JP6776510B2 - Electrochromic display elements, display devices, information equipment, manufacturing methods for electrochromic display elements, electrochromic dimming lenses - Google Patents

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 dimming lens.

In recent years, so-called electronic paper has been actively developed as an information medium to replace paper. Display elements used in electronic paper include display elements using reflective liquid crystals, display elements using electrophoresis, display elements using toner electrophoresis, display elements using electrochromic compounds (electrochromic display elements), and so on. And so on.

Electrochromic display devices are promising candidates for next-generation display devices because of their memory effect and low voltage drive. Currently, they are used for electrochromic display devices from material development to device design. A wide range of research and development is being carried out.

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

Therefore, the electrochromic display element is also expected as a display element capable of multicolor display, and for example, the following Patent Documents 1 to 4 are disclosed.
Patent Document 1 discloses an electrochromic device having an organic electrochromic layer in which a plurality of polymer fine particle layers are laminated.
Patent Document 2 discloses a multicolor display device 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.
In Patent Document 4, in order to realize a practical electronic paper using an electrochromic display element, a TFT (thin film transistor) is used as a driving element, and a plurality of TFTs are separated and formed on a pixel electrode (counter electrode). It is disclosed that a charge holding layer (high resistance layer) is formed as a continuous layer (solid film). As a result, an electrochromic display device having good display quality without color bleeding and image blurring and having excellent durability is disclosed.

In addition to the above-mentioned electronic paper, the electrochromic display element is also being studied for application to a light control element such as a light control lens, a light control window, and an antiglare mirror. For example, Patent Document 5 proposes an electrochromic dimming lens in which a thin film dimming function is laminated and formed on a single lens, which can be made thin and lightweight, and has excellent productivity at low cost.

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. Further, also in a reflective display element such as electronic paper, it is important that the constituent elements other than the reflective layer have high transparency in order to obtain high display quality as an element. As a component that affects the transparency of this electrochromic display element, there are particles carrying an electrochromic compound.

Conventionally, titanium oxide has been preferably used as supporting particles of an electrochromic compound in an electrochromic display device. The reason is that it has a chemical structure that easily adsorbs and supports an electrochromic compound, that is, a structure that has a hydroxyl group (OH group), and that the electrochromic compound is interposed between the electrode of the element and the electrochromic compound. It is mentioned that it has sufficient conductivity that enables the transfer of electric charges necessary for the color development and decolorization of the compound.

However, although titanium oxide is preferably used as supported particles of an electrochromic compound, it has a problem that it is difficult to secure sufficient transparency as a supported particle film. In order to suppress light scattering and ensure transparency, particles with a small particle size (100 nm or less) are usually used to form a film, but it is still difficult to obtain good transparency in the case of titanium oxide because of refraction. This is because the rate is relatively large.
From the above, an electrochromic display element having excellent transparency and good display quality has been desired.

Therefore, in view of the above problems, it is an object of the present invention to provide an electrochromic display device having excellent transparency and vivid color development.

In order to solve the above problems, the electrochromic display element of the present invention is provided with a display substrate, a display electrode, an electrochromic layer provided in contact with the display electrode, and facing the display substrate. An electrochromic display element having a facing substrate, a facing electrode, a charge holding layer provided in contact with the facing electrode, and an electrolyte layer provided between the display board and the facing substrate. The electrochromic layer contains at least tin oxide particles and an electrochromic compound supported on the tin oxide particles, and the electrochromic display element has the display electrode and the electrochromic layer on the display substrate. Ri der haze of not more than 1.02% when it is formed, the average primary particle size of the tin oxide particles is equal to or less than 30 nm.

According to the present invention, it is possible to provide an electrochromic display element having excellent transparency and vivid color development.

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 another 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 which concerns on this invention. It is a figure which shows the schematic structure of an example of the information device which concerns on this invention. It is a schematic diagram which shows an example of the electrochromic photochromic lens which concerns on this invention. It is a schematic diagram which shows an example of the structure of the eyeglass using the electrochromic dimming lens which concerns on this invention.

Hereinafter, the electrochromic display element, the display device, the information device, the manufacturing method of the electrochromic display element, and the electrochromic dimming lens according to the present invention will be described with reference to the drawings. The present invention is not limited to the embodiments shown below, and can be modified within the range conceivable by those skilled in the art, such as other embodiments, additions, modifications, and deletions. However, as long as the action and effect of the present invention are exhibited, it is included in the scope of the present invention.

The electrochromic display element of the present invention includes a display substrate, a display electrode, an electrochromic layer provided in contact with the display electrode, an opposing substrate provided facing the display substrate, and an opposing electrode. It has a charge holding layer provided so as to be in contact with the counter electrode and an electrolyte layer provided between the display substrate and the counter substrate, and the electrochromic layer contains at least tin oxide and is described as described above. Tin oxide is characterized by being formed from a tin oxide sol solution.

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

[First Embodiment]
The electrochromic display element according to this embodiment will be described. In this embodiment, FIGS. 1 and 2 will be described below as examples. In FIG. 1, a leading electrochromic display element is illustrated with a plurality of display electrodes and electrochromic layers, but as will be described later, the present invention is not limited to this, and even if there is only one display electrode and electrochromic layer. Good. Further, although the white reflective layer is shown in FIG. 1, it is included in the present invention even if it does not have the white reflective layer.

(Structure of electrochromic display element)
FIG. 1 shows an example of the structure of the electrochromic display element 20 according to the present 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. Insulation layer 27, third display electrode 28, third electrochromic layer 29, electrolyte layer 30, white reflection 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 substrates are filled with an electrolyte layer 30. There is. In addition, the electrochromic layer contains tin oxide.

As a detailed structure on the display board 21 side, a first display electrode 22 is provided in contact with the display board 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 facing substrate 35 side, a drive element layer 34 is provided in contact with the facing 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 holding 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 holding layer 32. In the case of a transmissive display element, a white reflective layer may not be provided. In the present invention, the case of having a white reflective layer may be referred to as a reflective display element, and the case of having a white reflective layer may be referred to as a transmissive display element.
Hereinafter, each layer will be described in detail.

<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, and a second. It is a substrate for supporting a laminated structure such as the display electrode 28 of No. 3 and the third electrochromic layer 29.

The material of the display substrate 21 is preferably a material having translucency. For example, glass, plastic film and the like can be mentioned.

<Display electrode>
The first display electrode 22 develops or decolorizes the first electrochromic layer 23 by the voltage generated between the electrode and the counter electrode 33. The second display electrode 25 develops or decolorizes the second electrochromic layer 26 by the voltage generated between the electrode and the counter electrode 33. The third display electrode 28 develops or decolorizes the third electrochromic layer 29 by the 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 tone of the color 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 conductive material having translucency. Examples thereof include inorganic materials such as tin-doped indium oxide (hereinafter ITO), fluorine-doped tin oxide (hereinafter FTO), and antimony-doped tin oxide (hereinafter ATO). Further, InSnO, GaZnO, _SnO, it is particularly preferable to use the _In 2 O 3, ZnO and 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 contains at least tin oxide 23b, and in FIG. 2, the electrochromic compound 23a is supported on the tin oxide 23b. The electrochromic compound 23a causes a redox reaction due to the voltage generated between the first display electrode 22 and the counter electrode 33, and develops or loses color (reversible reaction). The length of a single molecule of the electrochromic compound 23a is preferably 5 nm or less.

The average primary particle diameter of the tin oxide particles 23b (hereinafter, “average primary particle diameter” when referred to as “particle size”) is preferably 1 nm to 100 nm, and particularly preferably 3 to 8 nm. .. By setting the particle size to 1 nm to 100 nm, the first electrochromic layer 23 can be made a transparent layer. That is, in the reflective display element, a high white reflectance can be obtained when no color is developed. Further, in the transmissive display element, a vivid color can be obtained at the time of color development, and a colorless and transparent state can be obtained at the time of decolorization. Further, by setting the particle size to 3 to 8 nm, it is possible to obtain a high specific surface area.
Transparency largely depends on the refractive index and particle size of the tin oxide particles 23b. The closer the refractive index is to 1, the more advantageous it is in terms of transparency. Titanium oxide: 2.52 (anatase), 2.71 (rutile), and tin oxide is 2.

In the present invention, the tin oxide contained in the electrochromic layer is formed from a tin oxide sol solution. A sol solution is a colloid that uses a liquid as a dispersion medium. A colloid is one that passes through filter paper but not a semipermeable membrane.
When the tin oxide contained in the electrochromic layer is not formed from the tin oxide sol solution, for example, when it is formed by using a paste, the haze rate and the reflectance are lowered.

Further, it is preferable that the tin oxide contained in the electrochromic layer is formed of at least the tin oxide sol solution and the tin complex compound represented by the following general formula (1).

(In the formula, A, B, C and D represent an alkyl group, an alkoxy group, an ester group, a 1,3-dicarbonyl compound or a halogen atom, which may be the same or different, and A and B may be different. , Or C and D may be coupled to each other.)

As the halogen atom in the general formula (1), Cl is particularly preferable.
Examples of the tin complex compound represented by the general formula (1) include Tin (II) acetate, Tin (IV) acetate, Tin (II) 2-ethylhexanoate, Tin (II) oxalate, and Tin (II). trifluoromethanesulfonate, Tin (IV) isopropoxide, Tin (IV) tetra (t-butoxide), Bis (2,4-pentadionato) tin (IV) dichloride, Tin (II) acethylacetonate, Tin (II) chloride, Tin (IV) chloride And so on. By using the tin complex compound, the necking of the tin oxide particles can be improved by decomposing these tin compounds into tin oxide.
When A to D are bonded to each other, they are divalent groups.

In FIG. 2, the supported particles, that is, the tin oxide particles 23b, have a structure in which one type of electrochromic compound 23a is supported, but it is also possible to support a plurality of types of electrochromic compounds.

