of the electrochromic display element shown in FIG. 4 will be described below. In addition, the numerical value described below is a specific example, and is not limited to this.

<First display electrode forming step>
First, the first display electrode forming step shown in step S11 of FIG. 4 is performed.
An ITO film having a film thickness of about 100 nm and a surface resistance of about 200Ω / □ is formed on the display substrate 21 (for example, a glass substrate having a length of 40 mm and a width of 40 mm) by a sputtering method, and the first display electrode 22 is formed.
The film forming method is not limited to the sputtering method, and other vacuum film forming methods such as an ion plating method can be applied.

<First electrochromic layer forming step>
Next, the first electrochromic layer forming step shown in step S12 of FIG. 4 is performed.
First, a dispersion of supported particles, that is, insulating particles having a structure in which the surface is coated with titanium oxide (in the present invention, insulating particles having a structure in which the surface is coated with titanium oxide may be simply referred to as “supported particles”), Application is performed on the first display electrode 22 by spin coating. Thereafter, annealing is performed at 120 ° C. for 15 minutes so that the first display electrode 22 and the supported particles and the supported particles are partially joined. This forms a supported particle film.

  Then, 2,2,3,3-tetra, containing 1 wt% of electrochromic compound 4,4 ′-(isooxazole-3,5-diyl) bis (1- (2-phosphonoethyl) pyridinium) bromide on the supported particle film. A fluoropropanol (hereinafter referred to as “TFP”) solution is applied by spin coating and annealed at 120 ° C. for 10 minutes. Thus, the first electrochromic layer 23 composed of the titanium oxide particle film and the electrochromic compound is formed.

  Then, a protective layer is formed on the first electrochromic layer 23 by applying an ethanol solution containing 0.1 wt% poly-N-vinylamide and an aqueous solution containing 0.5 wt% polyvinyl alcohol by spin coating. To do.

<First insulating layer forming step>
Next, the first insulating layer forming step shown in step S13 of FIG. 4 is performed.
A ZnS—SiO ₂ film having a thickness of about 140 nm is formed on the protective layer by sputtering, and the first insulating layer 24 is formed. The composition ratio of ZnS and SiO ₂ is 8: 2.
As a film formation method, a vacuum film formation method such as an evaporation method, a sputtering method, or an ion plating method can be applied.

<Second display electrode forming step>
Next, a second display electrode forming step shown in step S14 of FIG. 4 is performed.
An ITO film having a thickness of about 100 nm and a surface resistance of about 200 Ω / □ is formed on the first insulating layer 24 by sputtering to form a second display electrode 25.

<Second Electrochromic Layer Formation Step>
Next, the second electrochromic layer forming step shown in step S15 of FIG. 4 is performed.
First, a dispersion of supported particles is applied onto the second display electrode 25 by spin coating. Thereafter, an annealing process is performed at 120 ° C. for 15 minutes so that the second display electrode 25, the supported particles, and the supported particles are partially bonded to each other. This forms a supported particle film.
Thereafter, TFP containing 1 wt% of electrochromic compound 4,4 ′-(1-phenyl-1H-pyrrole-2,5-diyl) bis (1- (4-phosphonomethyl) benzyl) pyridinium) bromide on the supported particle film. The solution is applied by spin coating and annealed at 120 ° C. for 10 minutes. Thus, the second electrochromic layer 26 made of the supported particle film and the electrochromic compound is formed.

  Thereafter, a protective layer is formed on the second electrochromic layer 26 by applying an ethanol solution containing 0.1 wt% poly-N-vinylamide and an aqueous solution containing 0.5 wt% polyvinyl alcohol by spin coating. To do.

<Second insulating layer forming step>
Next, a second insulating layer forming step shown in step S16 of FIG. 4 is performed.
A ZnS—SiO ₂ film having a thickness of about 140 nm is formed on the protective layer by sputtering, and the second insulating layer 27 is formed. The composition ratio of ZnS and SiO ₂ is 8: 2.
As a film formation method, a vacuum film formation method such as an evaporation method, a sputtering method, or an ion plating method can be applied.

<Third display electrode forming step>
Next, a third display electrode forming step shown in step S17 of FIG. 4 is performed.
An ITO film having a thickness of about 100 nm and a surface resistance of about 200 Ω / □ is formed on the second insulating layer 27 by sputtering to form the third display electrode 28.

<Third electrochromic layer forming step>
Next, a third electrochromic layer forming step shown in step S18 of FIG. 4 is performed.
First, a dispersion of supported particles is applied onto the third display electrode 28 by spin coating. Thereafter, an annealing process is performed at 120 ° C. for 15 minutes so that the third display electrode 28, the supported particles, and the supported particles are partially bonded. This forms a supported particle film.

  Thereafter, the electrochromic compound 4,4 ′-(4,4 ′-(1,3,4-oxadiazole-2,5-diyl) bis (4,1-phenylene)) bis (1- A TFP solution containing 1 wt% of (8-phosphonooctyl) pyridinium) bromide is applied by spin coating, and annealed at 120 ° C. for 10 minutes. Thus, the third electrochromic layer 29 made of the supported particle film and the electrochromic compound is formed.

<White reflective layer forming step>
Next, the white reflective layer forming step shown in step S19 of FIG. 4 is performed.
First, a TFP dispersion of titanium oxide particles and an aqueous polyurethane resin is applied onto the third electrochromic layer 29 by a spin coating method. Thereafter, annealing is performed at 120 ° C. for 10 minutes. As a result, the white reflective layer 31 made of titanium oxide particles in which metal hydroxide is dispersed inside and on the surface is formed.

  Thereafter, the first display electrode 22, the second display electrode 25, the third display electrode 28, the first electrochromic layer 23, the second electrochromic layer 26, the third electrochromic layer 29, and a white reflective layer 31 is surrounded by a wall member 36 (see FIG. 1).

<Driving element layer forming step>
Next, the driving element layer forming step shown in step S20 of FIG. 4 is performed.
A driving element layer 34 having a plurality of driving elements is formed on a counter substrate 35 (for example, a glass substrate 40 mm long × 40 mm wide) so as to have a pixel density of 140 ppi (Pixels per inch) by a known process. .

<Counter electrode formation process>
Next, the counter electrode forming step shown in step S21 of FIG. 4 is performed.
An ITO film having a thickness of about 100 nm is formed on the counter substrate 35 by sputtering. Thereafter, a plurality of counter electrodes 33 are formed by photolithography so as to correspond to the plurality of driving elements included in the driving element layer 34.

<Charge retention layer forming step>
Next, the charge retention layer forming step shown in step S22 of FIG. 4 is performed.
The charge retention layer 32 is formed by mixing a polymer material and a fine particle material and dispersing them in a dispersion medium, and applying the mixed material onto the drive element layer 34 and the counter electrode 33 by a spin coating method.

  Specifically, a TFP dispersion of an aqueous polyurethane resin and ATO particles is applied on the drive element layer 34 and the counter electrode 33 by a spin coating method. Thereafter, the charge retention layer 32 having a film thickness of about 640 nm and a surface resistance of about 1.0E + 06Ω / □ is formed by performing an annealing process at 120 ° C. for 15 minutes.

The weight ratio of the aqueous polyurethane resin and ATO can be set to 55%: 45%, for example.
As a coating method, other printing methods such as a spin coating method and a blade coating method can be applied.

  The aqueous polyurethane resin and the TFP solution of ATO particles do not need to be selectively applied only on the counter electrode 33, and the counter electrode 33 formed corresponding to the plurality of drive elements included in the drive element layer 34 You may apply | coat between the counter electrodes 33. FIG. Since it is not necessary to selectively apply the solution, the manufacturing process is simplified and the manufacturing cost is reduced in the case where the charge holding layer 32 is formed compared to the case where the charge holding layer 32 is not formed. Can do.

