WO2017159221A1

WO2017159221A1 - Electrochromic rendering/displaying device

Info

Publication number: WO2017159221A1
Application number: PCT/JP2017/006119
Authority: WO
Inventors: 英之牧; 昌芳樋口
Original assignee: 学校法人慶應義塾; 国立研究開発法人物質・材料研究機構
Priority date: 2016-03-14
Filing date: 2017-02-20
Publication date: 2017-09-21
Also published as: JP6775204B2; JPWO2017159221A1

Abstract

The present invention is provided with: a substrate 10; a lower conductive film 12 disposed on the substrate; an electrochromic material 14 and an electrolyte 16 disposed on the lower conductive film; an upper transparent conductive film 24, disposed on the electrochromic material and the electrolyte, with an insulating spacer 22 interposed therebetween; a transparent film 26 disposed on the upper transparent conductive film; and a means (28) for applying a voltage between the lower transparent conductive film and the upper transparent conductive film, wherein when the transparent film is pressed from the upper surface thereof, the transparent film is bent, a gap formed by the spacer disappears, the upper transparent conductive film is brought into electrical contact with the electrochromic material or the electrolyte thereunder so as to locally pass an electrical current, an electric field is applied only to a portion, of the electrochromic material, directly under the contact point, and thereby, a local color of the electrochromic material is changed. Accordingly, the electrochromic rendering/displaying device which allows a local color change (coloring, decoloring, discoloring) by means of a simple structure is provided.

Description

Electrochromic drawing / display device

The present invention relates to an electrochromic drawing / display device, and in particular, no special driving electronic circuit for local voltage / current is required, and local color change (coloring / decoloring / discoloration) with a simple structure. The present invention relates to an electrochromic drawing / display device that can be used.

An electrochromic material is known in which a color change can be obtained reversibly by electrochemical oxidation / reduction by applying voltage / current.

Such electrochromic materials include inorganic materials and organic materials. Inorganic materials include oxides (oxides such as tungsten oxide, vanadium oxide, molybdenum oxide, iridium oxide, rhodium oxide, nickel oxide, and chromium oxide), metal complex systems (complexes such as Prussian blue and ruthenium purple), and nitriding There are various material systems such as physical systems (such as indium nitride). As organic material systems, there are various material systems such as viologen-based compounds, leuco dye-based compounds, terephthalic acid compounds, polyoxotungstates, and polymer systems (such as conductive polymer compounds and metallo supramolecular polymers).

In an electrochromic device, an electrochromic material layer and an electrolyte layer are sandwiched between electrodes and a voltage is applied to cause a color change mainly by utilizing an electrochemical reaction such as oxidation / reduction. In such an electrochromic device, the electrochromic layer includes a liquid type and a solid type, and the electrolyte layer includes a liquid type, a gel type, and a solid type.

As applications of such electrochromic devices, display devices such as electronic paper, display and viewfinder, and light shielding devices such as light control glass, electronic curtain, sunglasses and anti-glare mirror are known.

As an electronic paper display, full-color electronic paper using a viologen compound system (Non-patent Document 1), color electronic paper using a metallo supramolecular polymer (Patent Document 1), and one using Prussian blue (non-patent) Reference 2). There is a viewfinder using an oxide electrochromic material. Light control glass, electronic curtains, sunglasses, and anti-glare mirrors are also in practical use.

Also, an electrochromic printing device that prepares a drawing tool (pen) with a liquid or solid electrolyte attached to the tip of the electrochromic film, injects colored ions from the electrolyte at the tip, and draws and erases. Yes (Patent Document 2). Moreover, regarding application methods, there are electronic whiteboards, electronic memo pads (notebooks), and the like as related applications using techniques other than electrochromic.

WO2013 / 115277 publication JP 2007-163758 A

In the electronic paper and display device, voltage and current are applied locally to the electrochromic material in the thickness direction of the screen mainly by combining wiring structures such as many transparent electrodes such as matrix type. The display is realized by changing the color locally. However, there are problems that it is necessary to pattern a large number of fine electrodes and a driving electronic circuit for applying a voltage / current to a specific position.

In addition, when changing the color of the part touched with a finger or a touch pen, a separate touch screen or touch panel (matrix switch, resistive film method, surface acoustic wave method, infrared method, electromagnetic induction) is used for electronic paper and display devices. System, capacitance method, etc.) and attaching to electronic paper or display device, the position information of the touch part is electrically read and displayed on the electronic paper or display based on the position information Since a mechanism is required, a separate driving electronic circuit is required in addition to a complicated structure, which increases costs.

In devices such as dimming glass, electronic curtains, sunglasses, and anti-glare mirrors, voltage and current can be applied to the color of the entire screen using a structure in which an electrochromic material is sandwiched between conductive thin-film sheet electrodes such as transparent conductive thin films. Can be changed. However, since a two-dimensional sheet-like electrode is used, local voltage / current application cannot be performed, so only the color of the entire screen is changed, and the local color cannot be changed. If it is desired to change the color partially, it is the same as the above-described electronic paper and display, and patterning of electrodes for applying a local voltage / current and a dedicated electronic circuit for driving it are required.