Further, the second electrochromic layer 26 and the third electrochromic layer 29 also have tin oxide 23b, similarly to the first electrochromic layer 23. Note that FIG. 2 shows a structure in which a single molecule of the electrochromic compound 23a is adsorbed on the supported particles as an ideal state, but the structure is not limited to this structure. The structure may be such that the electrochromic compound 23a is fixed at a high density so as not to move. Further, if the structure is such that the electrical connection between the first electrochromic layer 23 and the first display electrode 22 is ensured so that the transfer of electrons accompanying the redox reaction of the electrochromic compound 23a is not hindered. Good.
Further, the electrochromic compound 23a and the tin oxide particles 23b may be mixed to form a single layer. The same applies to the case of the second electrochromic layer 26 and the third electrochromic layer 29.

As the material of the electrochromic compound, either an inorganic electrochromic compound or an organic electrochromic compound may be used. Further, known electrochromic compound materials such as dye-based, polymer-based, metal complex-based, and metal oxide-based materials can be used.

For example, as dye-based and polymer-based electrochromic compounds, azobenzene-based, anthraquinone-based, diarylethene-based, dihydroprene-based, dipyridine-based, styryl-based, styrylspiryran-based, spiroxazine-based, spirothiopyran-based, thioindigo-based, tetrathiafluvalene-based , Telephthalic acid type, triphenylmethane type, triphenylamine type, naphthopyrane type, viologen type, pyrazoline type, phenazine type, phenylenediamine type, phenoxazine type, phenothiazine type, phthalocyanine type, fluorane type, flugide type, benzopyran type, Examples thereof include low molecular weight organic electrochromic compounds such as metallocene, and conductive polymer compounds such as polyaniline and polythiophene.

Further, for these materials, refer to a viologen-based compound (for example, Japanese Patent No. 3955641 and JP-A-2007-171781) or a dipyridine-based compound (for example, JP-A-2007-171781 and JP-A-2008-116718). ) Is preferably included. By including the viologen-based compound or the dipyridine-based compound, the electrochromic compound can exhibit a good color value at the time of color development and color erasing even if the voltage applied to the display electrode and the counter electrode is low. For example, it is preferable to contain a dipyridine compound represented by the following general formula (2).

In the above general formula (2), R1 and R2 represent an alkyl group or an aryl group having 1 to 8 carbon atoms which may independently have a substituent, and at least one of R1 and R2 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, l represent 0, 1, or 2. A, B, and C represent alkyl groups, aryl groups, and heterocyclic groups having 1 to 20 carbon atoms, each of which may have a substituent independently.

Further, for example, examples of the metal oxide-based electrochromic compound include tungsten oxide, molybdenum oxide, iridium oxide, indium oxide, titanium oxide, nickel oxide, vanadium oxide, and Prussian blue.
It is preferable that all the materials used for the electrochromic compounds in each electrochromic layer in the electrochromic display element 20 are oxidative coloring materials or all reducing coloring materials. ..

<Insulation layer>
In the first insulating layer 24, the first display electrode 22 provided with the first electrochromic layer 23 and the second display electrode 25 provided with the second electrochromic layer 26 are electrically formed. Isolate them so that they are insulated.
In the second insulating layer 27, 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 are electrically formed. Isolate them so that they are insulated.

If the resistance between the electrodes between the first display electrode 22 and the second display electrode 25 can be increased, the first insulating layer 24 may not be provided. For example, by increasing the film thickness of the first electrochromic layer 23, it is possible to increase the resistance between the electrodes between the first display electrode 22 and the second display electrode 25. Similarly, if the resistance between the electrodes 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 decolorization in each electrochromic layer can be controlled individually, so that high-definition full-color display becomes possible.
The material of the insulating layer may be a porous insulator, and is not particularly limited, but a material having high insulation and durability and excellent film forming property is preferable. A material containing at least ZnS is preferable. This is because ZnS can form a high-speed film by sputtering and can reduce damage to the electrochromic layer during film formation. For example, it is preferable to use ZnS-SiO ₂ , ZnS-SiC, ZnS-Si, ZnS-Ge and the like.

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

<Opposite board>
The facing substrate 35 is a substrate for supporting a laminated structure such as a driving element layer 34, a facing electrode 33, and a charge holding layer 32.
The material of the opposed substrate 35 is preferably a material having translucency. For example, glass, plastic film and the like can be mentioned.

<Counter electrode>
The counter electrode 33 develops or decolorizes the first electrochromic layer 23, the second electrochromic layer 26, and the third electrochromic layer 29 based on the voltage generated between the counter electrodes 33 and the display electrodes.
The material of the counter electrode 33 is not particularly limited as long as it is a conductive material. For example, examples of the conductive material having translucency include ITO, FTO, zinc oxide and the like. Further, examples of the conductive metal material include zinc and platinum. Moreover, carbon or the like may be used.

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

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

As the material of the charge holding layer 32, a conductor fine particle material or a semiconductor fine particle material (fine particle material) and a mixed material of a polymer material can be used.
The polymer material is not particularly limited, and examples thereof include acrylic type, alkyd type, fluorine type, isocyanate type, urethane type, amino type, epoxy type, and phenol type.
Examples of the conductor fine particles include ITO, FTO, ATO and the like.
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.

When the material used for the electrochromic compound in each electrochromic layer is an oxidative coloring material, it is particularly preferable to use ATO as the fine particle material to be mixed with the polymer material. When the material used for the electrochromic compound in each electrochromic layer is a reducing color-developing material, it is particularly preferable to use tungsten oxide as the fine particle material to be mixed with the polymer material. By using ATO when it is an oxidation color-developing material and tungsten oxide when it is a reduction color-developing material, it is possible to reduce the driving voltage of the electrochromic display element and improve the durability repeatedly.

<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, an ultraviolet curable resin material such as an acrylate type (radical polymerization type) or an epoxy type (cationic polymerization type), or a thermosetting resin material such as an epoxy type, a phenol type or a 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 preferably contains titanium oxide particles and metal hydroxides 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, more preferably 250 nm to 2 μm.

<Electrolyte layer>
The electrolyte layer 30 fills the space generated between the facing 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 transfers an 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 second. Promotes color development or decolorization of the electrochromic layer 26 and the third electrochromic layer 29.

As the material of the electrolyte layer 30, inorganic ion salts such as alkali metal salts and alkaline earth metal salts can be used, and quaternary ammonium salts, acids, supporting salts of alkalis and the like 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.

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

For example, examples of the cation component include imidazole derivatives such as N, N-dimethylimidazole salt, N, N-methylethyl imidazole salt, and N, N-methylpropyl imidazole salt. Further, pyridinium derivatives such as N, N-dimethylpyridinium salt, N, N-methylpropylpyridinium salt and the like can be mentioned. Examples thereof include aliphatic quaternary ammonium salts such as trimethylpropylammonium salt, trimethylhexylammonium salt and triethylhexylammonium salt.

Further, for example, as an anion component, it is preferable to use a compound containing fluorine in consideration of stability in the atmosphere. For _{^{example, BF 4 -, CF 3 SO}} 3 -, PF4 -, (CF 3 SO 2) 2 N -, and the like.

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 dissolved directly in any of the 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.) may be dissolved, and the solution may be mixed with any of photopolymerizable monomers, oligomers, and liquid crystal materials.

<Protective layer>
Further, if necessary, the 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 on the opposite side to the display substrate 21. By providing the protective layer, the adhesion to the layer adjacent to the first electrochromic layer 23 and the second electrochromic layer 26 (for example, the first insulating layer 24, the second insulating layer 27, etc.), the solvent, and the solvent. The durability of the electrochromic display element 20 can be improved by improving the solubility resistance to the solvent.

As the material of the protective layer, it is preferable to use an organic polymer material. For example, general resins such as polyvinyl alcohol, poly-N-vinylamide, polyester, polystyrene and polypropylene can be mentioned.
Further, the inorganic protective layer may be provided between the third electrochromic layer 29 and the electrolyte layer 30. By providing the inorganic protective layer, the solubility resistance, corrosion resistance, etc. of the third electrochromic layer 29 with respect to the electrolyte layer 30 can be improved, and the durability of the electrochromic display element 20 can be improved.

(Multicolor display of electrochromic display element)
Next, the multicolor display of the electrochromic display element will be described.
Since the electrochromic display element 20 shown in FIG. 1 has the above-mentioned structure, multicolor display can be easily performed.
In the electrochromic display element 20, for example, the first electrochromic layer 23 develops a cyan color, the second electrochromic layer 26 develops a magenta color, and the third electrochromic layer 29 develops a yellow color. To develop color.

Since the first display electrode 22 and the second display electrode 25 are provided so as to be separated from each other 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 voltage generated between the counter electrode 33 and the second display electrode 25 can be controlled independently.
Further, since the second display electrode 25 and the third display electrode 28 are provided so as to be separated from each other via the second insulating layer 27, the electrochromic display element 20 is the counter electrode 33 and the second display electrode 33. 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 independently colored or decolorized.

As a result, the electrochromic display element 20 can arbitrarily develop or decolorize each electrochromic layer based on the voltage applied to the counter electrode and each display electrode. For example, in a multi-step coloring pattern such as coloring only the first electrochromic layer 23, coloring only the second electrochromic layer 26, coloring only the first electrochromic layer 23 and the third electrochromic layer 29, and the like. The color can be arbitrarily developed. Further, the color, color density, brightness, etc. developed by each electrochromic layer can be appropriately adjusted based on the voltage applied to the counter electrode and each display electrode to perform a desired multicolor display.

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, and the third color is not limited to magenta. The color developed by the electrochromic layer 29 is not limited to yellow.

(Manufacturing method of electrochromic display element)
Next, a method for manufacturing the electrochromic display element of the present invention will be described.
The method for 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 step of forming a counter electrode on a counter substrate. It includes a step of forming a charge holding layer on the counter electrode and a step of laminating the display electric substrate and the counter substrate via an electrolyte layer.

Further, the method for 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. The step of forming, the step of forming the drive element layer on the counter substrate, the step of forming the counter electrode on the drive element layer, the step of forming the charge holding layer on the counter electrode, and the indication. It has a step of laminating an electric substrate and the facing substrate via an electrolyte layer.
Then, as described in the above embodiment, the electrochromic layer contains at least tin oxide, and the tin oxide is formed from the tin oxide sol solution.