<Lamination process>
Next, the bonding process shown by step S23 of FIG. 4 is performed.
The counter substrate 35 formed up to the charge retention layer 32 and the display substrate 21 formed up to the white reflective layer 31 are bonded with the electrolyte sandwiched so that the counter electrode and the display electrode face each other.
Specifically, in the display substrate 21 surrounded by the wall member 36, an electrolyte precursor material is injected from above the white reflective layer 31. The display substrate 21 and the counter substrate 35 are bonded together by sealing the injection port. Thereafter, ultraviolet light is irradiated for 2 minutes from the counter electrode 33 side by a high-pressure mercury lamp. Since the precursor material can be photopolymerized and phase-separated by irradiation with ultraviolet light, the electrolyte layer 30 can be formed between the two substrates. The ultraviolet light having a center wavelength of 365 nm and an intensity of 50 mW / cm ² can be used.

  The precursor material of the electrolyte layer 30 is adjusted before the electrochromic display element 20 is manufactured. In the bonding step in step S23, the precursor material of the electrolyte layer 30 adjusted in advance is used.

  As an example of a method for adjusting the precursor material of the electrolyte layer 30, first, a propylene carbonate solution of tetrabutylammonium perchlorate (TBAP) is used, and the molar concentration of TBAP is about 20 mol / Adjust so that l. Thereafter, a mixture of a liquid crystal composition for PNLC (Polymer Network Liquid Crystal), a monomer composition, and a polymerization initiator is mixed into the solution. Thereafter, the molar concentration of TBAP in the propylene carbonate solution is adjusted again to be about 0.04 mol / l. Thereafter, in order to regulate the film thickness of the electrolyte layer 30 to be manufactured, true spherical resin beads having a particle diameter of 10 μm are dispersed in the propylene carbonate solution at a concentration of 0.2 wt%. In this way, the precursor material of the electrolyte layer 30 can be obtained.

[Second Embodiment]
Next, other embodiments of the electrochromic display element according to the present invention will be described. In addition, the description about the same point as the said embodiment is abbreviate | omitted.
FIG. 3 shows an electrochromic display element according to this embodiment.
The above-described electrochromic display element 20 shown in FIG. 1 has three electrochromic layers including a first electrochromic layer 23, a second electrochromic layer 26, and a third electrochromic layer 29. The invention is not particularly limited. For the purpose of monochrome image display instead of full-color image display, for example, it may have only one electrochromic layer like the electrochromic display element 20A shown in FIG.

[Third Embodiment]
(Information equipment using electrochromic display elements)
In the present embodiment, a case where the electrochromic display element 20 according to the first embodiment is applied to an electronic book reader will be described. The present embodiment is not limited to an electronic book reader, and can be applied to any information device including a display device such as an electronic advertisement, a mobile personal computer, and a portable terminal.

FIG. 5 shows an example of a schematic structure of the electronic book reader 100.
The electronic book reader 100 includes a display device 101, a main controller 102, a ROM 103, a RAM 104, a flash memory 105, a character generator 106, and an interface 107. The display device 101 includes a display panel 111 with a touch panel, a touch panel driver 112, a display controller 113, and a VRAM 114.

In the structure shown in FIG. 5, the character generator 106 is provided outside the display device 101, but the character generator 106 may be provided inside the display device 101. The display panel 111 may not include a touch panel. If there is other input means, the display panel 111 may be provided with other input means. When the display panel 111 does not include a touch panel, the touch panel driver 112 is not necessary.
Note that the arrows shown in FIG. 5 represent the flow of typical signals and information, and do not represent all the connection relationships of the blocks.

  The display panel 111 with a touch panel individually drives the electrochromic display element 20 according to the first embodiment, the first electrochromic layer 23, the second electrochromic layer 26, and the third electrochromic layer 29. Includes a drive circuit. The drive circuit includes a drive element layer 34, and the drive element layer 34 has a plurality of drive elements corresponding to each counter electrode 33. The display panel 111 drives a drive element corresponding to the selected pixel based on the pixel selection signal output from the display controller 113, and applies a predetermined voltage to the selected pixel.

  The pixel selection signal is a signal that designates the vertical position and the horizontal position of the selected pixel. Further, based on the color designation signal output from the display controller 113, the display panel 111 applies a predetermined voltage to the corresponding display electrode according to the designated color. Based on signals such as a pixel selection signal and a color designation signal, the display panel 111 displays a moving image, a still image, or the like.

The display panel 111 outputs a signal based on the touch position to the touch panel driver 112 when the user touches the touch panel.
Since the display panel 111 includes the electrochromic display element 20 according to the first embodiment, high-definition full-color display (multicolor display) while maintaining high white reflectance and high contrast ratio. Can be realized. Actually, even after displaying and erasing a full-color image alternately 1000 times, no special change was observed in the image display state.
Further, the display panel 111 can switch between color development and color erasure at high speed. Actually, the time required from the start of driving to image acquisition and the time required to erase the acquired image were about 500 ms.

  The VRAM 114 stores display data for displaying a moving image or a still image on the display panel 111. The display data individually corresponds to a plurality of pixels included in the display panel 111. Therefore, the display data includes display color information corresponding to each pixel.

The display controller 113 reads display data stored in the VRAM 114 at every predetermined timing, and individually controls display colors of a plurality of pixels included in the display panel 111 according to the display data. The display controller 113 outputs to the display panel 111 a pixel selection signal for specifying a pixel to be colored and a color designation signal for specifying a color.
The touch panel driver 112 outputs position information corresponding to the position touched by the user on the display panel 111 to the main controller 102.

The main controller 102 comprehensively controls each unit such as the RAM 104, the flash memory 105, the character generator 106, the interface 107, and the VRAM 114 according to a program stored in the ROM 103.
For example, when the power is turned on by the user, the main controller 102 reads the initial menu screen data from the ROM 103, refers to the character generator 106, converts the initial menu screen data into dot data, and converts the dot data into , Transferred to the VRAM 114. As a result, the initial menu screen is displayed on the display panel 111. At this time, a list of contents stored in the flash memory 105 is displayed on the display panel 111. When one of the menus on the display panel 111 is selected by the user and the display portion is touched, the main controller 102 acquires the selection content of the user based on the position information from the touch panel driver 112.

  When the user designates the content and requests to view the content, the main controller 102 reads the electronic data of the content from the flash memory 105 and refers to the character generator 106 to convert the electronic data into dot data. The dot data is converted and transferred to the VRAM 114.

  In addition, the electronic book reader 100 may be connected to a public line. When the user requests to purchase content via the Internet, the main controller 102 connects to a predetermined purchase site via the interface 107. , Function as a normal browser. When the information from the purchase site is displayed on the display panel 111 and the user purchases the content, electronic data of the content is downloaded. The main controller 102 stores the electronic data of the content in the flash memory 105.

In addition, the ROM 103 stores various programs described in codes readable by the main controller 102 and various data necessary for executing the programs.
The RAM 104 is a working memory.
The flash memory 105 stores electronic data of books as contents.
The character generator 106 stores dot data corresponding to various character data.
The interface 107 controls connection with an external device. The interface 107 can connect a memory card, a personal computer, and a public line. The connection to the personal computer and the public line can be either wired or wireless.

  According to the electronic book reader 100 according to the present embodiment, since the electrochromic display element shown in the first embodiment is applied, it is excellent in transparency, and a vivid color can be obtained. Clear display characteristics can be obtained regardless of the type display.