Furthermore, when changing the color of the part touched with a finger or a touch pen, the touch screen / touch panel (matrix switch, resistive film method, surface acoustic wave method, infrared method, electromagnetic induction, etc. is used separately as with electronic paper and display devices. System, capacitance system, etc.), and it is necessary to attach to devices such as light control glass, electronic curtain, sunglasses, anti-glare mirror, etc. Therefore, a separate electronic circuit for driving is required as well as a complicated structure.

For this reason, touch-type electronic memo pads (notebooks) and electronic whiteboards that use electrochromic, and dimming glass, electronic curtains, sunglasses, and anti-glare mirrors that enable local color change are created. It will be expensive.

Further, in Patent Document 2, a drawing tool (pen) having a liquid or solid electrolyte portion attached to the tip is prepared for an electrochromic film, and colored ions are injected from the tip electrolyte to draw and erase. Although an electrochromic printing apparatus has been proposed, there is a problem that a special drawing tool is required to attach a liquid or solid electrolyte to the tip and inject colored ions from the tip.

In addition, some electronic notepads that do not use electrochromic currently use pressure-sensitive liquid crystal, but (1) cannot be colored only in black and white, (2) dark, (3) partial erasure However, it was impossible to correct a part of writing mistakes.

Electronic whiteboards that do not use electrochromics include electronic whiteboards that combine whiteboard projectors and hardware software, but they consist of a combination of complex and expensive software and hardware. Become.

The present invention has been made to solve the above-described conventional problems, and does not require a special driving electronic circuit for local voltage / current, and locally changes color (coloring / discharging) with a simple structure. It is an object of the present invention to provide an electrochromic drawing / display device that can be (color / discolored).

The present invention relates to a substrate, a lower conductive film disposed on the substrate, an electrochromic material and an electrolyte disposed on the lower conductive film, and a spacer having an insulating property on the electrochromic material and the electrolyte. A transparent film disposed on the upper transparent conductive film, and means for applying a voltage between the lower conductive film and the upper transparent conductive film, the transparent When the film is pushed from the upper surface, the transparent film is curved and the gap formed by the spacer is eliminated, and the upper transparent conductive film and the electrochromic material or electrolyte thereunder are in electrical contact and are locally energized. An electric field is applied only to the electrochromic material immediately below the contact point, so that the color of the electrochromic material changes locally. The transfected runner Mick drawing and display device is obtained by solving the above problems.

The present invention also provides a substrate, a lower conductive film disposed on the substrate, an electrochromic material and an electrolyte disposed on the lower conductive film, a conductor drawing tool, the drawing tool and the electro Means for applying a voltage between the chromic material and the electrolyte, and when the drawing tool is brought into contact with the electrochromic material and the electrolyte, the contact point is locally energized, and an electric field is applied only to the electrochromic material immediately below the contact point. The above-mentioned problem is similarly solved by an electrochromic drawing / display device characterized in that, when applied, the color of the electrochromic material changes locally.

Here, the electrochromic material can be disposed under or on the electrolyte.

Also, a conductive film can be disposed on the electrochromic material and the electrolyte.

Moreover, the electrochromic material can be a metallo supramolecular polymer or a conductive polymer compound.

In addition, carbon nanotubes can be mixed in the electrochromic material.

Moreover, a power source can be built in the drawing tool.

Also, local erasure and discoloration can be achieved by changing the magnitude and polarity of the voltage.

Further, it is possible to provide a means for applying a voltage between the electrochromic material and the conductive film on the electrolyte and the lower conductive film, thereby enabling the entire erasure.

In addition, an erasing electrode can be disposed on the electrochromic material and the electrolyte or conductive film.

Also, a higher voltage can be applied as the distance increases according to the distance from the erasing electrode disposed on the conductive film.

According to the present invention, a pen-type and touch-type electrochromic device capable of drawing without using a special electrode pattern, a driving electronic circuit, and a special drawing tool is realized, and in an apparatus using an electrochromic material A device that changes the color of only the part touched with a finger or a touch pen can be provided. In the present invention, since voltage / current application in a matrix format is not required, the local color at an arbitrary position can be changed without using a fine and complicated wiring structure. In addition, the pen-type and touch-type electrochromic device based on the principle of the present invention does not require a special driving electronic circuit for local voltage / current, and has a simple structure for local color change (coloring and coloring). Erasing / discoloring). Also, there is no need for electronic devices such as touch panels and touch screens that read the position information of the touch part, and the color of the touch part can be changed directly, eliminating the need for position detection and driving electronic circuits required for the touch panel and touch screen. It is. Furthermore, the local color at an arbitrary position can be changed without using a special drawing tool such as attaching an electrolyte part to the tip as in Patent Document 2. This enables display devices such as touch-type or pen-type electronic memo pads (notebooks) and electronic whiteboards that use electrochromic materials, and light-control glass, electronic curtains, sunglasses, and anti-reflection that enable local color changes. New devices such as light-shielding devices such as glare mirrors can be manufactured at a low cost with a simple structure.