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

The method for manufacturing the electrochromic display element 20 is shown in steps S11 to S23 of FIG. The outline of steps S11 to S23 is as follows.
Step S11: First display electrode forming step of forming the first display electrode 22 on the display electric substrate 21. Step S12: Forming the first electrochromic layer for forming the first electrochromic layer 23 on the first display electrode 22. Step S13: First insulating layer forming step of forming the first insulating layer 24 on the first insulating layer 24 ・ Step S14: Second display electrode forming step of forming the second display electrode 25 on the first insulating layer 24 ・ Step S15 : Second electrochromic layer forming step of forming the second electrochromic layer 26 on the second electrochromic layer 26-Step S16: Second insulating layer forming step of forming the second insulating layer 27 on the second electrochromic layer-Step S17: Third display electrode forming step of forming the third display electrode 28 on the top-Step S18: Third electrochromic layer forming step of forming the third electrochromic layer 29 on the third display electrode forming step-Step S19: On top of it White reflective layer forming step of forming the white reflective layer 31-Step S20: Driving element layer forming step of forming the driving element layer 34 on the facing substrate 35-Step S21: Countering electrode forming step of forming the facing electrode 33 on the driving element layer 34 Step S22: Charge holding layer forming step of forming the charge holding layer 32 on the charge holding layer 32. Step S23: Bonding step of bonding the display substrate 21 and the facing substrate 35.

Next, an example of a method for manufacturing the electrochromic display element shown in FIG. 4 will be described below. The numerical values described below are specific examples and are not limited thereto.

<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 200 Ω / □ 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 is formed. 22 is formed.
The film forming method is not limited to the sputtering method, and other vacuum film forming methods such as the 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 sol solution of supported particles, that is, tin oxide particles (hereinafter, may be simply referred to as “supported particles” in the present invention) is applied onto the first display electrode 22 by a spin coating method or the like. Then, an annealing treatment is performed at 120 ° C. for 15 minutes so that the first display electrode 22, the supported particles, and the supported particles are partially bonded to each other. As a result, a supported particle film is formed.

Then, 2,2,3,3-tetra containing 1 wt% of the 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 a spin coating method, and annealing treatment is performed at 120 ° C. for 10 minutes. As a result, the first electrochromic layer 23 composed of the tin oxide particle film and the electrochromic compound is formed.

Then, a protective layer is formed by applying an ethanol solution containing 0.1 wt% of poly-N-vinylamide and an aqueous solution containing 0.5 wt% of polyvinyl alcohol on the first electrochromic layer 23 by a spin coating method. 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 film thickness of about 140 nm is formed on the protective layer by a sputtering method to form the first insulating layer 24. The composition ratio of ZnS and SiO ₂ is 8: 2.
As the film forming method, a vacuum film forming method such as a vapor deposition method, a sputtering method, or an ion plating method can be applied.

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

<Second electrochromic layer forming process>
Next, the second electrochromic layer forming step shown in step S15 of FIG. 4 is performed.
First, the sol solution of the supported particles is applied onto the second display electrode 25 by a spin coating method or the like. Then, an annealing treatment 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. As a result, a supported particle film is formed.
Then, a TFP containing 1 wt% of the 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 a spin coating method and annealed at 120 ° C. for 10 minutes. As a result, a second electrochromic layer 26 composed of the supported particle film and the electrochromic compound is formed.

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

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

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

<Third electrochromic layer forming process>
Next, the third electrochromic layer forming step shown in step S18 of FIG. 4 is performed.
First, the sol solution of the supported particles is applied onto the third display electrode 28 by a spin coating method or the like. Then, an annealing treatment 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 to each other. As a result, a supported particle film is formed.

Then, on the supported particle film, 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 a spin coating method, and annealing treatment is performed at 120 ° C. for 10 minutes. As a result, a third electrochromic layer 29 composed of the supported particle film and the electrochromic compound is formed.

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

After that, 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 the white reflective layer 31 is surrounded by a wall member 36 (see FIG. 1).

<Drive element layer forming process>
Next, the drive element layer forming step shown in step S20 of FIG. 4 is performed.
A drive element layer 34 having a plurality of drive elements is formed on an opposed substrate 35 (for example, a glass substrate having a length of 40 mm and a width of 40 mm) so that the pixel density is 140 ppi (Pixels per Inch) by a known process. ..

<Counter electrode forming process>
Next, the counter electrode forming step shown in step S21 of FIG. 4 is performed.
An ITO film having a film thickness of about 100 nm is formed on the facing substrate 35 by a sputtering method. After that, a plurality of counter electrodes 33 are formed by photolithography in correspondence with the plurality of drive elements included in the drive element layer 34.

<Charge retention layer forming process>
Next, the charge holding layer forming step shown in step S22 of FIG. 4 is performed.
The charge holding 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 on the driving 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 onto the drive element layer 34 and the counter electrode 33 by a spin coating method. Then, by performing an annealing treatment at 120 ° C. for 15 minutes, a charge holding layer 32 having a film thickness of about 640 nm and a surface resistance of about 1.0E + 06Ω / □ is formed.

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

It is not necessary to selectively apply the TFP solution of the aqueous polyurethane resin and the ATO particles 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. It may be applied between the counter electrode 33 and the counter electrode 33. Since it is not necessary to selectively apply the solution, the case of forming the charge holding layer 32 simplifies the manufacturing process and suppresses the manufacturing cost as compared with the case of not forming the charge holding layer 32. Can be done.

<Lasting process>
Next, the bonding step shown in step S23 of FIG. 4 is performed.
The counter substrate 35 on which the charge holding layer 32 is formed and the display substrate 21 on which the white reflection layer 31 is formed are bonded to each other with an 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, the precursor material of the electrolyte is injected from above the white reflective layer 31. The display board 21 and the facing board 35 are bonded together by sealing the injection port. Then, ultraviolet light is irradiated from the counter electrode 33 side for 2 minutes by a high-pressure mercury lamp. Since the precursor material can be separated into photopolymerized phases by irradiation with ultraviolet light, an electrolyte layer 30 can be formed between the two substrates. As the ultraviolet light, one having a central 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 manufacture of the electrochromic display element 20. In the laminating step in step S23, the precursor material of the pre-prepared electrolyte layer 30 is used.

As an example of the method for preparing the precursor material of the electrolyte layer 30, first, a solution of Tetra Butyl Ammonium Perchlorate (TBAP) in propylene carbonate is used, and the molar concentration of TBAP is about 20 mol / mol /. Adjust so that it becomes l. Then, a mixture of a liquid crystal composition for PNLC (Polymer Network Liquid Crystal), a monomer composition, and a polymerization initiator is mixed with the solution. Then, the molar concentration of TBAP in the propylene carbonate solution is adjusted again to be about 0.04 mol / l. Then, in order to regulate the thickness of the produced electrolyte layer 30, spherical resin beads having a particle size of 10 μm are dispersed in the propylene carbonate solution at a concentration of 0.2 wt%. In this way, it can be used as a precursor material for the electrolyte layer 30.

[Second Embodiment]
Next, other embodiments of the electrochromic display device according to the present invention will be described. The description of the same points as in the above embodiment will be omitted.
The electrochromic display element according to this embodiment is shown in FIG.
The electrochromic display element 20 shown in FIG. 1 described above has three electrochromic layers, a first electrochromic layer 23, a second electrochromic layer 26, and a third electrochromic layer 29. The invention is not particularly limited. When the purpose is to display a monochrome image instead of displaying a full-color image, it may have only one electrochromic layer, for example, the electrochromic display element 20A shown in FIG.

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

FIG. 5 shows an example of the 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. Further, 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. Further, the display panel 111 does not have to be provided with a touch panel. If there are other input means, the display panel 111 may be provided with the other input means. If the display panel 111 does not have a touch panel, the touch panel driver 112 is not required.
The arrows shown in FIG. 5 represent typical signal and information flows, and do not represent all the connection relationships of each block.

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

Further, when the user touches the touch panel, the display panel 111 outputs a signal based on the touch position to the touch panel driver 112.
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. In fact, no particular change was observed in the display state of the image even after the display and erasure of the full-color image were alternately repeated 1000 times.
Further, the display panel 111 can switch between color development and color erasing at high speed. In fact, the time required from the start of driving to the acquisition of an image and the time required to erase the acquired image were measured and found to be 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 out the display data stored in the VRAM 114 at predetermined timings, and individually controls the display colors of the plurality of pixels included in the display panel 111 according to the display data. The display controller 113 outputs a pixel selection signal for specifying the pixel to be colored and a color designation signal for specifying the color to the display panel 111.
The touch panel driver 112 outputs the 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 part such as the RAM 104, the flash memory 105, the character generator 106, the interface 107, and the VRAM 114 according to the 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 dot data. , Transfer to 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 user's selection contents based on the position information from the touch panel driver 112.

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

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

Further, the ROM 103 stores various programs described by codes that can be decoded 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 and the like as contents.
The character generator 106 stores dot data corresponding to various character data.
The interface 107 controls the connection with the external device. The interface 107 can be connected to a memory card, a personal computer, and a public line. It should be noted that 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, excellent transparency and vivid color development can be obtained, and reflection type display and transmission can be obtained. In either case, clear display characteristics can be obtained.

[Fourth Embodiment]
(Structure of electrochromic photochromic lens)
The electrochromic dimming lens according to the present embodiment includes a lens and a thin film dimming function unit laminated on the lens. The thin film dimming function unit is provided on the first electrode layer laminated on the lens, the first electrically active layer laminated on the first electrode layer, and the first electrically active layer. The laminated insulating porous layer, the second electrode layer which is porous laminated on the insulating porous layer, and the upper side of the second electrode layer in contact with the second electrode layer. The second electroactive layer formed on either one or both of the lower surfaces, and the first electroactive layer and the first electroactive layer, which are filled between the first electrode layer and the second electrode layer, and It has an electrolyte layer provided in contact with the second electrically active layer. One of the first electrically active layer and the second electrically active layer is an electrochromic layer, and the other is a deterioration prevention layer. Then, in the electrochromic layer, the electrochromic layer contains at least tin oxide, and the tin oxide is formed from a tin oxide sol solution.
According to this embodiment, it is possible to provide an electrochromic photochromic lens having display characteristics excellent in transparency.