[Fourth Embodiment]
(Structure of electrochromic light control lens)
The electrochromic light control lens according to the present embodiment has a lens and a thin film light control function unit laminated on the lens. The thin film dimming function unit includes: a first electrode layer stacked on the lens; a first electroactive layer stacked on the first electrode layer; and the first electroactive layer. A laminated insulating porous layer; a porous second electrode layer laminated on the insulating porous layer; and an upper side of the second electrode layer in contact with the second electrode layer; A second electroactive layer formed on one or both of the lower side, a space between the first electrode layer and the second electrode layer, and the first electroactive layer and And an electrolyte layer provided in contact with the second electroactive layer. One of the first electroactive layer and the second electroactive layer is an electrochromic layer, and the other is a deterioration preventing layer. The electrochromic layer includes at least particles made of an insulating material and an electrochromic compound, and the particles made of the insulating material are coated with titanium oxide on the surface.
According to the present embodiment, an electrochromic light control lens having display characteristics with excellent transparency can be provided.

  FIG. 6 is a cross-sectional view illustrating an electrochromic light control lens according to this embodiment. Referring to FIG. 6, the electrochromic light control lens 110 includes a lens 120 and a thin film light control function unit 130 stacked on the lens 120. The planar shape of the electrochromic light control lens 110 can be, for example, a round shape.

  The thin-film light control function unit 130 has a structure in which a first electrode layer 131, an electrochromic layer 132, an insulating porous layer 133, a second electrode layer 134, a deterioration preventing layer 135, and a protective layer 136 are sequentially stacked. It is a part which performs electrochromic layer 132 light emission / discoloration (light control). Note that the protective layer 136 may be formed on the upper surface (the surface opposite to the lens 120) of the deterioration preventing layer 135, and is not necessarily limited to the first electrode layer 131, the electrochromic layer 132, and the insulating porous layer. 133, the second electrode layer 134, and the deterioration prevention layer 135 may not be formed on the respective side surfaces.

In the electrochromic dimming lens 110, a first electrode layer 131 is provided on the lens 120, and an electrochromic layer 132 is provided in contact with the first electrode layer 131. Further, a second electrode layer 134 is provided on the electrochromic layer 132 so as to face the first electrode layer 131 with the insulating porous layer 133 interposed therebetween.
The insulating porous layer 133 is provided to insulate the first electrode layer 131 and the second electrode layer 134, and the insulating porous layer 133 contains insulating metal oxide fine particles. . The insulating porous layer 133 sandwiched between the first electrode layer 131 and the second electrode layer 134 is filled with an electrolyte (not shown).

  The second electrode layer 134 is a porous electrode layer in which a large number of through holes penetrating in the thickness direction are formed. A deterioration preventing layer 135 is provided outside the second electrode layer 134. The deterioration preventing layer 135 is also a porous material having a large number of through holes penetrating in the thickness direction, and is filled with an electrolyte (not shown).

  In the electrochromic dimming lens 110, by applying a voltage between the first electrode layer 131 and the second electrode layer 134, the electrochromic layer 132 undergoes an oxidation-reduction reaction due to the transfer of electric charges, and the color changes. .

  The manufacturing process of the electrochromic dimming lens 110 includes a process of sequentially laminating the first electrode layer 131 and the electrochromic layer 132 on the lens 120, and a first process through the insulating porous layer 133 on the electrochromic layer 132. A step of laminating a second electrode layer 134, which is a porous electrode layer having through holes formed so as to face the electrode layer 131, and a porous layer in which through holes are formed on the second electrode layer 134 The step of laminating the deterioration prevention layer 135 and the insulating porous layer 133 sandwiched between the first electrode layer 131 and the second electrode layer 134 via the deterioration prevention layer 135 and the second electrode layer 134. And a step of filling the electrolyte from the through holes formed in the deterioration preventing layer 135 and the second electrode layer 134 and a step of forming the protective layer 136 on the deterioration preventing layer 135.

  Here, the respective through holes formed in the deterioration preventing layer 135 and the second electrode layer 134 are injected when the insulating porous layer 133 or the like is filled with an electrolyte in the manufacturing process of the electrochromic light control lens 110. It is a hole.

  Thus, in the electrochromic light control lens 110 according to the present embodiment, the deterioration preventing layer 135 and the second layer are formed on the insulating porous layer 133 and the like sandwiched between the first electrode layer 131 and the second electrode layer 134. It is possible to fill the electrolyte from the through holes formed in the electrode layer 134. Therefore, it is possible to form the low-resistance second electrode layer 134 before filling the electrolyte, and the performance of the electrochromic light control lens 110 can be improved.

Moreover, since the deterioration preventing layer 135 is provided on the second electrode layer 134, an electrochromic light control lens that operates repeatedly and stably can be realized.
In the present embodiment, since a through-hole is formed in the second electrode layer 134, the second electrode layer 134 is in contact with the outside of the second electrode layer 134 (outside of the two opposing electrode layers). Thus, the deterioration preventing layer 135 can be formed. This is because ions can move between the front and back of the second electrode layer through the through-hole formed in the second electrode layer 134. As a result, since it is not necessary to form the deterioration preventing layer 135 below the second electrode layer 134, the deterioration preventing layer 135 is prevented from being damaged by sputtering or the like when forming the second electrode layer 134. it can.

  In addition, when the deterioration preventing layer 135 is formed, a process that can form either a homogeneous deterioration preventing layer 135 is formed on the permeable insulating porous layer 133 and the second electrode layer 134. You can choose as appropriate. Alternatively, the deterioration preventing layer 135 may be formed both above and below the second electrode layer 134 as necessary.

  In FIG. 6, the electrochromic layer 132 is formed in contact with the first electrode layer 131 and the deterioration preventing layer 135 is formed in contact with the second electrode layer 134. Have a reductive reaction, and when one carries out a reductive reaction, the other carries out an oxidation reaction. Therefore, the position to be formed may be reversed. That is, the deterioration preventing layer 135 may be in contact with the first electrode layer 131 and the electrochromic layer 132 may be formed in contact with the second electrode layer 134.

  Alternatively, the electrochromic layer 132 may be formed in contact with the first electrode layer 131, and the deterioration preventing layer may be formed on both the upper and lower sides of the second electrode layer 134 in contact with the second electrode layer 134. Good. Further, the deterioration preventing layer 135 is formed in contact with the first electrode layer 131, and the electrochromic layer 132 is formed in both the upper and lower sides of the second electrode layer 134 in contact with the second electrode layer 134. Also good.

  In the present invention, the deterioration preventing layer and the electrochromic layer may be referred to as an electroactive layer. That is, in the electrochromic light control lens 110 according to the present embodiment, the thin film light control function unit 130 includes the first electrode layer 131 stacked on the lens 120 and the first electrode layer 131 stacked on the first electrode layer 131. 1 electroactive layer, an insulating porous layer 133 laminated on the first electroactive layer, a porous second electrode layer 134 laminated on the insulating porous layer 133, A porous second electroactive layer formed on one or both of the upper side and the lower side of the second electrode layer 134 in contact with the second electrode layer 134, and the first electroactive layer One of the second electroactive layers is the electrochromic layer 132 and the other is the deterioration preventing layer 135.

In the electrochromic light control lens 110 according to the present embodiment, since the protective layer 136 is formed in the coating process after the electrolyte is injected, the thickness can be reduced with respect to the configuration in which the two lenses are bonded, and the weight is also reduced. The weight can be reduced and the cost can be reduced.
In addition, it is preferable that the thickness of the thin film light control function part 130 shall be 2 micrometers-200 micrometers. If the thickness of the thin-film light control function unit 130 is greater than 200 μm, cracks and peeling may occur during processing of the round lens, and the optical characteristics of the lens may be affected. Moreover, it is not preferable that the thickness of the thin-film light control function unit 130 is less than 2 μm because a sufficient light control function may not be obtained.