Sectional drawing which shows (A) structure and (B) operation principle of the touch-type electrochromic device which concerns on 1st Embodiment of this invention. Figure showing the drawing example Diagram comparing the switching characteristics of electrochromic devices in polymer only and polymer / CNT blends The figure which compares and shows the electron microscope image of (A) polymer only and (B) polymer CNT mixture The figure which compares the difference of the performance by (A) existence (B) existence of the conductive film in comparison Sectional drawing which shows the structure of the touch-type electrochromic device which concerns on 2nd Embodiment of this invention. Sectional drawing which shows the structure of the touch-type electrochromic device which concerns on 3rd Embodiment of this invention. The figure which shows the example of partial deletion in 2nd Embodiment of this invention Sectional drawing which shows the structure of the touch-type electrochromic device which concerns on 4th Embodiment of this invention which added the structure for erasing the whole screen. Sectional drawing which similarly shows the structure of the touch-type electrochromic device which concerns on 5th Embodiment of this invention Sectional drawing which similarly shows the structure of the touch-type electrochromic device which concerns on 6th Embodiment of this invention. Sectional drawing which similarly shows the structure of the touch-type electrochromic device which concerns on 7th Embodiment of this invention The figure which shows the experimental example of the erasure | elimination of printing by 7th Embodiment Sectional drawing which shows the structure of the pen-type electrochromic device using the drawing tool which concerns on 8th Embodiment of this invention. Sectional drawing which shows the structure of the pen-type electrochromic device using the drawing tool which concerns on 9th Embodiment of this invention. Sectional drawing which shows the structure of the pen-type electrochromic device using the drawing tool which concerns on 10th Embodiment of this invention. Sectional drawing which shows the structure of the pen-type electrochromic device using the drawing tool which concerns on 11th Embodiment of this invention. Sectional drawing which shows the structure of the pen-type electrochromic device using the drawing tool which concerns on 12th Embodiment of this invention. Diagram showing an example of drawing by drawing a conductive bar

Hereinafter, modes for suitably carrying out the present invention (hereinafter referred to as embodiments) will be described in detail. In addition, this invention is not limited by the content described in the following embodiment and an Example. In addition, constituent elements in the embodiments and examples described below include those that can be easily conceived by those skilled in the art, those that are substantially the same, and those in a so-called equivalent range. Furthermore, the constituent elements disclosed in the embodiments and examples described below may be appropriately combined or may be appropriately selected and used.

FIG. 1A shows the configuration of a touch-type electrochromic device according to the first embodiment of the present invention. In the first embodiment, an electrochromic material 14 is disposed on a glass or plastic substrate 10 having a conductive film (lower conductive film) 12 such as a transparent conductive film, and a liquid, gel, or solid electrolyte is formed thereon. 16 is arranged. A conductive film 18 can be disposed on the electrolyte 16. A transparent film 26 with an upper transparent conductive film 24 sandwiching an insulator 20 and a spacer 22 is disposed thereon.

As shown in FIG. 1B, when the upper surface of the transparent film 26 with the upper transparent conductive film 24 is pressed with an object such as a conductive / non-conductive finger 30 or a touch pen, the transparent film 26 is bent and the insulator 20 The gap formed by the spacer 22 is eliminated, and the upper transparent conductive film 24 and the conductive film 18 or the electrolyte 16 thereunder are in electrical contact with each other and are locally energized. Here, if a voltage is applied from the power source 28 between the upper transparent conductive film 24 and the lower conductive film 12, an electric field B is applied from the local contact A obtained by bending toward the lower conductive film 12. Therefore, since the electric field B is applied only to the electrochromic material 14 immediately below the contact A, the electrochromic material 14 immediately below the contact A can be locally changed (colored, decolored, discolored) C.

According to the present embodiment, a touch-type electrochromic device is realized, and in an apparatus using an electrochromic material, the color of a part touched by an object of any shape, such as a finger or a touch pen, regardless of conductivity or non-conductivity is locally applied. Device can be provided.

According to this embodiment, since voltage / current application in a matrix format is not required, it is possible to change a local color at an arbitrary position without using a fine and complicated wiring structure.

The touch-type electrochromic device based on this embodiment does not require a touch panel or touch screen for detecting the touch part, and can directly change the color of the touch part. Therefore, there is no need for position detection and driving electronic circuits required for touch panels and touch screens, and there is no need for special driving electronic circuits for local voltages and currents. Color change is possible.

In addition, the object to be pressed for color change may be any object regardless of the presence or absence of conductivity or the shape. Since objects that are necessary for pressing do not need electrostatic conductivity, they may be worn with bare hands and fingers, or with gloves, and can be touch pens or sticks, both conductive and non-conductive. Any material or shape can be used as long as it can be pressed regardless of whether it is conductive or non-conductive, such as an object, a shape with a large contact area such as an eraser or a blackboard eraser.

This enables display devices such as touch-type electronic memo pads (notebooks) and electronic whiteboards that use electrochromic, and dimming glass, electronic curtains, sunglasses, and anti-glare mirrors that enable local color changes. New devices can be fabricated at a low cost with a simple structure.

Fig. 2 shows an actual photograph during operation of the touch-type electrochromic device. In a state where the color is erased by the touch electrochromic device, a line or a picture having an arbitrary shape can be drawn by pressing the transparent film with the upper transparent conductive film with a non-conductive touch pen.