FIG. 6 is a cross-sectional view illustrating the electrochromic photochromic lens according to the present embodiment. With reference to FIG. 6, the electrochromic dimming lens 110 has a lens 120 and a thin film dimming function unit 130 laminated on the lens 120. The planar shape of the electrochromic photochromic lens 110 can be, for example, a round shape.

The thin film dimming 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 prevention layer 135, and a protective layer 136 are sequentially laminated. It is a portion that has and performs color emission (dimming) of the electrochromic layer 132. The protective layer 136 may be formed on the upper surface of the deterioration prevention layer 135 (the surface opposite to the lens 120), and is not necessarily the first electrode layer 131, the electrochromic layer 132, and the insulating porous layer. It does not have to be formed on each side surface of 133, the second electrode layer 134, and the deterioration prevention layer 135.

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, on the electrochromic layer 132, a second electrode layer 134 is provided so as to face the first electrode layer 131 via the insulating porous layer 133.
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 prevention layer 135 is provided on the outside of the second electrode layer 134. The deterioration prevention layer 135 is also porous with a large number of through holes penetrating in the thickness direction, and is filled with an electrolyte (not shown).

In the electrochromic photochromic lens 110, by applying a voltage between the first electrode layer 131 and the second electrode layer 134, the electrochromic layer 132 undergoes a redox reaction by exchanging electric charges to develop and decolorize. ..

The manufacturing process of the electrochromic photochromic lens 110 includes a step of sequentially laminating a first electrode layer 131 and an electrochromic layer 132 on the lens 120, and a first step of laminating the first electrode layer 131 and the electrochromic layer 132 on the electrochromic layer 132 via an insulating porous layer 133. 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 of the above, and a porous structure having through holes formed on the second electrode layer 134. In 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, the deterioration prevention layer 135 and the second electrode layer 134 are interposed. The process includes a step of filling the electrolyte through the through holes formed in the deterioration prevention layer 135 and the second electrode layer 134, and a step of forming the protective layer 136 on the deterioration prevention layer 135.

Here, the through holes formed in the deterioration prevention 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 photochromic lens 110. It is a hole.

As described above, in the electrochromic photochromic lens 110 according to the present embodiment, the deterioration prevention layer 135 and the second deterioration prevention layer 135 and the second 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 through the through holes formed in the electrode layer 134 of the above. Therefore, it is possible to form the second electrode layer 134 having low resistance before filling with the electrolyte, and the performance of the electrochromic dimming lens 110 can be improved.

Further, since the deterioration prevention layer 135 is provided on the second electrode layer 134, it is possible to realize an electrochromic photochromic lens that operates repeatedly and stably.
In the present embodiment, since the 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). Therefore, the deterioration prevention layer 135 can be formed. This is because ions can move between the front and back surfaces of the second electrode layer through the through holes formed in the second electrode layer 134. As a result, since it is not necessary to form the deterioration prevention layer 135 under the second electrode layer 134, it is possible to prevent the deterioration prevention layer 135 from being damaged by sputtering or the like when forming the second electrode layer 134. it can.

Further, when the deterioration prevention layer 135 is formed, a process capable of forming a homogeneous deterioration prevention layer 135 on either the permeable insulating porous layer 133 or the second electrode layer 134 can be performed. You can choose as appropriate. Alternatively, if necessary, the deterioration prevention layer 135 may be formed both above and below the second electrode layer 134.

In FIG. 6, the electrochromic layer 132 is in contact with the first electrode layer 131 and the deterioration prevention layer 135 is in contact with the second electrode layer 134, but when one of them undergoes an oxidation reaction, the other is formed. Reduces, and when one undergoes a reduction reaction, the other undergoes an oxidation reaction. Therefore, the formed positions may be reversed. That is, the deterioration prevention layer 135 may be formed in contact with the first electrode layer 131, and the electrochromic layer 132 may be formed in contact with the second electrode layer 134.

Further, even if the electrochromic layer 132 is formed in contact with the first electrode layer 131 and the deterioration prevention layer is formed on both the upper side and the lower side of the second electrode layer 134 in contact with the second electrode layer 134. Good. Further, the deterioration prevention layer 135 is formed in contact with the first electrode layer 131, and the electrochromic layer 132 is formed on both the upper side and the lower side of the second electrode layer 134 in contact with the second electrode layer 134. May be good.

In the present invention, the deterioration prevention layer and the electrochromic layer may be referred to as an electrically active layer. That is, in the electrochromic dimming lens 110 according to the present embodiment, the thin film dimming function unit 130 has a first electrode layer 131 laminated on the lens 120 and a first electrode layer 131 laminated on the first electrode layer 131. 1. The electrically active layer, the insulating porous layer 133 laminated on the first electrically active layer, the second electrode layer 134 which is porous laminated on the insulating porous layer 133, and the first The first electroactive layer includes a second electroactive layer which is porous and is formed on either 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. One of the second electrically active layers is the electrochromic layer 132, and the other is the deterioration prevention layer 135.

In the electrochromic photochromic 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 together, and the weight is also increased. It is possible to reduce the weight and the cost.
The thickness of the thin film dimming function unit 130 is preferably 2 μm to 200 μm. If the thickness of the thin film dimming function unit 130 is made thicker than 200 μm, cracks and peeling may occur during processing of the round lens, and the optical characteristics of the lens may be affected, which is not preferable. Further, if the thickness of the thin film dimming function unit 130 is made thinner than 2 μm, a sufficient dimming function may not be obtained, which is not preferable.

FIG. 7 is a perspective view illustrating the electrochromic dimming glasses according to the present embodiment. Referring to FIG. 7, the electrochromic dimming spectacle 150 includes an electrochromic dimming lens 151, a spectacle frame 152, a switch 153, and a power supply 154. The electrochromic dimming lens 151 is a processed electrochromic dimming lens 110 into a desired shape.

The two electrochromic dimming lenses 151 are incorporated in the spectacle frame 152. The spectacle frame 152 is provided with a switch 153 and a power supply 154. The power supply 154 is electrically connected to the first electrode layer 131 and the second electrode layer 134 via a switch 153 by 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. The state can be selected.

As the switch 153, for example, any switch such as a slide switch or a push switch can be used. However, at least the above-mentioned three states should be switchable. As the power source 154, for example, any DC power source such as a button battery or a solar cell can be used. The power supply 154 can apply a voltage of about plus or minus several V 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 dimming lenses 151 develop a predetermined color. Further, by applying a negative voltage between the first electrode layer 131 and the second electrode layer 134, the two electrochromic dimming lenses 151 are decolorized and become transparent.

However, due to the characteristics of the material used for the electrochromic layer 132, the color is developed by applying a negative voltage between the first electrode layer 131 and the second electrode layer 134, and the color is decolorized by applying a positive voltage. It may be transparent. After the color is developed once, the color development continues even if no voltage is applied between the first electrode layer 131 and the second electrode layer 134.

Hereinafter, the materials and the film forming method of each component constituting the electrochromic photochromic lens 110 according to the present embodiment will be described in detail.
<Lens>
The material of the lens 120 is not particularly limited as long as it functions as a lens for spectacles, but a material having high transparency, thin thickness, and 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 coefficient of linear expansion are preferable.

Specifically, in addition to glass, any of those described in the technical outline document on high-refractive-index spectacle lenses of the Patent Office can be used, and episulfide resin, thiourethane resin, methacrylate resin, and polycarbonate can be used. System resins, urethane resins, etc. and mixtures thereof can be used. Further, if necessary, a hard coat or a primer for improving adhesion may be formed.
In the present invention, the lens includes a lens whose power (refractive index) has not been adjusted (such as a simple glass plate).

<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 it is used as a dimming glass, light transmission is ensured. Since it is necessary, a transparent conductive material that is transparent and has excellent conductivity is used. As a result, the transparency of the glass can be obtained and the contrast of coloring can be further enhanced.
As the transparent conductive material, an inorganic material such as ITO, FTO, or ATO can be used. In particular, either 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 deposition. It is preferable to use an inorganic material containing one.

In oxide, Sn oxide, and Zn oxide are materials that can be easily formed into a film by a sputtering method, and also have good transparency and electrical conductivity. Further, a particularly preferred material is _{InSnO, GaZnO, SnO, In 2} O 3, ZnO. Furthermore, transparent network electrodes such as silver, gold, carbon nanotubes, and metal oxides and composite layers thereof are also useful. The network electrode is an electrode obtained by forming carbon nanotubes, other highly conductive non-permeable materials, or the like into a fine network to have transmittance.

The film thickness of each of the first electrode layer 131 and the second electrode layer 134 is adjusted so that the electric resistance value required for the redox reaction of the electrochromic layer 132 can be obtained. When ITO is used as the material of the first electrode layer 131 and the second electrode layer 134, the film thickness of each of the first electrode layer 131 and the second electrode layer 134 may be, for example, 50 to 500 nm. it can.

As a method for producing each of the first electrode layer 131 and the second electrode layer 134, a vacuum vapor deposition method, a sputtering method, an ion plating method, or the like can be used. Further, if the materials of the first electrode layer 131 and the second electrode layer 134 can be applied and formed, the spin coating method, the casting method, the microgravure coating method, the gravure coating method, the bar coating method, and the roll coating method are used. Method, Wirer 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 the above can be used.

In the present embodiment, the second electrode layer 134 is formed with 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 method shown below. That is, a method can be used in which a layer having irregularities is formed in advance as a base layer before the second electrode layer 134 is formed, and the second electrode layer 134 having irregularities is used as it is.

Further, a method may be used in which a convex structure such as a micropillar is formed before the second electrode layer 134 is formed, and the convex structure is removed after the formation of the second electrode layer 134. Further, a method is used in which a foamable polymer polymer or the like is sprayed before forming the second electrode layer 134, and after the second electrode layer 134 is formed, treatment such as heating or deaeration is performed to foam the second electrode layer 134. You may. Further, a method of forming pores by radiating various types of radiation directly onto the second electrode layer 134 may be used.

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

As a method for 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, a desired photoresist pattern is first formed, then a second electrode layer 134 is formed, and then an unnecessary portion on the photoresist pattern is removed by removing the photoresist pattern, so that the second electrode layer 134 is formed. This is a method of forming fine through holes in the electrode layer 134 of the above.

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 on the object can be small in order to avoid damage to the lower layer due to light irradiation. It is preferable to use a negative type photoresist.