  FIG. 7 is a perspective view illustrating electrochromic light control glasses according to this embodiment. Referring to FIG. 7, the electrochromic dimming glasses 150 include an electrochromic dimming lens 151, a spectacle frame 152, a switch 153, and a power source 154. The electrochromic light control lens 151 is obtained by processing the electrochromic light control lens 110 into a desired shape.

  The two electrochromic dimming lenses 151 are incorporated in the spectacle frame 152. The eyeglass frame 152 is provided with a switch 153 and a power source 154. The power source 154 is electrically connected to the first electrode layer 131 and the second electrode layer 134 through a switch 153 and a wiring (not shown). By switching the switch 153, for example, one of a state in which a positive voltage is applied between the first electrode layer 131 and the second electrode layer 134, a state in which a negative voltage is applied, and a state in which no voltage is applied are selected. The state can be selected.

As the switch 153, for example, an arbitrary switch such as a slide switch or a push switch can be used. However, a switch that can switch at least the above-described three states is used. As the power source 154, for example, an arbitrary DC power source such as a button battery or a solar battery can be used. The power source 154 can apply a voltage of about plus or minus several volts between the first electrode layer 131 and the second electrode layer 134.
For example, by applying a positive voltage between the first electrode layer 131 and the second electrode layer 134, the two electrochromic light control lenses 151 are colored in a predetermined color. Further, by applying a negative voltage between the first electrode layer 131 and the second electrode layer 134, the two electrochromic light control lenses 151 are decolored and become transparent.

  However, depending on the characteristics of the material used for the electrochromic layer 132, color is developed by applying a negative voltage between the first electrode layer 131 and the second electrode layer 134, and the color is erased by applying a positive voltage. However, it may be transparent. Note that once the color is developed, the color continues even if no voltage is applied between the first electrode layer 131 and the second electrode layer 134.

Hereinafter, the material of each component constituting the electrochromic light control lens 110 according to the present embodiment, the film forming method, and the like will be described in detail.
<Lens>
The material of the lens 120 is not particularly limited as long as it functions as a spectacle lens, but a material having high transparency, a thin thickness, and a light weight is preferable. Further, it is preferable that the expansion due to the thermal history is as small as possible, and a material having a high glass transition point Tg and a material having a small linear expansion coefficient are preferable.

Specifically, in addition to glass, any of those described in the technical summary document on the high refractive index glasses lens of the JPO can be used. Episulfide resin, thiourethane resin, methacrylate resin, polycarbonate Resin, urethane resin, etc., and mixtures thereof can be used. Moreover, you may form the primer for improving a hard coat and adhesiveness as needed.
In the present invention, the lens includes a lens whose power (refractive index) is not adjusted (simple glass plate or the like).

<First electrode layer, second electrode layer>
The material of the first electrode layer 131 and the second electrode layer 134 is not particularly limited as long as it is a conductive material, but when used as a light control glass, light transmittance is ensured. Since it is necessary, a transparent conductive material that is transparent and excellent in conductivity is used. Thereby, the transparency of the glass can be obtained and the coloring contrast can be further increased.
Examples of the transparent conductive material include indium oxide doped with tin (hereinafter referred to as ITO), tin oxide doped with fluorine (hereinafter referred to as FTO), tin oxide doped with antimony (hereinafter referred to as ATO), and the like. Inorganic materials can be used. In particular, one of indium oxide (hereinafter referred to as In oxide), tin oxide (hereinafter referred to as Sn oxide) or zinc oxide (hereinafter referred to as Zn oxide) formed by vacuum film formation. It is preferable to use an inorganic material including one.

In oxides, Sn oxides, and Zn oxides are materials that can be easily formed by a sputtering method, and that can provide good transparency and electrical conductivity. Particularly preferable materials are InSnO, GaZnO, SnO, In ₂ O ₃ and ZnO. Furthermore, transparent network electrodes such as silver, gold, carbon nanotube, and metal oxide, and composite layers thereof are also useful. Note that the network electrode is an electrode in which carbon nanotubes or other highly conductive non-permeable materials are formed in a fine network to have transmittance.

  The thickness of each of the first electrode layer 131 and the second electrode layer 134 is adjusted so that an electric resistance value necessary for the oxidation-reduction reaction of the electrochromic layer 132 is obtained. When ITO is used as the material of the first electrode layer 131 and the second electrode layer 134, the thickness of each of the first electrode layer 131 and the second electrode layer 134 is, for example, 50 to 500 nm. it can.

  As a manufacturing method of each of the first electrode layer 131 and the second electrode layer 134, a vacuum evaporation method, a sputtering method, an ion plating method, or the like can be used. In addition, as long as each material of the first electrode layer 131 and the second electrode layer 134 can be formed by coating, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method. Method, wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, inkjet printing method Various printing methods such as these can be used.

  In the present embodiment, the second electrode layer 134 has a large number of fine through holes penetrating in the thickness direction. For example, a fine through hole can be provided in the second electrode layer 134 by the following method. That is, before forming the second electrode layer 134, a method can be used in which a layer having unevenness is formed in advance as a base layer, and the second electrode layer 134 having unevenness is used as it is.

  Alternatively, a method may be used in which a convex structure such as a micro pillar is formed before the second electrode layer 134 is formed, and the convex structure is removed after the second electrode layer 134 is formed. Further, before forming the second electrode layer 134, a foaming polymer or the like is sprayed, and after the second electrode layer 134 is formed, a process such as heating or degassing is performed to foam. May be. Alternatively, a method may be used in which various radiations are directly emitted to the second electrode layer 134 to form pores.

  Further, as a method for forming a fine through hole in the second electrode layer 134, a colloidal lithography method may be used. The colloidal lithography method is as follows. That is, fine particles are dispersed in the lower layer on which the second electrode layer 134 is laminated, and the conductive film that becomes the second electrode layer 134 is formed on the surface on which the fine particles are dispersed using the dispersed fine particles as a mask by a vacuum film forming method or the like. Form. Thereafter, patterning is performed by partially removing the conductive film together with the fine particles.

  As a method of forming fine through holes in the second electrode layer 134, a general lift-off method using a photoresist, a dry film, or the like may be used in addition to the colloidal lithography method. Specifically, first, a desired photoresist pattern is formed, then a second electrode layer 134 is formed, and then the photoresist pattern is removed to remove unnecessary portions on the photoresist pattern. In this method, fine through holes are formed in the electrode layer 134.

  When a fine through hole is formed in the second electrode layer 134 by a general lift-off method, it is used so that the light irradiation area to the object may be small in order to avoid damage to the lower layer due to light irradiation. It is preferable to use a negative type photoresist.

  Negative photoresists include, for example, polyvinyl cinnamate, styrylpyridinium formalized polyvinyl alcohol, glycol methacrylate / polyvinyl alcohol / initiator, polyglycidyl methacrylate, halomethylated polystyrene, diazoresin, bisazide / diene rubber, polyhydroxystyrene / Mention may be made of melamine / photoacid generators, methylated melamine resins, methylated urea resins and the like.

  Furthermore, it is possible to form fine through holes in the second electrode layer 134 by a processing apparatus using laser light.

  The diameter of the fine through hole provided in the second electrode layer 134 is preferably 10 nm or more and 100 μm or less. When the diameter of the through hole is smaller than 10 nm (0.01 μm), there arises a problem that the permeation of electrolyte ions is deteriorated. Further, when the diameter of the fine through-hole is larger than 100 μm, the level is visually observable (the size of one pixel electrode (one counter electrode) in a normal display), and the display performance just above the fine through-hole is defective. It will be.