The substrate 10 may be any material. Any material system may be used, such as all solid materials such as glass, ceramics, and semiconductors, and plastic materials such as PET. The thickness of the substrate 10 may be any thickness. When it is thin, it becomes a flexible device, and a flexible display device and a light control device capable of bending can be realized. The color of the substrate 10 may be transparent, may have color, or may be opaque. In particular, when using transmitted light as in a light control device, it is better to be transparent. In the case of transparency, it is also possible to place a background panel behind it or arrange another display, and it can be used in combination with what is placed on the background. If there is a color, for example, if a white substrate is used, it can also be used as the background of a display device such as an electronic notepad (notebook) or electronic whiteboard having a white background. In the case of an electronic memo pad (notebook) or an electronic whiteboard, a transparent substrate may be used and a colored background film or substrate may be attached separately behind the transparent substrate.

The lower conductive film 12 on the substrate 10 may be transparent or not transparent. In a display device, a light control device, or the like where light transmission is required or an application using a background color, it is better to use a transparent conductive film such as ITO, an oxide semiconductor, or an organic conductive film. When light transmittance is not required, an opaque electrode such as metal may be used.

The electrochromic material 14 may be any material type electrochromic material as long as the color changes with voltage and current. For example, such a material system includes an inorganic material system and an organic material system. Examples of inorganic materials include oxides (tungsten oxide, vanadium oxide, molybdenum oxide, iridium oxide, rhodium oxide, nickel oxide, chromium oxide, etc.), metal complexes (prussian blue, ruthenium purple, and other complexes). ) And nitride materials (such as indium nitride). Examples of organic material systems include various material systems such as viologen-based compounds, leuco dye-based compounds, terephthalic acid compounds, polyoxotungstates, and polymer systems (such as conductive polymer compounds and metallo supramolecular polymers). The conductive polymer compound refers to an organic polymer that exhibits electrical conductivity by chemical or electrochemical doping. Metallo supramolecular polymers are obtained by complex formation of transition metal ions such as iron, ruthenium, copper and cobalt, transition metal ions such as europium and organic ligands having two or more sites that can coordinate with them. Refers to a polymeric supramolecule. The electrochromic layer includes a liquid type and a solid type, and any material system may be used.

Electrochromic materials differ in voltage and speed required for color change (coloring / decoloring / discoloration) depending on the material. In an electrochromic device, it is more preferable that the response of the color change is faster, and when an electrochromic material that can change the color at high speed is used, the drawing speed in the electrochromic device is improved and the operability can be improved. is there. For example, a metallo supramolecular polymer or a conductive polymer compound has a response of about 1 second or less, and is an electrochromic device suitable for drawing.

According to the inventor's experiment, by mixing an electrochromic material such as a metallo supramolecular polymer and the carbon nanotube CNT, as shown in FIG. The improvement of the contrast of the color change was confirmed. This is presumably because pores were formed in the polymer by mixing the carbon nanotubes CNT as shown in FIG.

The electrolyte 16 disposed on the electrochromic material 14 may be any of liquid, gel, and solid electrolytes. In the case of a liquid electrolyte, it can be sealed with a conductive film or the like disposed immediately above the electrolyte. In the case of a gel / solid electrolyte, it can be placed on the electrochromic material 14 without sealing. The material system of the electrolyte 16 may be an electrolyte of any component as long as it can conduct ions necessary for an electrochemical reaction such as oxidation / reduction of the electrochromic material 14. It suffices if the electrochromic material layer and the electrolyte layer are sandwiched between electrodes and a voltage is applied to cause a color change mainly by utilizing an electrochemical reaction such as oxidation / reduction.

The conductive film 18 disposed on the electrolyte 16 may or may not be present. The conductive film 18 only needs to have conductivity in the thickness direction of the film. When a liquid is used as the electrolyte 16, the liquid can be sealed by the conductive film 18. When a gel or solid electrolyte is used, the conductive film 18 may or may not be present. When this conductive film 18 is present, compared to the case without the conductive film 18, the shape, hardness, elasticity, adhesiveness of the surface of the electrolyte 16, mechanical contact with the upper transparent conductive film 24, Electrical contact with the upper transparent conductive film 24 and the electrolyte 16 can be improved. For example, when the electrolyte 16 is mechanically soft, the shape and hardness can be imparted by providing the conductive film 18, and the elasticity and adhesiveness of the electrolyte 16 can be adjusted. Thereby, it is possible to suppress mechanical consumption of the electrolyte 16 and the upper transparent conductive film 24 and sticking of the upper transparent conductive film 24, and to improve the operational feeling of the touch panel. In addition, it is possible to adjust and improve the electrical contact from the electrolyte 16 to the upper transparent conductive film 24 for color change. Further, by adjusting the physical property value such as the work function of the conductive film 18, it is possible to adjust the voltage and the speed necessary for oxidation / reduction from the electrolyte 16 to the upper transparent conductive film 24. Adjustment and improvement of the voltage value and current value necessary for the color change of the electrochromic material 14 can also be performed. This makes it possible to improve the durability, lower power consumption, higher speed operation, and improved operability of the electrolyte 16, the conductive film 18, and the upper transparent conductive film 24.