Examples of negative photoresists include polyvinyl cinnamate, styrylpyridinium formalized polyvinyl alcohol, glycol methacrylate / polyvinyl alcohol / initiator, polyglycidyl methacrylate, halomethylated polystyrene, diazoresin, bisazide / diene rubber, and polyhydroxystyrene /. Examples thereof include a melamine / photoresist generator, a methylated melamine resin, and a methylated urea resin.

Further, it is also possible to form a fine through hole in the second electrode layer 134 by a processing apparatus using a laser beam.

The diameter of the fine through holes provided in the second electrode layer 134 is preferably 10 nm or more and 100 μm or less. If the diameter of the through hole is smaller than 10 nm (0.01 μm), there is a problem that the permeation of electrolyte ions is deteriorated. Further, when the diameter of the fine through hole is larger than 100 μm, it is at a level that can be visually recognized (the size of one pixel electrode (one counter electrode) in a normal display), and a problem occurs in the display performance directly above the fine through hole. It will be.

The ratio of the hole area (hole density) to the surface area of the second electrode layer 134 of the fine through holes provided in the second electrode layer 134 can be appropriately set, and is, for example, 0.01 to 40%. be able to. If the hole density is too high, the surface resistance of the second electrode layer 134 becomes large, so that a problem occurs in which a chromic defect occurs due to a large area without the second electrode layer 134. Further, if the hole density is too low, the permeability of the electrolyte ions deteriorates, which also causes a problem in driving.

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

<Insulating porous layer>
The insulating porous layer 133 has a function of separating 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 may be porous, and is not particularly limited, but is an organic material or an inorganic material having high insulation and durability and excellent film forming property, and a composite thereof. It is preferable to use the body.

As a method for forming the insulating porous layer 133, for example, a sintering method (a polymer fine particles or inorganic particles are partially fused by adding a binder or the like to utilize pores formed 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 a solvent-soluble organic substance or inorganic substance and a binder that is insoluble in the solvent, etc., the organic substance or the inorganic substance is dissolved with a solvent to form a fine layer. (To obtain a hole) or the like may be used.

Further, as a method for forming the insulating porous layer 133, a foaming method in which a polymer polymer or the like is heated or degassed to foam it, or a good solvent and a poor solvent are operated to phase-separate a mixture of polymers. A forming method such as a phase conversion method or a radiation irradiation method in which various types of radiation are radiated to form pores may be used. Specific examples include a polymer mixed particle film containing metal oxide fine particles (SiO ₂ particles, Al ₂ O ₃ particles, etc.) and a polymer binder, a porous organic film (polyurethane resin, polyethylene resin, etc.), and a porous film. Examples thereof include an inorganic insulating material film formed in.

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

Further, the insulating porous layer 133 is preferably used in combination with the inorganic film. This causes damage to the organic substances of the lower insulating porous layer 133 and the electrochromic layer 132 when the second electrode layer 134 formed on the surface of the insulating porous layer 133 is formed by the sputtering method. This is to reduce it.

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 formed at high speed by a sputtering method without damaging the electrochromic layer 132 or the like. Further, ZnS-SiO ₂ , ZnS-SiC, ZnS-Si, ZnS-Ge and the like may be used as a material containing ZnS as a main component.

Here, the content of ZnS 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-mentioned material as the insulating porous layer 133, a good insulating effect can be obtained with a thin film, and a decrease in film strength and a film peeling can be prevented.

<Deterioration prevention layer>
The role of the deterioration prevention layer 135 is to undergo a chemical reaction opposite to that of the electrochromic layer 132, and the first electrode layer 131 and the second electrode layer 134 are corroded or deteriorated by an irreversible redox reaction by balancing the electric charges. It is to suppress what you do. As a result, the repeatability of the electrochromic photochromic lens 110 is improved. The reverse reaction includes not only the case where the deterioration prevention layer is redox-reduced but also the case where it acts as a capacitor.

The material of the deterioration prevention 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 the irreversible redox reaction. As the material of the deterioration prevention layer 135, for example, antimony oxide, nickel oxide, titanium oxide, zinc oxide, tin oxide, or a conductive or semiconductor metal oxide containing a plurality of them can be used. Further, if the coloring of the deterioration prevention layer is not a problem, the same material as the above-mentioned electrochromic material can be used.

The deterioration prevention layer 135 can be made of a porous thin film that does not hinder the injection of the electrolyte. For example, conductive or semiconductor metal oxide fine particles such as antimony oxide, nickel oxide, titanium oxide, zinc oxide, and tin oxide, for example, acrylic, alkyd, isocyanate, urethane, epoxy, and phenolic binders. By immobilizing it on the second electrode layer 134, it is possible to obtain a suitable porous thin film that satisfies the permeability of the electrolyte and the function as a deterioration prevention layer.

Alternatively, as the material of the deterioration prevention layer 135, a material that maintains a transparent state as the electric charge is transferred may be used. For example, conductive polymers such as polypyrrole-based, polythiophene-based, polyaniline-based, or derivatives thereof, hybrid polymers of metal complexes and organic ligands, radical polymers, and the like can be mentioned. When these are used, it is necessary to adjust the film density so as not to hinder 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 semiconductor fine particles described above may be used 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 the deterioration prevention layer 135. As a specific example, titanium oxide, tin oxide, zinc oxide, or compound particles or a mixture containing a plurality of them, which are composed of primary particle size particles of 100 nm or less, can be used.

Further, when these deterioration prevention layers 135 are used, it is preferable that the electrochromic layer 132 is 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 polymeric material. A film can be easily formed by a coating forming process or the like, and the color can be adjusted and controlled by the molecular structure. Examples of these organic polymer materials are poly (3,4-ethylenedioxythiophene) -based materials, bis (terpyridine) and iron ion complex-forming polymers.

As a method for forming the deterioration prevention layer 135, a vacuum vapor deposition method, a sputtering method, an ion rating method, or the like can be used. If the material of the deterioration prevention layer 135 can be applied and formed, the spin coating method, casting method, microgravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, etc. 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) is used as the electrolytic solution through the deterioration prevention layer 135 and from the fine through holes formed in the second electrode layer 134 to the first electrode layer 131 and the second electrode layer 131. The insulating porous layer 133 arranged between the electrode layer 134 and 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, is in contact with the electrochromic layer 132, and penetrates the second electrode layer 134. It is provided so as to be in contact with the deterioration prevention layer 135 through the holes. As the electrolytic solution, a liquid electrolyte such as an ionic liquid or a solution in which a solid electrolyte is dissolved in a solvent can be used.

As the material of the electrolyte, for example, inorganic ionic salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, acids and supporting salts of alkalis 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 (ClO ₄ ) ₂ . BF ₄ ) ₂ etc. can be used.

Ionic liquids can also be used. The ionic liquid may be any substance that is generally researched and reported. In particular, organic ionic liquids have a molecular structure that exhibits a liquid in a wide temperature range including room temperature.

Examples of the molecular structure include imidazole derivatives such as N, N-dimethylimidazole salt, N, N-methylethyl imidazole salt, N, N-methylpropyl imidazole salt as cation components, N, N-dimethylpyridinium salt, N, Examples include aromatic salts such as pyridinium derivatives such as N-methylpropylpyridinium salt, and aliphatic quaternary ammonium salts such as tetraalkylammonium such as trimethylpropylammonium salt, trimethylhexylammonium salt and triethylhexylammonium salt.
The anionic component often containing fluorine in view of stability compounds in an _{^{air, BF 4 -, CF 3 SO}} 3 -, PF 4 -, (CF 3 SO 2) 2 N - , and the like. An ionic liquid formulated by combining these cation components and anion components can be used.

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

Further, the electrolytic solution does not have to be a low-viscosity liquid, and can take various forms such as a gel form, a polymer crosslinked type, and a liquid crystal dispersed type. It is preferable to form the electrolytic solution in the form of a gel or a solid from the viewpoint of improving the device strength, improving the reliability, and preventing color diffusion. As the solidification method, a method of retaining 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 as compared with a method of forming a thin film by thermal polymerization or evaporation of a solvent.

<Protective layer>
The role of the protective layer 136 is unnecessary for protecting the element from external stress and chemicals in the cleaning process, preventing leakage of electrolytes, and for stable operation of electrochromic elements such as atmospheric moisture and oxygen. 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 type resin or a thermosetting type resin can be used, and specifically, an acrylic type, urethane type, epoxy type resin or the like is preferably used. As the process for forming 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.
Further, it is preferable that the electrochromic photochromic lens 110 is provided with a hard coat layer for preventing scratches and an antireflection layer for suppressing reflection, if necessary, in addition to the protective layer 136.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.

(Example 1)
According to the description of (Manufacturing method of electrochromic display element) in the first embodiment described above, the electrochromic display element shown in FIG. 1 was manufactured as follows. At this time, the transparency of the supported particle film formed on the ITO glass substrate in the manufacturing process was measured, and the transparency of the completed transmissive element was measured. In the case of a reflective element, the reflectance at the time of 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 of a liquid crystal composition for PNLC manufactured by DIC Corporation, a monomer composition, and a polymerization initiator (product name: PNM-170) was mixed thereto. 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 specify the layer thickness of the produced electrolyte layer, spherical resin beads having a particle size of 10 μm were dispersed in the precursor material of the electrolyte at a concentration of 0.2 wt%.

(2) Preparation 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 a display substrate 21 by a sputtering method, and a first display electrode is formed. 22 was made. The surface resistance of the first display electrode 22 was about 200Ω.
A coating film having tin oxide was formed on this. The coating liquid was prepared as follows. Further, the tin oxide sol solution used is a transparent solution and does not cause any precipitation even when left to stand.

Tin oxide sol solution (manufactured by Nissan Chemical Industries, Ltd., Cernax CX-S510M): 5.50 g, ethyl cellulose (10 cp, 10 wt%, ethanol solution): 1.00 g, Tin (IV) tetra (t-butoxide): 0.50 g , Terpineol: 9.05 g was mixed, treated with an ultrasonic homogenizer for 2 minutes, and then volatile components were removed with an evaporator to obtain a desired paste. This paste was applied to a film thickness of 1 μm with a screen printing machine, dried with warm air (120 ° C. for 5 minutes), and then subjected to UV / ozone treatment (150 ° C. for 30 minutes) to form a supported particle film. In this state, that is, when the ITO glass substrate on which the supported particles were formed was measured with a haze meter (Nippon Denshoku Kogyo: NDH 7000), the haze (haze (1)) was 0.78%.