  Although the ratio (hole density) of the hole area with respect to the surface area of the 2nd electrode layer 134 of the fine through-hole provided in the 2nd electrode layer 134 can be set suitably, it shall be 0.01 to 40%, for example be able to. If the hole density is too high, the surface resistance of the second electrode layer 134 is increased, which causes a problem that chromic defects are generated due to an increase in the area of the area where the second electrode layer 134 is absent. Further, if the hole density is too low, the permeability of the electrolyte ions is deteriorated.

<Electrochromic layer>
The electrochromic layer 132 can have the same mode as the electrochromic layer described in the first embodiment.

<Insulating porous layer>
The insulating porous layer 133 has a function of isolating the first electrode layer 131 and the second electrode layer 134 so as to be electrically insulated and holding an electrolyte. The material of the insulating porous layer 133 is not particularly limited as long as the material is porous. However, organic materials and inorganic materials having high insulating properties and durability and excellent film forming properties, and composites thereof. It is preferable to use a body.

  As a method of forming the insulating porous layer 133, for example, a sintering method (using fine holes or inorganic particles partially fused by adding a binder or the like to use holes generated between the particles) is used. be able to. As a method for forming the insulating porous layer 133, for example, an extraction method (after forming a constituent layer with an organic or inorganic substance soluble in a solvent and a binder that does not dissolve in the solvent, the organic or inorganic substance is dissolved in a solvent to To obtain holes) or the like.

Further, as a method for forming the insulating porous layer 133, a foaming method in which a high molecular polymer or the like is foamed by heating or degassing, etc., and a mixture of polymers is phase-separated by operating a good solvent and a poor solvent. Forming methods such as a phase inversion method and a radiation irradiation method in which various radiations are radiated to form pores may be used. Specific examples include polymer mixed particle films containing metal oxide fine particles (such as SiO ₂ particles and Al ₂ O ₃ particles) and a polymer binder, porous organic films (such as polyurethane resins and polyethylene resins), and porous film shapes. An inorganic insulating material film formed in the above.

  The unevenness of the insulating porous layer 133 depends on the thickness of the second electrode layer 134. For example, when the thickness of the second electrode layer 134 is 100 nm, the surface roughness of the insulating porous layer 133 is as follows. Must satisfy the requirement of less than 100 nm in average roughness (Ra). When the average roughness exceeds 100 nm, the surface resistance of the second electrode layer 134 is greatly lost, which causes display defects. The film thickness of the insulating porous layer 133 can be set to 0.5 to 2 μm, for example.

  The insulating porous layer 133 is preferably used in combination with an inorganic film. This is because when the second electrode layer 134 formed on the surface of the insulating porous layer 133 is formed by sputtering, damage to the organic material of the insulating porous layer 133 or the electrochromic layer 132 as a lower layer is prevented. This is to reduce.

As the inorganic film, it is preferable to use a material containing ZnS in addition to SiO ₂ . ZnS has a feature that it can be deposited at high speed by sputtering without damaging the electrochromic layer 132 or the like. Furthermore, ZnS—SiO ₂ , ZnS—SiC, ZnS—Si, ZnS—Ge, or the like may be used as a material containing ZnS as a main component.

Here, the ZnS content is preferably about 50 to 90 mol% in order to maintain good crystallinity when the insulating layer is formed. Therefore, particularly preferred materials are ZnS—SiO ₂ (8/2), ZnS—SiO ₂ (7/3), ZnS, ZnS—ZnO—In ₂ O ₃ —Ga ₂ O ₃ (60/23/10/7). ). By using the above materials as the insulating porous layer 133, a good insulating effect can be obtained with a thin film, and a decrease in film strength and film peeling can be prevented.

<Deterioration prevention layer>
The role of the deterioration preventing layer 135 is to perform a chemical reaction opposite to that of the electrochromic layer 132, and to balance the charge, the first electrode layer 131 and the second electrode layer 134 are corroded or deteriorated by an irreversible oxidation-reduction reaction. Is to suppress it. As a result, the repeated stability of the electrochromic dimming lens 110 is improved. In addition, the reverse reaction includes acting as a capacitor in addition to the case where the degradation preventing layer is oxidized and reduced.

  The material of the deterioration preventing layer 135 is not particularly limited as long as it is a material that plays a role of preventing corrosion of the first electrode layer 131 and the second electrode layer 134 due to an irreversible oxidation-reduction reaction. As the material of the deterioration preventing layer 135, for example, antimony tin oxide, nickel oxide, titanium oxide, zinc oxide, tin oxide, or a conductive or semiconductive metal oxide containing a plurality of them can be used. Furthermore, when coloring of the deterioration preventing layer does not become a problem, the same material as the above-described electrochromic material can be used.

  The deterioration preventing layer 135 can be composed of a porous thin film that does not hinder electrolyte injection. For example, conductive or semiconductive metal oxide fine particles such as antimony tin oxide, nickel oxide, titanium oxide, zinc oxide, tin oxide, etc., binders such as acrylic, alkyd, isocyanate, urethane, epoxy, phenol, etc. By fixing to the second electrode layer 134, a suitable porous thin film satisfying the electrolyte permeability and the function as a deterioration preventing layer can be obtained.

  Alternatively, as the material of the deterioration preventing layer 135, a material that maintains a transparent state with charge exchange may be used. For example, conductive polymers such as polypyrrole, polythiophene, polyaniline, or derivatives thereof, hybrid polymers of metal complexes and organic ligands, radical polymers, and the like can be given. When these are used, it is necessary to adjust the film density so as not to inhibit the injection of the electrolyte, or to form through holes by laser processing or the like. Alternatively, these materials may be used as the electrochromic layer 132, and the organic electrochromic compound supported on the conductive or semiconductive fine particles described above may be used as the deterioration preventing layer 135.

  As the deterioration prevention layer 135, it is preferable to use highly transparent n-type semiconductor oxide fine particles (n-type semiconductor metal oxide). As a specific example, titanium oxide, tin oxide, zinc oxide, or compound particles containing a plurality of them, or a mixture of particles having a primary particle size of 100 nm or less can be used.

  Furthermore, when these deterioration preventing layers 135 are used, the electrochromic layer 132 is preferably a material that changes from colored to transparent by an oxidation reaction. This is because the n-type semiconductor metal oxide is easily reduced (electron injection) at the same time as the electrochromic layer 132 undergoes an oxidation reaction, and the driving voltage can be reduced.

  In such a form, a particularly preferred electrochromic material is an organic polymer material. The film can be easily formed by a coating process or the like, and the color can be adjusted and controlled by the molecular structure. Examples of these organic polymer materials include poly (3,4-ethylenedioxythiophene) -based materials, complex polymers of bis (terpyridine) s and iron ions, and the like.

  As a method for forming the deterioration preventing layer 135, a vacuum deposition method, a sputtering method, an ion rating method, or the like can be used. If the material of the deterioration preventing layer 135 can be applied and formed, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, Various printing methods such as a slit coating method, a capillary coating method, a spray coating method, a nozzle coating method, a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, and an inkjet printing method can be used.

<Electrolyte>
In the present embodiment, the electrolyte (not shown) includes the first electrode layer 131 and the second electrode as an electrolytic solution from a minute through-hole formed in the second electrode layer 134 via the deterioration preventing layer 135. The insulating porous layer 133 disposed between the electrode layer 134 is filled. That is, the electrolyte (not shown) is filled between the first electrode layer 131 and the second electrode layer 134 so as to be in contact with the electrochromic layer 132 and is formed in the second electrode layer 134. It is provided so as to be in contact with the deterioration preventing layer 135 through the hole. As the electrolytic solution, a liquid electrolyte such as an ionic liquid or a solution obtained by dissolving a solid electrolyte in a solvent can be used.