The conductive film 18 on the electrolyte 16 may be made of any material as long as it has translucency and conductivity. In particular, in this electrochromic device, since it is necessary to apply an electric field to the conductive film 18 in the film thickness direction (perpendicular direction), the resistance decreases in the film thickness direction (perpendicular direction). Then, the locality of color change, operating voltage / current, durability, high speed, and operability of the electrochromic device can be improved. Therefore, in the case of a conductive film having no electrical resistance anisotropy, the thinner the conductive film 18 is, the locality of color change of the electrochromic device, operating voltage / current, durability, high speed, Operability is improved. In particular, when a material having a low resistivity of the conductive film is used, when the film thickness of the conductive film is increased to some extent and the resistance in the film thickness direction is increased, the in-plane direction of the conductive film is more than the resistance of the electrolyte. The electric resistance tends to be relatively low, and the entire potential in the in-plane direction of the film in the conductive film approaches the equipotential. Therefore, the locality of the color change of the electrochromic device tends to be lost. In an extreme case, the local color change cannot be performed, and only the color change of the entire electrochromic film can be obtained. Therefore, it is preferable that the resistance in the film thickness direction is low, and the locality of the color change is improved by reducing the thickness of the conductive film. If a conductive film having anisotropy in electric resistance is used, the characteristics of the electrochromic device are improved by reducing the electric resistance in the film thickness direction. In addition, when the film thickness cannot be sufficiently reduced, the locality of the color change can be maintained by using a sheet having a slightly higher sheet resistance in the in-plane direction of the conductive film.

The material of the conductive film 18 on the electrolyte may be any material as long as it is translucent and conductive in the film thickness direction. For example, any material system that is mainly used as a transparent conductive film may be used. For example, carbon-based materials such as graphite, carbon nanofibers, carbon nanotubes, graphene, etc. used as transparent conductive films and composite materials containing them, ultrathin metal films, metal thin films such as silver nanofibers, nanowires, fine particles, Any material may be used as long as it is light-transmitting and conductive, such as a conductive film using the composite material, an organic conductive film such as PEDOT, an oxide-based or semiconductor-based conductive film such as ITO or ZnO. In particular, as the electroconductive film of the electrochromic device of the present invention, since it operates by energization by an electric field in the film thickness direction, a low sheet resistance in the in-plane direction required for a normal transparent conductive film or the like is unnecessary. Even a conductive film having a high inward sheet resistance can be used. In particular, in the case of ultra-thin thin films, fine particles, fibers, and polymer-shaped conductive films, physical contact between grains, fine particles, fibers, and polymers is suppressed when trying to improve light transparency. The sheet resistance in the in-plane direction may become high, but even in such a high sheet resistance conductive film, the conductivity in the film thickness (perpendicular) direction is ensured because the film thickness is thin. In this case, an electric field is applied in the film thickness direction, so that it can be used as the conductive film of the present invention.

According to the inventor's experiment, by transferring ITO onto the electrolyte (gel) 16 as the conductive film 18, as shown in FIG. 5B, as compared with the case without the conductive film, FIG. As shown in FIG. 4, the adhesion between the electrolyte 16 and the upper transparent conductive film 24 was prevented, and the operability and durability of the touch-type upper electrode (24) could be improved.

On the electrolyte 16 or the conductive film 18, an insulator 20 to the panel frame and a spacer 22 to the inside of the panel are formed in order to provide electrical insulation by providing a gap between the upper transparent conductive film 24 and the upper transparent conductive film 24. To do. As long as the insulator 20 and the spacer 22 are insulated from the upper transparent conductive film 24, any material system may be used. If the spacer placed inside the panel should be inconspicuous when used as a display device or a light control device, it is better to use a material that is transparent or close to white, but a very small spacer is recommended so that it is difficult to see. If used, there is no problem with any color. Further, the shape, width, height, and interval of the spacer 22 are energized by pressing the film with a finger, a pen, or the like to bend while electrically insulating the electrolyte 16 or the conductive film 18 and the upper transparent conductive film 24. As long as there is a gap, it may be in the form of dots, lines, lattices, etc., and the width, height, spacing, etc. may be any size. In consideration of the mechanical and electrical properties of the electrolyte 16, the conductive film 18, and the upper transparent conductive film 24 used in the electrochromic device, by determining the shape, width, height, and interval of the spacer 22, Durability improvement, low power consumption, high speed operation, and operability improvement can be performed. In addition, when a color change (color erasure) function for the entire panel, which will be described later, is provided, the lower portion of the spacer can be provided with conductivity.

The transparent film 26 coated with the upper transparent conductive film 24 disposed on the spacer 22 only needs to have translucency and flexibility to bend by pressing.

The upper transparent conductive film 24 may be any material as long as it is transparent and conductive. Any transparent conductive material such as an oxide system such as ITO / ZnO, a semiconductor system, an organic system, a metal system, or a carbon system may be used. The material system may be used. In particular, when the conductivity in the in-plane direction is higher, low voltage driving or higher speed operation is possible. In addition, since the color change is obtained by bringing the electrolyte 16 and the conductive film 18 into electrical and physical contact with each other by pressing, the performance changes depending on the characteristics of the material such as the work function. Therefore, the material of the electrolyte 16 and the conductive film 18 It is also possible to improve the performance by selecting the material of the upper transparent conductive film 24 according to the above. Moreover, since bending distortion is applied not only to the transparent film 26 but also to the upper transparent conductive film 24 by pressing, it is preferable that durability against bending is high.