A TFP solution containing 1 wt% of the electrochromic compound "4,4'-(isooxazole-3,5-diyl) bis (1- (2-phosphonoethyl) pyridinium) bromide" was spin-coated on this, and 120 The first electrochromic layer 23 was formed by annealing at ° C. for 10 minutes. When the haze was measured at this point, the haze (haze (2)) was 0.84%.

A protective layer was formed by applying a 0.1 wt% ethanol solution of poly-N-vinylamide and a 0.5 wt% aqueous solution of polyvinyl alcohol on this by a spin coating method.
On this, ZnS-SiO ₂ having a composition ratio of 8: 2 was formed by a sputtering method so as to have a film thickness of 140 nm to form a first insulating layer 24.
A second display electrode 25 was formed on the ITO film by forming a film with a thickness of about 100 nm by a sputtering method. The surface resistance of the second display electrode 25 was about 200Ω.
On this, a coating film having tin oxide as described above was formed in the same manner.
A TFP containing 1 wt% of the electrochromic compound "4,4'-(1-Phenyl-1H-pyrrole-2,5-diyl) bis (1- (4-phosphonomethyl) benzyl) pyridinium" broimide. The solution was applied by a spin coating method and subjected to annealing treatment at 120 ° C. for 10 minutes to form the second electrochromic layer 26.
A protective layer was formed by applying a 0.1 wt% ethanol solution of poly-N-vinylamide and a 0.5 wt% aqueous solution of polyvinyl alcohol on this by a spin coating method.
On this, ZnS-SiO ₂ having a composition ratio of 8: 2 was formed by a sputtering method so as to have a film thickness of 140 nm to form a second insulating layer 27.
A third display electrode 28 was formed on the ITO film by a sputtering method so as to have a thickness of about 100 nm. The surface resistance of the third display electrode 28 was about 200Ω.

A coating film having tin oxide as described above was formed on the coating film in the same manner.
On top of that, the electrochromic compounds [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 was applied by a spin coating method and annealed at 120 ° C. for 10 minutes to form a third electrochromic layer 29.
Titanium oxide particles (average particle size: 300 nm) and a TFP dispersion of an aqueous polyurethane resin were spin-coated onto the white reflective layer 31 by annealing at 120 ° C. for 10 minutes.
Then, each display electrode, each electrochromic layer, and the white reflective layer 31 were surrounded by the wall member 36.
The structure composed of each display electrode, each electrochromic layer, the white reflection layer 31, and the wall member created here is referred to as a "first structure" for convenience.

(3) Preparation of a plurality of counter electrodes and charge holding layers A TFT layer 34 (drive element layer) having a plurality of drive elements at a density of 140 ppi was formed on a glass substrate (40 mm × 40 mm) as the counter substrate 35.
After forming an ITO film having a diameter of about 100 nm on the entire surface of the TFT layer 34 by a sputtering method, a plurality of counter electrodes 33 corresponding to a plurality of driving elements were produced by photolithography.
On top of this, a TFP dispersion of aqueous polyurethane resin and ATO nanoparticles (manufactured by Mitsubishi Materials) (mixing ratio of ATO and polymer is 45:55 by weight) is spin-coated and annealed at 120 ° C. for 15 minutes. , The charge holding layer 32 was formed. Here, the thickness of the charge holding layer 32 was 0.64 μm, and its surface resistance was 1.0E + 06 (Ω / □).
The structure composed of the plurality of counter electrodes 33 and the charge holding layer 32 created here is referred to as a "second structure" for convenience.

(4) Preparation of Electrochromic Display Element The precursor material of the electrolyte prepared in (1) above was applied (injected) from above the white reflective layer 31 in the first component prepared in (2) above.
On top of this, the charge holding layer 32 in the second structure produced in the step (3) was superposed.
An ultraviolet ray having a center wavelength of 365 nm was irradiated from a plurality of pixel electrodes for 2 minutes at an irradiation light intensity of 50 mW / cm ² by a high-pressure mercury lamp, and the precursor material was photopolymerized and phase-separated to form an electrolyte layer 30. ..

Next, when the driving element of the electrochromic display element thus produced was driven by a predetermined method, the first electrochromic layer 23, the second electrochromic layer 26, and the third electrochromic layer were driven. Each of the 29 displayed the 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. Also, the time required to erase the image was about 500 milliseconds. In addition, there was no phenomenon in which the color did not completely disappear and remained after the image was erased (hereinafter referred to as "color residue").

When a charge of 1.0 mC / cm ² was driven to develop a color only in the first electrochromic layer 23 of this electrochromic display element, a bright cyan color was displayed and the reflectance at 650 nm was measured. As a result, it was 2.0%.

(Comparative Example 1)
An electrochromic display element was produced in the same manner as in Example 1. However, as the supported particles, a paste made of titanium oxide particles (manufactured by Nippon Aerosil Co., Ltd., P-25) having an average particle size of 21 nm was used to form a supported particle film having a thickness of about 1 μm. The method for producing this paste is as follows. The other two supported particle films were formed in the same manner.

Titanium oxide: 2.7 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 to obtain a primary dispersion. It was. This primary dispersion: 22.2 g, ethyl cellulose (10 wt%, ethanol solution): 1.0 g, terpineol: 10 g are mixed, treated with an ultrasonic homogenizer for 2 minutes, and then volatile components are removed with an evaporator to remove the desired paste. Got This paste was applied to a film thickness of 1 μm with a screen printing machine, dried with warm air (120 ° C. for 5 minutes), and then subjected to UV / ozone treatment (150 ° C. for 30 minutes) to form a titanium oxide coating film.

When the haze was measured at the same timing as in Example 1, it was 5.91% when only one layer of the supported particle film was formed, and when the electrochromic compound solution was applied to form the first electrochromic layer 23. It was 6.14%. Further, when it was driven in the same manner as in Example 1, the time required to obtain an image was about 500 ms, which was equivalent to that of Example 1, but the time required to erase the image was about 3000 ms. The result was very slow as compared with Example 1. Further, unlike Example 1, color residue was generated and could not be completely erased.

Then, when a charge of 1.0 mC / cm ² was applied only to the first electrochromic layer 23 of the completed electrochromic display element to develop a color, a slight white turbidity was felt in the cyan color. The reflectance at 650 nm was measured and found to be 8.9%, which was inferior to that of Example 1.

(Comparative Example 2)
An electrochromic display device was produced using titanium oxide particles in the same manner as in Comparative Example 1. However, the display element was manufactured without forming the white reflective layer 31.
When the haze was measured at the same timing as in Example 1, 6.01% was obtained when only one supported particle film was formed, and when the first electrochromic layer 23 was formed by applying the electrochromic compound solution. It was 6.22%.
Then, when the haze of the completed transmissive display element was measured, the haze (haze (3)) was 10.7%, which was higher than that of Example 1.

(Comparative Example 3)
An electrochromic display element was produced in the same manner as in Example 1. However, as the supported particles, a paste made of tin oxide particles (manufactured by CI Kasei Co., Ltd., Nanotech) having an average particle size of 30 nm was used, and a supported particle film having a film thickness of about 1 μm was formed by spin coating. The method for producing this paste is as follows. In addition, the other two supported particle films were formed in the same manner.

Tin oxide (manufactured by CI Kasei Co., Ltd., Nanotech): 2.7 g, Tin (IV) tetra (t-butoxide): 0.5 g, methanol: 20 g, dispersed for 2 hours using zirconia beads and a paint shaker 1 The next dispersion was obtained. This primary dispersion was an opaque liquid and precipitated when left to stand for 2 hours. This primary dispersion: 22.2 g, ethyl cellulose (10 wt%, ethanol solution): 1.0 g, terpineol: 10 g are mixed, treated with an ultrasonic homogenizer for 2 minutes, and then volatile components are removed with an evaporator to remove the desired paste. Got This paste was applied to a film thickness of 1 μm with a screen printing machine, dried with warm air (120 ° C. for 5 minutes), and then subjected to UV / ozone treatment (150 ° C. for 30 minutes) to form a tin oxide coating film. Except for this, a display element was produced and evaluated in the same manner as in Example 1.

When the haze was measured at the same timing as in Example 1, it was 2.47% when only one supported particle film was formed, and when the electrochromic compound solution was applied to form the first electrochromic layer 23. It was 2.77%. Further, when driven in the same manner as in Example 1, the time required to obtain an image was about 500 ms, and the time required to erase the image was about 500 ms, which was equivalent to that of Example 1. In addition, no color residue occurred as in Example 1.
Then, when a charge of 1.0 mC / cm ² was applied only to the first electrochromic layer 23 of the completed electrochromic display element to develop a color, a slight white turbidity was felt in the cyan color. When the reflectance at 650 nm was measured, it was 6.2%, which was the result that the reflectance was inferior as described in Example 1.

As is clear from the above, the supported particle film prepared by dispersing and applying tin oxide powder has the same responsiveness as the supported particle film of tin oxide prepared from the sol solution, but has a haze rate. And the reflectance is inferior.

(Example 2)
An electrochromic display element was produced in the same manner as in Example 1. However, the display element was manufactured without forming the white reflective layer 31.
When the haze was measured at the same timing as in Example 1, 0.88% was obtained when only one supported particle film was formed, and 0.88% was obtained when the electrochromic compound solution was applied to form the first electrochromic layer 23. It was 0.91%.
The haze of the completed transmissive display element was measured and found to be 2.1%.
From the comparison with Comparative Example 2, it was confirmed that the transparency of the device was improved by using tin oxide formed from the sol solution.