As the electrolyte material, for example, inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, acids, and alkali supporting salts can be used. Specifically, LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ COO, KCl, NaClO ₃ , NaCl, NaBF ₄ , NaSCN, KBF ₄ , Mg (ClO ₄ ) ₂ , Mg ( BF ₄ ) ₂ or the like can be used.

  An ionic liquid can also be used. The ionic liquid may be any substance that is generally studied and reported. In particular, an organic ionic liquid has a molecular structure that exhibits a liquid in a wide temperature range including room temperature.

Examples of molecular structures include cation components such as N, N-dimethylimidazole salt, N, N-methylethylimidazole salt, N, N-methylpropylimidazole salt, N, N-dimethylpyridinium salt, N, Examples thereof include aromatic salts such as pyridinium derivatives such as N-methylpropylpyridinium salts, and aliphatic quaternary ammonium systems such as tetraalkylammonium such as trimethylpropylammonium salt, trimethylhexylammonium salt, and triethylhexylammonium salt.
As the anion component, a compound containing fluorine is preferable in terms of stability in the atmosphere, and examples thereof include BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , PF ₄ ⁻ , (CF ₃ SO ₂ ) ₂ N ^{− and the} like. An ionic liquid formulated by a combination of these cationic components and anionic components can be used.

  Examples of the solvent include propylene carbonate, acetonitrile, γ-butyrolactone, ethylene carbonate, sulfolane, dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, and polyethylene. Glycols, alcohols and mixed solvents thereof can be used.

  Further, the electrolytic solution does not need to be a low-viscosity liquid, and can take various forms such as a gel, a polymer crosslinked type, and a liquid crystal dispersion type. It is preferable to form the electrolyte in a gel or solid form from the viewpoint of improving element strength, improving reliability, and preventing color diffusion. As the solidification method, a method of holding the electrolyte and the solvent in the polymer resin is preferable. This is because high ionic conductivity and solid strength can be obtained. Further, it is preferable to use a photocurable resin as the polymer resin. This is because the device can be manufactured at a low temperature and in a short time compared to thermal polymerization or a method of thinning the film by evaporating the solvent.

<Protective layer>
The role of the protective layer 136 is unnecessary for protecting the device from external stress and chemicals in the cleaning process, preventing leakage of electrolyte, and stable operation of electrochromic devices such as moisture and oxygen in the atmosphere. For example, to prevent intrusion. At the same time, transparency, surface smoothness, refractive index, heat resistance, and light resistance are required so as not to impair the function as a lens. The thickness is preferably in the range of 1 μm to 200 μm. As the material, an ultraviolet curable resin or a thermosetting resin can be used. Specifically, an acrylic resin, a urethane resin, an epoxy resin, or the like is preferably used. As a formation process of the protective layer 136, various film forming methods such as a spin coating method, a dip coating method, a spray coating method, and a casting method can be used.
In addition to the protective layer 136, the electrochromic light control lens 110 preferably includes a hard coat layer for preventing scratches and an antireflection layer for suppressing reflection as necessary.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example.

Example 1
The electrochromic display element shown in FIG. 1 was produced as described below in accordance with the description in (Method for producing electrochromic display element) in the first embodiment described above. At this time, the transparency of the supported particle film formed on the ITO glass substrate during the production process was measured, and the transparency of the completed transmission element was measured. In the case of a reflective element, the reflectance during color development was measured.

(1) Preparation of electrolyte precursor material A propylene carbonate solution of tetrabutylammonium perchlorate (TBAP) was prepared. The TBAP concentration here was 2 mol / l. A mixture (product name: PNM-170) of a liquid crystal composition for PNLC manufactured by DIC, a monomer composition, and a polymerization initiator was mixed therewith. The TBAP concentration in this solution was adjusted to about 0.04 mol / l, and used as a precursor material for the electrolyte layer. Then, in order to regulate the thickness of the electrolyte layer to be produced, true spherical resin beads having a particle diameter of 10 μm were dispersed in the electrolyte precursor material at a concentration of 0.2 wt%.

(2) Production of each display electrode, each electrochromic layer, and white reflective layer An ITO film of about 100 nm is formed on the entire surface of a glass substrate (40 mm × 40 mm) as the display substrate 21 by a sputtering method, and the first display electrode 22 was produced. The surface resistance of the first display electrode 22 was about 200Ω.
A coating film of alumina particles whose surface was coated with titanium oxide was formed thereon. As the alumina, Cai Kasei NanoTek series alumina (average particle size 31 nm) was used, and as the titanium oxide, SAD-M (15% dispersion) manufactured by Sakai Chemical Industry Co., Ltd. was used. In addition, the average particle diameter of titanium oxide here is 7 nm.

  Alumina: 2.1 g, SAD-M: 4 g, Bis (2,4-pentanedionate) titanium (IV) Oxide: 0.5 g, methanol: 20 g. Dispersed for 2 hours using zirconia beads and a paint shaker. A primary dispersion was obtained. Next, primary dispersion: 22.2 g, ethyl cellulose (10 wt%, ethanol solution): 1 g, terpineol: 10 g are mixed, treated with an ultrasonic homogenizer for 2 minutes, and then the volatile components are removed with an evaporator to obtain the desired paste. Obtained. This paste is applied to a film thickness of 1 μm with a screen printer, dried with warm air (120 ° C., 5 minutes), UV / ozone treatment (150 ° C., 30 minutes), and then coated with alumina particles whose surface is coated with titanium oxide. A film was formed. In this state, that is, when a supported particle film (a coated film of alumina particles whose surface is coated with titanium oxide) formed on an ITO-formed glass substrate was measured with a haze meter (Nippon Denshoku Industries Co., Ltd .: NDH 7000), haze was measured. Was 1.83%.

  On top of this, 2, 4, 3, 3- containing 1 wt% of “4,4 ′-(isoxazole-3,5-diyl) bis (1- (2-phosphoethyl) pyridinium) bromide”, which is an electrochromic compound. A tetrafluoropropanol (hereinafter referred to as “TFP”) solution was spin-coated, and the first electrochromic layer 23 was formed by annealing at 120 ° C. for 10 minutes. When the haze was measured at this time, it was 1.92%.

A protective layer was formed on this by applying a 0.1 wt% ethanol solution of poly-N-vinylamide and a 0.5 wt% aqueous solution of polyvinyl alcohol by spin coating.
On top of this, ZnS—SiO ₂ having a composition ratio of 8: 2 was formed to a thickness of 140 nm by a sputtering method to form an insulating layer 24.

A second display electrode 25 was formed thereon by depositing an ITO film to a thickness of about 100 nm by sputtering. The surface resistance of the second display electrode 25 was about 200Ω.
On top of this, a coating film of alumina particles having the above-described surface coated with titanium oxide was similarly formed.
On top of this, 1 wt% of an electrochromic compound, “4,4 ′-(1-phenyl-1H-pyrrole-2,5-diyl) bis (1- (4- (phosphomethyl) benzyl) pyridine) bromide”. The second electrochromic layer 26 was formed by applying the included TFP solution by spin coating and performing an annealing treatment at 120 ° C. for 10 minutes.
A protective layer was formed on this by applying a 0.1 wt% ethanol solution of poly-N-vinylamide and a 0.5 wt% aqueous solution of polyvinyl alcohol by spin coating.
On top of this, an insulating layer 27 was formed by depositing ZnS—SiO ₂ having a composition ratio of 8: 2 to a thickness of 140 nm by a sputtering method.
A third display electrode 28 was formed thereon by depositing an ITO film to a thickness of about 100 nm by sputtering. The surface resistance of the third display electrode 28 was about 200Ω.