The material of the transparent film 26 is flexible so that it can be bent by pressing, and may be any material as long as it is transparent, and may be a solid material such as thin glass, or a plastic / vinyl material such as PET or PVC. . The thickness of the transparent film 26 may be anything, but the flexibility and the pressing feeling change depending on the thickness, so that the locality of color change and the operational feeling of the device can be adjusted.

The upper transparent conductive film 24, the conductive film 18, and the lower conductive film 12 are not only one type of conductive film, but also a thin coating of two or more types of electrode materials as different materials, or a patterned electrode. It may be used. As an example, when a transparent conductive film such as ITO is used as the conductive film, other kinds of conductive

dissimilar materials

12B and 18D are formed on the

conductive films

12 and 18 as in the second embodiment shown in FIG. A thin coating in the form of dots (in the example of FIG. 6, D material is formed on the lower conductive film 12B made of B material on the lower conductive film 12A made of A material and the conductive film 18C made of C material (lower in the figure)) The conductive film 18D) can be arranged in a pattern such as a dot shape, a line shape, or a lattice shape. When a conductive film composed of two or more materials as described above is used as an electrode of an electrochromic device, the potential (potential) and contact resistance required for oxidation / reduction differ depending on the material, so color change (coloring / Decolorization and discoloration) can be reduced in voltage and speed, and the durability and operability of electrochromic devices can be improved. For example, in the case of an electrochromic material, when one type of electrode is used, the work function of the electrode material is constant on the electrode, and the ease of oxidation and reduction is different. The speed of change varies greatly, for example, coloring may be at a low voltage and high speed, but decoloring may be at a high voltage and low speed. On the other hand, for example, as shown in FIG. 6, when the lower conductive film 12 is formed of an electrode using two types of materials, A material 12A and B material 12B, the A material 12A and the B material 12B are necessary for oxidation and reduction. Since the voltage and speed are different, the material advantageous for oxidation and reduction acts spontaneously, so that both lowering the voltage and increasing the speed of both coloring and decoloring are possible. When using thin lines / lattice patterns or thin and small dots as a different material, it is preferable to use a transparent conductive material with translucency, while using a metal material with low translucency, for example, By preparing gaps between these dots and patterns, it is possible to ensure translucency from the gaps, so that different materials can be used regardless of whether or not translucency exists. In addition, since the contact resistance of the electrode (for example, the conductive film 18) that contacts the electrolyte 16 differs depending on the material, for example, the electrode (C material 18C and D material 18D in the case of FIG. 6) When the conductive film 18) is made, the contact resistance can be reduced, and the voltage can be lowered, the speed can be improved, and the characteristics can be improved. The use of two or more similar electrode materials can also be applied to the upper transparent conductive film 24.

In FIG. 1, the electrochromic material 14 is the lower part and the electrolyte 16 is the upper part. However, as in the third embodiment shown in FIG. But it ’s okay.

Since the electrochromic material 14 can reversibly change its color by oxidation / reduction associated with voltage application, it is possible to select coloring / decoloring / discoloration according to the magnitude and polarity of the applied voltage. Therefore, by changing the voltage magnitude or polarity between the upper transparent conductive film 24 and the lower conductive film 12, it is possible to select coloration / decoloration / discoloration. For this reason, for example, in the above-described embodiment, when the electrochromic material can be colored with minus 2V and erased with plus 3V, the upper transparent film 26 is pressed with a finger or a pen when the minus 2V is applied. Then, after printing by coloring, it is possible to switch to plus 3V and press the upper transparent film 26 to partially erase the part that is partially rubbed like an eraser. FIG. 8 shows an example of partial erasure in a touch type electrochromic device. On the contrary, after the voltage for erasing was applied, the upper transparent film 26 was partially pressed to erase the color, and then the voltage was switched to color. It is also possible to erase the drawing by pressing the upper transparent film 26 partially and coloring. In addition, some electrochromic materials change color depending on the magnitude of the voltage. In that case, various colors can be drawn by drawing after switching the applied voltage according to the color to be drawn. is there. Such partial coloring / decoloring / discoloration enables display devices such as electronic memo pads (notebooks) and electronic whiteboards using electrochromics, and local color changes (coloring / decoloring / discoloration). It can be used for light-shielding devices such as light control glass, electronic curtains, sunglasses, and anti-glare mirrors.

Further, not only partial erasure by partial pressing of the upper transparent film 26 described above, but also erasure between the conductive film 18 on the electrolyte 16 and the lower conductive film 12 as in the fourth embodiment shown in FIG. It is also possible to erase the drawing on the entire screen by applying a voltage from the power supply 32.

Further, as in the fifth embodiment shown in FIG. 10, it is possible to apply a voltage to the upper transparent conductive film 24 simultaneously with the voltage application to the conductive film 18 by the common power source 34. The partial pressing of can assist in erasing the drawing on the entire screen.