(Example 3)
Tin oxide sol solution (manufactured by Nissan Chemical Industries, Ltd., Cernax CX-S510M): 5.50 g, ethyl cellulose (10 cp, 10 wt%, ethanol solution): 1.00 g, Tin (IV) tetra (t-but oxide): 0.50 g , Terpineol: 9.05 g, tin oxide sol solution (manufactured by Nissan Chemical Industries, Ltd., Cernax CX-S510M): 5.50 g, ethyl cellulose (10 cp, 10 wt%, ethanol solution): 1.00 g, Tin (IV) tetra ( Example 1 except that t-butoxide): 0.25 g, Tetrakis (2,4-pentadionato) titanium (IV) (ca.63% in 2-Propanol): 0.397 g, and terpineol: 9.05 g. A display element was produced and evaluated in the same manner as in the above.

When the haze was measured at the same timing as in Example 1, it was 0.79% when only one layer of the supported particle film was formed, and 0.79% when the electrochromic compound solution was applied to form the first electrochromic layer 23. It was 0.86%. Further, when driven in the same manner as in Example 1, the time required to obtain an image was about 500 ms, and the time required to erase the image was about 500 ms, which was the same result as in Example 1. there were. Further, as in Example 1, no color residue was generated and the color was completely erased.
Then, when a charge of 1.0 mC / cm ² was applied only to the first electrochromic layer 23 of the completed electrochromic display element to develop a color, a slight white turbidity was felt in the cyan color. When the reflectance at 650 nm was measured, it was 1.8%, and good performance was obtained.

(Example 4)
Tin oxide sol solution (manufactured by Nissan Chemical Industries, Ltd., Cernax CX-S510M): 5.50 g, ethyl cellulose (10 cp, 10 wt%, ethanol solution): 1.00 g, Tin (IV) tetra (t-but oxide): 0.50 g , Terpineol: 9.05 g, tin oxide sol solution (manufactured by Nissan Chemical Industries, Ltd., Cernax CX-S510M): 5.50 g, ethyl cellulose (10 cp, 10 wt%, ethanol solution): 1.00 g, Tin (IV) acetate: Displayed in the same manner as in Example 1 except that it was changed to 0.25 g, Tetrakis (2,4-pentadionato) titanium (IV) (ca.63% in 2-Propanol): 0.397 g, and terpineol: 9.05 g. The device was made and evaluated.

When the haze was measured at the same timing as in Example 1, it was 0.75% when only one supported particle film was formed, and when the electrochromic compound solution was applied to form the first electrochromic layer 23. It was 0.83%. Further, when driven in the same manner as in Example 1, the time required to obtain an image was about 500 ms, and the time required to erase the image was about 500 ms, which was the same result as in Example 1. there were. Further, as in Example 1, no color residue was generated and the color was completely erased.
Then, when a charge of 1.0 mC / cm ² was applied only to the first electrochromic layer 23 of the completed electrochromic display element to develop a color, a slight white turbidity was felt in the cyan color. When the reflectance at 650 nm was measured, it was 1.9%, and good performance was obtained.

(Example 5)
Tin oxide sol solution (manufactured by Nissan Chemical Industries, Ltd., Cernax CX-S510M): 5.50 g, ethyl cellulose (10 cp, 10 wt%, ethanol solution): 1.00 g, Tin (IV) tetra (t-but oxide): 0.50 g , Terpineol: 9.05 g, tin oxide sol solution (Nissan Chemical Industries, Ltd., Cernax CX-S510M): 5.50 g, ethyl cellulose (10 cp, 10 wt%, ethanol solution): 1.00 g, Bis (2,4-2,4- Pentadionato) tin (IV) dichloride: 0.25g, Tetrakis (2,4-pentadionato) titanium (IV) (ca.63% in 2-Propanol): 0.397g, terpineol: 9.05g A display element was produced and evaluated in the same manner as in Example 1.

When the haze was measured at the same timing as in Example 1, 0.77% was obtained when only one supported particle film was formed, and 0.77% was obtained when the electrochromic compound solution was applied to form the first electrochromic layer 23. It was 0.84%. Further, when driven in the same manner as in Example 1, the time required to obtain an image was about 500 ms, and the time required to erase the image was about 500 ms, which was the same result as in Example 1. there were. Further, as in Example 1, no color residue was generated and the color was completely erased.
Then, when a charge of 1.0 mC / cm ² was applied only to the first electrochromic layer 23 of the completed electrochromic display element to develop a color, a slight white turbidity was felt in the cyan color. When the reflectance at 650 nm was measured, it was 1.8%, and good performance was obtained.

(Example 6)
Tin oxide sol solution (manufactured by Nissan Chemical Industries, Ltd., Cernax CX-S510M): 5.50 g, ethyl cellulose (10 cp, 10 wt%, ethanol solution): 1.00 g, Tin (IV) tetra (t-but oxide): 0.50 g , Terpineol: 9.05 g, tin oxide sol solution (Nissan Chemical Industries, Ltd., Cernax CX-S510M): 5.50 g, ethyl cellulose (10 cp, 10 wt%, ethanol solution): 1.00 g, Bis (2,4-2,4- A display element was prepared and evaluated in the same manner as in Example 1 except that pentadionato) tin (IV) dichloride: 0.25 g, Titanium (IV) tetraisopropoxide: 0.25 g, and terpineol: 9.05 g.

When the haze was measured at the same timing as in Example 1, 0.77% was obtained when only one supported particle film was formed, and 0.77% was obtained when the electrochromic compound solution was applied to form the first electrochromic layer 23. It was 0.83%. Further, when driven in the same manner as in Example 1, the time required to obtain an image was about 500 ms, and the time required to erase the image was about 500 ms, which was the same result as in Example 1. there were. Further, as in Example 1, no color residue was generated and the color was completely erased.
Then, when a charge of 1.0 mC / cm ² was applied only to the first electrochromic layer 23 of the completed electrochromic display element to develop a color, a slight white turbidity was felt in the cyan color. When the reflectance at 650 nm was measured, it was 2.0%, and good performance was obtained.

(Example 7)
Examples except that the UV / ozone (150 ° C., 30 minutes) treated after applying and drying the paste formed from tin oxide sol was changed to microwave (microwave oven: Toshiba ER-BS10, 1000 W, 2 minutes). An element was produced and evaluated in the same manner as in 1.

When the haze was measured at the same timing as in Example 1, 0.82% was obtained when only one supported particle film was formed, and 0.82% was applied when the electrochromic compound solution was applied to form the first electrochromic layer 23. It was 0.90%. Further, when driven in the same manner as in Example 1, the time required to obtain an image was about 500 ms, and the time required to erase the image was about 500 ms, which was the same result as in Example 1. there were. Further, as in Example 1, no color residue was generated and the color was completely erased.
Then, when a charge of 1.0 mC / cm ² was applied only to the first electrochromic layer 23 of the completed electrochromic display element to develop a color, a bright cyan color was displayed. When the reflectance at 650 nm was measured, it was 1.9%, and good performance was obtained.

(Example 8)
Examples except that the UV / ozone (150 ° C., 30 minutes) treated after applying and drying the paste formed from tin oxide sol was changed to microwave (microwave oven: Toshiba ER-BS10, 700W, 10 minutes). An element was produced and evaluated in the same manner as in 1.

When the haze was measured at the same timing as in Example 1, it was 0.79% when only one layer of the supported particle film was formed, and 0.79% when the electrochromic compound solution was applied to form the first electrochromic layer 23. It was 0.88%. Further, when driven in the same manner as in Example 1, the time required to obtain an image was about 500 ms, and the time required to erase the image was about 500 ms, which was the same result as in Example 1. It was. Further, as in Example 1, no color residue was generated and the color was completely erased.
Then, when a charge of 1.0 mC / cm ² was applied only to the first electrochromic layer 23 of the completed electrochromic display element to develop a color, a bright cyan color was displayed. When the reflectance at 650 nm was measured, it was 1.8%, and good performance was obtained.

(Example 9)
The same as in Example 1 except that the UV / ozone (150 ° C. for 30 minutes) treated after applying and drying the paste formed from tin oxide sol was changed to heat treatment (250 ° C. for 10 minutes) on a hot plate. The device was manufactured and evaluated.

When the haze was measured at the same timing as in Example 1, 0.84% was obtained when only one supported particle film was formed, and 0.84% was obtained when the electrochromic compound solution was applied to form the first electrochromic layer 23. It was 1.02%. Further, when driven in the same manner as in Example 1, the time required to obtain an image was about 500 ms, and the time required to erase the image was about 500 ms, which was the same result as in Example 1. there were. Further, as in Example 1, no color residue was generated and the color was completely erased.
Then, when a charge of 1.0 mC / cm ² was applied only to the first electrochromic layer 23 of the completed electrochromic display element to develop a color, a bright cyan color was displayed. When the reflectance at 650 nm was measured, it was 2.1%, and good performance was obtained.

From the above results, the performance of the electrochromic display device of the present invention may deteriorate as compared with Example 1 and Comparative Example 3 even if the same tin oxide is not formed from the sol solution. I understand. Further, from Examples 1 to 9 and Comparative Examples 1 and 2, it can be seen that the performance is further lowered when titanium oxide is used instead of tin oxide.

(Example 10)
In Example 10, an example of manufacturing the electrochromic dimming lens 110 shown in FIG. 6 is shown.
<Formation of the first electrode layer and electrochromic layer>
First, a lens having a diameter of 65 nm was prepared, and an ITO film was formed into a 25 mm × 45 mm region and a lead-out portion via a metal mask to a thickness of about 100 nm by a sputtering method to form a first electrode layer 131. ..
A tin oxide coating film was formed on the ITO film in the same manner as in Example 1 with a thickness of about 1 μm.
Next, the paste prepared in Example 1 was applied onto an ITO glass substrate with a screen printing machine to a thickness of 1 μm, dried with warm air (120 ° C. for 5 minutes), and then UV / ozone treated (150 ° C. for 30 minutes). ) To form a supported particle film. In this state, that is, the supported particle film (tin oxide) formed on the ITO glass substrate was measured with a haze meter (NDH 7000 manufactured by Nippon Denshoku Kogyo Co., Ltd.), and the haze was 0.76%.

Subsequently, as an electrochromic compound, a TFP solution containing 1.5 wt% of the compound represented by the following structural formula (1) was applied by the spin coating method. Then, it was supported (adsorbed) on the tin oxide coating film by annealing at 120 ° C. for 10 minutes to form the electrochromic layer 132.