On top of that, a coating film of alumina particles in which the above-described surface was coated with titanium oxide was similarly formed.
Furthermore, the electrochromic compound “4,4 ′-(4,4 ′-(1,3,4-oxadiazole-2,5-diyl) bis (4,1-phenylene)) bis (1- ( A third electrochromic layer 29 was formed by applying a TFP solution containing 1 wt% of “8-phosphotyryl) pyridinium) bromide” by spin coating and performing an annealing treatment at 120 ° C. for 10 minutes.
On top of this, a TFP dispersion of titanium oxide particles (average particle size: 300 nm) and an aqueous polyurethane resin was spin-coated, and a white reflective layer 31 was formed by annealing at 120 ° C. for 10 minutes.
Each display electrode, each electrochromic layer, and the white reflective layer 31 were surrounded by a wall member 36.
In addition, the structure which consists of each display electrode created here, each electrochromic layer, the white reflection layer 31, and a wall member is called a "1st structure" for convenience.

(3) Production of a plurality of counter electrodes and charge holding layers On a glass substrate (40 mm × 40 mm) as the counter substrate 35, a TFT layer 34 (drive element layer) having a plurality of drive elements at a density of 140 ppi was formed.
An ITO film having a thickness of about 100 nm was formed on the entire surface of the TFT layer 34 by sputtering, and a plurality of counter electrodes 33 corresponding to a plurality of driving elements were produced by photolithography.
On top of that, spin coating of a TFP dispersion of an aqueous polyurethane resin and ATO nanoparticles (Mitsubishi Materials Co., Ltd.) (ATO / polymer mixing ratio is 45:55 by weight), followed by annealing at 120 ° C. for 15 minutes. The charge retention layer 32 was formed. Here, the thickness of the charge retention layer was 0.64 μm, and the surface resistance was 1.0E + 06 (Ω / □).
In addition, the structure which consists of the some counter electrode 33 and charge holding layer 32 produced here is called "the 2nd structure" for convenience.

(4) Production of Electrochromic Display Element The electrolyte precursor material prepared in (1) above was applied (injected) onto the white reflective layer 31 in the first structure produced in (2) above.
On top of that, the charge retention layer 32 in the second structure produced in the step (3) was overlaid.
The high pressure mercury lamp is used to irradiate ultraviolet light having a central wavelength of 365 nm at an irradiation light intensity of 50 mW / cm ² for 2 minutes from the side of the plurality of counter electrodes 33 to cause photopolymerization phase separation of the precursor material, thereby forming the electrolyte layer 30 did.

  Next, when the driving element of the electrochromic display element thus manufactured is driven by a predetermined method, the first electrochromic layer 23, the second electrochromic layer 26, and the third electrochromic layer 29 are driven. Each displayed a corresponding image, and a clear color image could be obtained. At this time, the time from the start of driving until the image was obtained was about 500 milliseconds. The time required for erasing the image was about 500 milliseconds.

When the first electrochromic layer 23 of this electrochromic display element is driven and colored so as to charge 1.0 mC / cm ² , a bright cyan color is displayed and the reflectance at 450 nm is measured. As a result, it was 2.6%.

(Comparative Example 1)
An electrochromic display element was produced in the same manner as in Example 1. However, a supported particle film having a film thickness of about 1 μm was formed using titanium oxide particles having an average particle size of 30 nm (TTO-51N, manufactured by Ishihara Sangyo Co., Ltd.) as the supported particles. The other two supported particle films were formed in the same manner.
When the haze was measured at the same timing as in Example 1, it was 6.70% when only one supported particle film was formed, and 6.70% when the first electrochromic layer was formed by applying the electrochromic compound solution. It was 98%.

Then, when a color of 1.0 mC / cm ² was applied to only the first electrochromic layer of the completed electrochromic display element to develop a color, a slight turbidity in cyan color was felt. The reflectance at 450 nm was measured and found to be 4.9%.

(Comparative Example 2)
An electrochromic display element was produced in the same manner as in Comparative Example 1. However, a display element was produced without forming a white reflective layer.
When the haze was measured at the same timing as in Example 1, it was 6.71% when only one supported particle film was formed, and 7.1 when the first electrochromic layer was formed by applying the electrochromic compound solution. It was 01%.
And when the haze of the completed transmission type display element was measured, it was 12.4%.

(Example 2)
An electrochromic display element was produced in the same manner as in Example 1. However, a display element was produced without forming a white reflective layer.
When the haze was measured at the same timing as in Example 1, it was 1.82% when only one supported particle film was formed, and 1. when the first electrochromic layer was formed by applying the electrochromic compound solution. It was 91%.
And when the haze of the completed transmission type display element was measured, it was 3.8%.

From a comparison between Example 1 and Comparative Example 1, in Example 1, the particles of the insulating material whose surface was coated with titanium oxide were used as the supported particles, so that the transparency of the supported particle film was improved. It can be seen that the saturation has improved.
Further, it was confirmed from the comparison between Example 2 and Comparative Example 2 that the transparency as the element was improved by using the particles of the insulating material whose surfaces were coated with titanium oxide as the supporting particles.

(Example 3)
In Example 3, an example in which the electrochromic light control lens 110 shown in FIG. 6 is manufactured will be described.
<Formation of first electrode layer and electrochromic layer>
First, a lens having a diameter of 65 mm was prepared, and an ITO film was formed to a thickness of about 100 nm by a sputtering method through a metal mask in a 25 mm × 45 mm region and a lead portion to form the first electrode layer 131. .
Next, an alumina particle coating film having a surface coated with titanium oxide was formed on the ITO film in the same manner as in Example 1. In this state, that is, when a supported particle film (a coated film of alumina particles whose surface is coated with titanium oxide) formed on an ITO-formed glass substrate was measured with a haze meter (Nippon Denshoku Industries Co., Ltd .: NDH 7000), haze was measured. Was 1.79%.

  Subsequently, as an electrochromic compound, a 2,2,3,3-tetrafluoropropanol solution containing 1.5 wt% of the compound represented by the following structural formula (1) was applied by a spin coating method. Then, an electrochromic layer 132 was formed by carrying out an annealing treatment at 120 ° C. for 10 minutes so that the surface was supported (adsorbed) on a coating film of alumina particles coated with titanium oxide.

<Formation of Insulating Porous Layer, Second Electrode Layer with Fine Through Hole>
Subsequently, a SiO ₂ fine particle dispersion liquid (silica solid content concentration 24.8% by weight, polyvinyl alcohol 1.2% by weight, water 74% by weight) having an average primary particle diameter of 20 nm is spin-coated on the electrochromic layer 132 and insulated. The porous layer 133 was formed. The film thickness of the formed insulating porous layer 133 was about 2 μm. Further, a fine SiO ₂ fine particle dispersion (silica solid content concentration 1 wt%, 2-propanol 99 wt%) having an average primary particle diameter of 450 nm was spin-coated to form a fine through-hole forming mask (colloidal mask).

Subsequently, an inorganic insulating layer of ZnS—SiO ₂ (8/2) was formed to a thickness of 40 nm on the fine through hole forming mask by a sputtering method. Further, an ITO film having a thickness of about 100 nm is formed on the inorganic insulating layer by a sputtering method in a region of 25 mm × 45 mm overlapping with the ITO film formed by the first electrode layer 131 and in a region different from the first electrode layer 131. A second electrode layer 134 was formed using a mask. Note that the ITO film formed in a region different from the first electrode layer 131 is a lead-out portion of the second electrode layer 134.