Further, when the entire screen is erased, if the sheet resistance in the surface of the conductive film 18 is high in FIG. 9, the color of the electrochromic material 14 near the voltage terminal attached to the conductive film 18 is preferentially changed. Therefore, it becomes difficult to obtain a color change of the electrochromic material far from the voltage terminal. Therefore, as in the sixth embodiment shown in FIG. 11, if a higher voltage is applied as the distance increases according to the distance from the erasing electrode 36 attached to the conductive film 18, the electrochromic material portion becomes a position. A sufficient voltage can be applied to the color change without shifting. As the distance from the erasing electrode 36 to the conductive film 18 increases, any circuit may be used as long as the voltage applied to the lower conductive film 12 is higher. For example, as shown in FIG. 11, consider a structure in which the lower conductive film is formed as a pattern electrode 12 'such as a line-and-space, and the line of each pattern electrode is connected by an appropriate resistor 38. In this case, a high voltage is applied to the portion farthest from the erasing electrode 36 (the center portion of the screen), and the resistance is reduced by using a voltage drop due to the resistor 38 as the erasing electrode 36 at the edge of the screen is approached. Is designed and arranged, a higher voltage can be applied to each pattern electrode 12 ′ as it approaches the center, so that uniform color erasure can be performed on the entire screen. Such a pattern electrode 12 ′ and a resistor 38 can be attached with a normal resistance element when the number of lines of the pattern electrode is small, and when the number of lines is increased, a seal, sheet, or paste If a resistor such as a thin film or a thin film is attached to a large number of line patterns, a pseudo distributed resistance circuit can be easily obtained. In that case, the distribution of resistance, which is a pseudo-distribution constant, can be made by simply changing the shape of the resistor in the form of a seal, sheet, paste, or thin film. is there.

When the entire screen is erased, the entire screen may be erased by attaching a fine erasing electrode 42 on the electrolyte 16 or the conductive film 18 as in the seventh embodiment shown in FIG. Is possible. In the figure, reference numeral 44 denotes an insulating layer for the erasing electrode 42. Here, for example, in the case of FIG. 12, a thin line-and-space (stripe) erasing electrode 42 is formed on the conductive film 18. When a voltage for erasing the drawing pattern is applied to the erasing electrode 42, an electric field having a slight spread is applied from the erasing electrode 42 toward the lower conductive film 12. If the line-and-space erasing electrodes 42 are arranged at intervals, the entire screen can be colored, decolored and discolored. The distance between the erasing electrodes 42 may be any distance as long as the color change of the entire screen can be obtained, but when drawing, the electrolyte 16 is pressed by pressing the upper transparent conductive film 24 and the transparent film 26 thereabove. Or, since it is necessary to draw in contact with the conductive film 18, the upper transparent conductive film 24 enters between the erasing electrodes 42 by the pressing of the transparent film 26 on the upper side, and the electrolyte 16 and the conductive film 18. It is necessary to prepare enough space for contact. Further, the width of the stripe-like erasing electrode 42 may be any width as long as it is designed so as to obtain the color change of the entire screen. However, as described above, the upper transparent conductive film 24 is used for erasing. Since it is necessary to secure a space to enter between the electrodes 42, it is easier to secure the interval between the erasing electrodes 42 if the width of the erasing electrodes 42 is narrowed. In order to ensure the translucency of the device, the width of the erasing electrode 42 is preferably narrow. In addition, an insulating film 44 that ensures insulation is required between the erasing electrode 42 and the transparent conductive film 24 thereabove. The insulating film 44 prevents electrical conduction between the upper transparent conductive film 24 and the erasing electrode 42 when the transparent film 26 is pressed. Therefore, when the transparent film 26 is pressed during drawing, No voltage is applied to the erasing electrode 42, and it is possible to avoid erroneous drawing of the electrochromic material in the stripe-like portion immediately below the erasing electrode 42. In addition, since the width of the erasing electrode 42 is sufficiently narrow, only the lower part of the erasing electrode 42 is drawn because only the lower part of the erasing electrode 42 pressed against the transparent film 26 is partially changed in color. The problem of not being able to be avoided. The erasing electrode 42 and its insulating film 44 are preferably made of a translucent material in order to ensure translucency. However, if the width of the erasing electrode 42 can be made so thin that it cannot be seen, the transparency is improved. It is not necessary. In FIG. 12, the spacer 22 is separately used in addition to the erasing electrode 42 and the erasing electrode insulator 44 thereabove, but the erasing electrode 42 and the erasing electrode insulation can be obtained without preparing a separate spacer. The body 44 itself can be used as a spacer.

FIG. 13 shows an experimental example of printing erasure in a device having a comb-shaped electrode for erasing. It is shown that characters printed by coloring can be erased by a comb-shaped erasing electrode.