<Formation of an insulating porous layer and a second electrode layer in which fine through holes are formed>
Subsequently, a SiO ₂ fine particle dispersion having an average primary particle size of 20 nm (silica solid content concentration 24.8% by weight, polyvinyl alcohol 1.2% by weight, water 74% by weight) is spin-coated on the electrochromic layer 132 for insulation. A porous porous layer 133 was formed. The film thickness of the formed insulating porous layer 133 was about 2 μm. Further, a SiO ₂ fine particle dispersion having an average primary grain of 450 nm (silica solid content concentration 1% by weight, 2-propanol 99% by weight) was spin-coated to form a mask for forming fine through holes (colloidal mask).

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

After that, ultrasonic irradiation was performed in 2-propanol for 2 minutes to remove fine particles of SiO ₂ having a diameter of 450 nm, which is a colloidal mask. By observing with a scanning electron microscope (SEM), it was confirmed that the second electrode layer 134 having fine through holes of about 250 nm was formed. The sheet resistance of the second electrode layer 134 was about 100 Ω / □.

<Formation of deterioration prevention layer>
Subsequently, an ATO particle dispersion liquid was applied as a deterioration prevention layer 135 on the second electrode layer 134 by a spin coating method. Then, by performing an annealing treatment at 120 ° C. for 15 minutes, a nanostructured semiconductor material composed of an ATO particle film of about 1.0 μm was formed.
<filling of electrolyte>
A solution prepared by mixing tetrabutylammonium perchlorate as an electrolyte and dimethyl sulfoxide and polyethylene glycol (molecular weight: 200) as a solvent at a ratio of 12/54/60 was used as an electrolytic solution. Then, the element formed up to the deterioration prevention 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, an ultraviolet curable adhesive (trade name: SD-17, manufactured by DIC Corporation) was spin-coated and cured by irradiation with ultraviolet light to form a protective layer 136 having a thickness of about 3 μm. As a result, the electrochromic photochromic lens 110 shown in FIG. 6 was obtained.

The haze of the electrochromic photochromic lens completed in this way was measured and found to be 1.04%. Next, when a charge of 1.0 mC / cm ² was applied to this electrochromic photochromic lens to develop color, the transmittance at 550 nm was 9.8%, good performance was obtained, and vivid magenta color was observed. did.

(Example 11)
Tin oxide sol solution in Example 1 (manufactured by Nissan Chemical Industries, Ltd., Cernax CX-S510M): 5.50 g, ethyl cellulose (10 cp, 10 wt%, ethanol solution): 1.00 g, Tin (IV) tetra (t-but oxide) : 0.50 g, terpineol: 9.05 g, tin oxide sol solution (manufactured by Nissan Chemical Industries, Ltd., Cernax CX-S510M): 5.00 g, ethyl cellulose (10 cp, 10 wt%, ethanol solution): 1.00 g, Tin ( IV) Change to tetra (t-butoxide): 0.50 g, cyclohexanone: 2.05 g, apply spin coat (3000 rpm, 30 seconds) to a film thickness of 1 μm on an ITO glass substrate, and dry with warm air ( A display element was prepared and evaluated in the same manner as in Example 10 except that a supported particle film was formed by UV / ozone treatment (150 ° C. for 30 minutes) after 120 ° C. for 5 minutes).

As a result, the haze of the completed electrochromic photochromic lens was measured and found to be 0.67%. Next, when a charge of 1.0 mC / cm ² was applied to this electrochromic photochromic lens to develop a color, the transmittance at 550 nm was 9.5%, good performance was obtained, and a vivid magenta color was obtained. Observed.

(Comparative Example 4)
An electrochromic display element was produced in the same manner as in Example 10. However, as the supported particles, a paste made of tin oxide particles (manufactured by CI Kasei Co., Ltd., Nanotech) having an average particle size of 30 nm was used, and a supported particle film having a film thickness of about 1 μm was formed by spin coating. The method for producing this paste is as follows. In addition, the other two supported particle films were formed in the same manner.

Tin oxide (manufactured by CI Kasei Co., Ltd., Nanotech): 2.7 g, Tin (IV) tetra (t-butoxide): 0.5 g, methanol: 20 g, dispersed for 2 hours using zirconia beads and a paint shaker 1 The next dispersion was obtained. This primary dispersion was an opaque liquid and precipitated when left to stand for 2 hours. This primary dispersion: 22.2 g, ethyl cellulose (10 wt%, ethanol solution): 1.0 g, terpineol: 10 g are mixed, treated with an ultrasonic homogenizer for 2 minutes, and then volatile components are removed with an evaporator to remove the desired paste. Got This paste was applied to a film thickness of 1 μm with a screen printing machine, dried with warm air (120 ° C. for 5 minutes), and then subjected to UV / ozone treatment (150 ° C. for 30 minutes) to form a tin oxide coating film. Except for this, a display element was produced and evaluated in the same manner as in Example 10.

As a result, the haze of the completed electrochromic photochromic lens was measured and found to be 2.49%. Next, when a charge of 1.0 mC / cm ² was applied to this electrochromic photochromic lens to develop color, the transmittance at 550 nm was 21.2%, which was lower than that of Examples 10 and 11. there were. The magenta color also felt pale turbidity.

As is clear from the above, it was found that the supported particle film prepared by dispersing and applying tin oxide powder was inferior in haze rate and color development performance as compared with the supported particle film of tin oxide prepared from the sol solution. ..

(Comparative Example 5)
An electrochromic photochromic lens was produced in the same manner as in Example 3. However, as the supported particles, titanium oxide particles having an average particle size of 30 nm (manufactured by Ishihara Sangyo Co., Ltd., TTO-51N) are used to form a supported particle film having a thickness of about 1 μm, and in this state, that is, on an ITO-formed glass substrate. The haze of the supported particle film formed in was measured and found to be 5.92%. When a charge of 1.0 mC / cm ² was applied to this electrochromic photochromic lens to develop color, the transmittance at 550 nm was 28.9%, which was lower than that of Examples 10 and 11. The magenta color also felt pale turbidity.

From the above, it can be seen that the electrochromic photochromic lens of the present invention exhibits high performance by forming a porous film of tin oxide using a tin oxide sol solution as shown in Examples 10 and 11. Further, it can be seen that even if the same tin oxide is used as shown in Comparative Example 4, the performance is deteriorated unless it is formed from the sol solution. Further, as shown in Comparative Example 5, it can be seen that the performance is further lowered when titanium oxide is used instead of tin oxide.

20 Electrochromic display element 21 Display board 22, 25, 28 Display electrodes 23, 26, 29 Electrochromic layer 23a Electrochromic compound 23b Tin oxide 30 Electrolyte layer 31 White reflective layer 32 Charge holding layer 33 Opposite electrode 34 Drive element layer 35 Opposing Board 36 Wall member 100 Information equipment (electronic book reader)
101 Display device 102 Control device (main controller)
110, 151 Electrochromic dimming lens 113 Display controller 114 VRAM
120 Lens 130 Thin film dimming function 131 First electrode layer 132 Electrochromic layer 133 Insulating porous layer 134 Second electrode layer 135 Deterioration prevention layer 136 Protective layer 150 Electrochromic dimming glasses 152 Eyeglass frame 153 Switch 154 Power supply

Japanese Unexamined Patent Publication No. 2003-121883 Japanese Unexamined Patent Publication No. 2006-106669 JP-A-2010-33016 Japanese Unexamined Patent Publication No. 2012-137736 JP-A-2015-14743

Claims (7)

Display board and
Display electrode and
An electrochromic layer provided in contact with the display electrode and
An opposing substrate provided facing the display substrate and
With the counter electrode
A charge holding layer provided in contact with the counter electrode and
An electrochromic display element having an electrolyte layer provided between the display substrate and the facing substrate.
The electrochromic layer contains at least tin oxide particles and an electrochromic compound supported on the tin oxide particles.
The electrochromic display element state, and are haze of not more than 1.02% when the display electrode and the electrochromic layer on the display substrate is formed,
An electrochromic display device characterized in that the average primary particle diameter of the tin oxide particles is less than 30 nm . The electrochromic display device according to claim 1, wherein the tin oxide particles have an average primary particle diameter of 3 to 8 nm. The electrochromic display element according to claim 2 , wherein a white reflective layer is provided between the electrochromic layer and the charge holding layer. The electrochromic display device according to any one of claims 1 to 3 .
VRAM to store display data and
A display device including a display controller that controls the electrochromic display element based on the display data. The display device according to claim 4 and
An information device including a control device for controlling information displayed on the display device. The process of forming display electrodes on the display board and
A step of forming an electrochromic layer on the display electrode and
The process of forming the counter electrode on the counter substrate and
A step of forming a charge holding layer on the counter electrode and
It has a step of laminating the display electric board and the facing board via an electrolyte layer.
In the step of forming the electrochromic layer, after forming a supporting particle layer containing tin oxide particles having an average primary particle diameter of less than 30 nm by using a tin oxide sol solution and a tin complex compound represented by the following general formula (1). , A method for manufacturing an electrochromic display element, which comprises supporting an electrochromic compound on the tin oxide particles to form the electrochromic layer.
(In the formula, A, B, C and D represent an alkyl group, an alkoxy group, an ester group, a 1,3-dicarbonyl compound or a halogen atom, which may be the same or different, and A and B may be different. , Or C and D may be coupled to each other.) The process of forming display electrodes on the display board and
A step of forming an electrochromic layer on the display electrode and
The step of forming a white reflective layer on the electrochromic layer and
The process of forming the drive element layer on the facing substrate and
A step of forming a counter electrode on the driving element layer and
A step of forming a charge holding layer on the counter electrode and
It has a step of laminating the display electric board and the facing board via an electrolyte layer.
In the step of forming the electrochromic layer, after forming a supporting particle layer containing tin oxide particles having an average primary particle diameter of less than 30 nm by using a tin oxide sol solution and a tin complex compound represented by the following general formula (1). , A method for manufacturing an electrochromic display element, which comprises supporting an electrochromic compound on the tin oxide particles to form the electrochromic layer.
(In the formula, A, B, C and D represent an alkyl group, an alkoxy group, an ester group, a 1,3-dicarbonyl compound or a halogen atom, which may be the same or different, and A and B may be different. , Or C and D may be coupled to each other. )