Thereafter, 2-in-propanol performs ultrasonic irradiation for 3 minutes, subjected to SiO ₂ removal treatment of the fine particles of 450nm is colloidal masks. It was confirmed by SEM observation that the second electrode layer 134 in which minute through holes of about 250 nm were formed was formed. The sheet resistance of the second electrode layer 134 was about 100Ω / □.

<Formation of deterioration prevention layer>
Subsequently, an antimony tin oxide particle dispersion was applied as a deterioration preventing layer 135 on the second electrode layer 134 by a spin coating method. And the nanostructure semiconductor material which consists of about 1.0 micrometer antimony tin oxide particle film was formed by performing an annealing process for 15 minutes at 120 degreeC.

<Electrolyte filling>
A solution obtained by mixing tetrabutylammonium perchlorate as an electrolyte and dimethyl sulfoxide and polyethylene glycol (molecular weight: 200) as a solvent in a ratio of 12:54:60 was used as an electrolytic solution. The element formed up to the deterioration preventing layer 135 was immersed for 1 minute and then dried on a hot plate at 120 ° C. for 1 minute to fill the electrolyte.

<Formation of protective layer>
Further, a protective layer 136 was formed to a thickness of about 3 μm by spin-coating an ultraviolet curable adhesive (SD-17, manufactured by DIC) and curing it by irradiation with ultraviolet light. Thereby, the electrochromic light control lens 110 shown in FIG. 6 was obtained.

The haze of the electrochromic light control lens thus completed was measured and found to be 2.03%. Next, when an electric charge of 1.0 mC / cm ² was applied to the electrochromic light control lens to develop a color, a bright magenta color was developed.

Example 4
An electrochromic light control lens was produced in the same manner as in Example 3. However, instead of alumina particles whose surfaces were coated with titanium oxide, silica particles whose surfaces were coated with titanium oxide were used as the material of the supported particles. As the silica, NanoTek series silica (average particle size: 25 nm) manufactured by CI Kasei Co., Ltd. was used, and a supported particle film was formed in the same manner as in Example 3. In this state, that is, when a supported particle film (coated film of silica particles whose surface is coated with titanium oxide) formed on an ITO-formed glass substrate was measured with a haze meter (Nippon Denshoku Industries Co., Ltd .: NDH 7000), the haze was 1 .58%.
The completed electrochromic light control lens had a haze of 1.89%. When this electrochromic light control lens was charged with 1.0 mC / cm ² of charge, it developed a bright magenta color.

(Comparative Example 3)
An electrochromic light control lens was produced in the same manner as in Example 3. However, as the support particles, titanium oxide particles having an average particle size of 30 nm (Ishihara Sangyo Co., Ltd., TTO-51N) are used to form a support particle film having a thickness of about 1 μm. In this state, that is, on the ITO-formed glass substrate. When the haze of the formed supported particle film was measured, it was 5.81%. Otherwise, the electrochromic light control lens was completed in the same manner as in Example 3. When the haze of the completed electrochromic light control lens was measured, it was 6.24%. When this electrochromic light control lens was charged with 1.0 mC / cm ² to develop color, a slight turbidity was felt in the magenta color.

  From the comparison between Examples 3 and 4 and Comparative Example 3, in Example 3 and Example 4, the particles of alumina and silica whose surfaces were coated with titanium oxide were used as the supported particles, so that the transparency of the supported particle film was improved. The improvement was confirmed.

DESCRIPTION OF SYMBOLS 20 Electrochromic display element 21 Display substrate 22, 25, 28 Display electrode 23, 26, 29 Electrochromic layer 23b Insulating material particle 23c Titanium oxide 30 Electrolyte layer 31 White reflective layer 32 Charge retention layer 33 Counter electrode 34 Drive element layer 35 counter substrate 36 wall member 100 information equipment (electronic book reader)
101 Display device 102 Control device (main controller)
110, 151 Electrochromic light control lens 113 Display controller 114 VRAM
DESCRIPTION OF SYMBOLS 120 Lens 130 Thin film light control function part 131 1st electrode layer 132 Electrochromic layer 133 Insulating porous layer 134 2nd electrode layer 135 Deterioration prevention layer 136 Protective layer 150 Electrochromic light control glasses 152 Eyeglass frame 153 Switch 154 Power supply

JP 2003-121883 A JP 2006-106669 A JP 2010-33016 A JP 2012-137736 A JP 2015-14743 A

Claims (9)

A display board;
Display electrodes;
An electrochromic layer provided in contact with the display electrode;
A counter substrate provided facing the display substrate;
A counter electrode;
A charge retention layer provided in contact with the counter electrode;
An electrolyte layer provided between the display substrate and the counter substrate,
The electrochromic layer includes at least particles made of an insulating material and an electrochromic compound,
An electrochromic display element, wherein the particles made of the insulating material have a surface coated with titanium oxide. A display board;
Display electrodes;
An electrochromic layer provided in contact with the display electrode;
A counter substrate provided facing the display substrate;
A counter electrode;
A charge retention layer provided in contact with the counter electrode;
A white reflective layer provided between the electrochromic layer and the charge retention layer;
An electrolyte layer provided between the display substrate and the counter substrate,
The electrochromic layer includes at least particles made of an insulating material and an electrochromic compound,
An electrochromic display element, wherein the particles made of the insulating material have a surface coated with titanium oxide.   The electrochromic display element according to claim 1, wherein the insulating material is alumina or silica.   The electrochromic display element according to claim 1, wherein 10 to 50 parts by weight of the titanium oxide is included with respect to 100 parts by weight of the particles made of the insulating material. The electrochromic display element according to any one of claims 1 to 4,
A VRAM for storing display data;
And a display controller that controls the electrochromic display element based on the display data. A display device according to claim 5;
And a control device that controls information to be displayed on the display device. Forming a display electrode on the display substrate;
Forming an electrochromic layer on the display electrode;
Forming a counter electrode on the counter substrate;
Forming a charge retention layer on the counter electrode;
A step of bonding the display substrate and the counter substrate through an electrolyte layer,
The electrochromic layer includes at least particles made of an insulating material, titanium oxide, and an electrochromic compound.
The electrochromic layer includes at least particles made of an insulating material and an electrochromic compound,
The method for producing an electrochromic display element, wherein the particles made of the insulating material are coated with titanium oxide on the surface. Forming a display electrode on the display substrate;
Forming an electrochromic layer on the display electrode;
Forming a white reflective layer on the electrochromic layer;
Forming a drive element layer on the counter substrate;
Forming a counter electrode on the drive element layer;
Forming a charge retention layer on the counter electrode;
A step of bonding the display substrate and the counter substrate through an electrolyte layer,
The electrochromic layer includes at least particles made of an insulating material, titanium oxide, and an electrochromic compound.
The electrochromic layer includes at least particles made of an insulating material and an electrochromic compound,
The method for producing an electrochromic display element, wherein the particles made of the insulating material are coated with titanium oxide on the surface. A lens, and a thin-film light control function unit laminated on the lens,
The thin film light control function unit includes a first electrode layer laminated on the lens,
A first electroactive layer laminated on the first electrode layer;
An insulating porous layer laminated on the first electroactive layer;
A second electrode layer that is porous laminated on the insulating porous layer;
A second electroactive layer formed on one or both of the upper and lower sides of the second electrode layer in contact with the second electrode layer;
An electrolyte layer filled between the first electrode layer and the second electrode layer and provided so as to be in contact with the first electroactive layer and the second electroactive layer. And
One of the first electroactive layer and the second electroactive layer is an electrochromic layer, and the other is a deterioration preventing layer,
The electrochromic layer includes at least particles made of an insulating material and an electrochromic compound,
The electrochromic light control lens, wherein the particles made of the insulating material have a surface coated with titanium oxide.