In the present invention, a pen that can be directly drawn on the electrolyte 16 or the conductive film 18 by using a drawing tool instead of the upper transparent film 26 and the upper transparent conductive film 24 in the above embodiment. An electrochromic device of the formula can be realized. FIG. 14 shows an eighth embodiment as an example. Instead of the transparent film 26 and the upper transparent conductive film 24 in the embodiment, a drawing tool 50 such as a pen whose tip is a conductor is used with a hand 48. The electric field B is locally applied and the electrochromic material 14 under the contact point A is locally color-changed (colored / decolored / discolored) C when held in contact with the electrolyte 16 or the conductive film 18. Can do. Here, the color can be changed by applying a voltage by wiring (52) between the conductor part 50A at the tip of the drawing tool and the lower conductive film 12, and any one of coloring, decoloring, and discoloration can be applied. The voltage can be selected based on the polarity and magnitude of the voltage to be applied. Such a switch to be selected based on the polarity and magnitude of the voltage can be provided by installing a switch on the electrochromic device side, and a remote voltage switch mechanism using a remote controller or the like can also be introduced. Similar to the above-described embodiment, the conductive film 18 on the electrolyte 16 may or may not be present, but if present, the shape, hardness, elasticity, adhesiveness of the surface of the electrolyte 16 and the electrolyte 16 The electrical contact with can be improved. The characteristics of the materials required for the conductive film 18, the electrolyte 16, the electrochromic material 14, the lower conductive film 12, and the substrate 10 used in the present embodiment are the same as those in the previous embodiment. The material used as the drawing tool 50 may be any material and material as long as the tip has conductivity, such as conductive metal, conductive polymer, carbon material, conductive rubber, and composite materials thereof. There is no need for light transparency.

FIG. 15 shows a ninth embodiment in which the direct electric wiring 52 provided between the lower conductive film 12 and the drawing tool 50 is cut off and a potential by grounding is applied in the eighth embodiment. A voltage is applied between the drawing tool 50 and the lower conductive film 12 via a grounded potential. This eliminates the need to connect the wiring from the drawing tool 50 directly to the lower conductive film 12 and enables drawing even if the drawing tool 50 and the electrochromic device are not physically connected. The handling of tools becomes easy and drawing becomes easy. Any method may be used for grounding, such as the ground, device housing, drawing person's body, ground wire, etc., without using physical wiring by using indirect grounding such as corona discharge. It may be grounded.

In addition, in the electrochromic device using this drawing tool, it is possible to erase the drawn printing by the applied voltage, and the drawing tool can be used like an eraser. Furthermore, the entire screen erasing technique shown in the above fourth to eighth embodiments can be used as it is, and the partial erasing shown in FIG. 8 and the conductive film 18 similar to the fourth embodiment shown in FIG. The same as in the fifth embodiment shown in FIG. 10, the erasing by the conductive film 18 using the assist by the drawing tool 50 instead of the finger 30, the same as the sixth embodiment shown in FIG. 11. The erasing by patterning of the lower conductive film 12 'and the erasing by patterning the erasing electrode 42 / insulating layer 44 on the electrolyte 16 / conductive film 18 similar to those of the seventh embodiment shown in FIG. 12 and FIG. 13 can be applied.

Further, in a pen-type electrochromic device using a drawing tool, as in the tenth embodiment shown in FIG. 16, a short-circuit between the drawing tool 50 and the human body (such as a hand 48 holding the drawing tool 50) is used to pass the human body. Can be connected to the ground or the power source 28. In this case, it is necessary to perform electrical wiring to the drawing tool 50 by connecting the human body to the ground or the power supply 28 via the ground, the device housing, the human body of the drawing person, the ground wire, the corona discharge, or the like. There is no. The short-circuiting method from the human body to the ground or the power source 28 may be a short circuit via a user's shoes or clothing, a short circuit due to contact of the human body with a device housing or wiring, a short circuit via a conductive band, etc. Any method is acceptable. With this method, the drawing tool 50 is independent like a normal pen, so that physical handling is easy, drawing operability is improved, and electric wiring is not required, so that the drawing tool 50 is a simple material. And can be made inexpensively with a structure. The wiring through the human body can be connected to the ground, or can be connected to a power source wired from the lower conductive film.

In the eighth to tenth embodiments, the power source 28 is disposed on the lower conductive film 12 side. However, as shown in the eleventh embodiment shown in FIG. An electrochromic device that can be drawn is also possible. In this case, if you prepare a switch that switches the polarity and magnitude of the voltage in the drawing tool itself, you can select coloring, decoloring, and discoloration at hand with the drawing tool, making drawing and erasing operability easier. improves. The wiring in this case is selectively used depending on the object as well as the electrical wiring to the body portion of the drawing tool 50 as in the eleventh embodiment, as well as the wiring due to a short circuit through the human body as in the twelfth embodiment shown in FIG. Is possible.

FIG. 19 shows an example of drawing with a conductive rod drawing tool. An arbitrary shape can be drawn with a drawing tool.

(1) Regarding the electronic memo pad (notebook), an electronic memo pad (notebook) that does not use paper can be realized by using the touch-type or pen-type electrochromic device according to the present invention. In the touch electrochromic device having the transparent film 26 and the upper transparent conductive film 24 as in the first to seventh embodiments, it is possible to draw with any shape of material, such as a finger or a stick, regardless of conductivity or non-conductivity. It can be used as a notepad. The pen-type electrochromic device as in the eighth to twelfth embodiments can be used as a memo pad by using a conductor pen.

In contrast to conventional electronic notepads that have problems such as black and white that cannot be colored, dark drawing, and partial erasing, the electrochromic device of the present invention can be colored, bright, and partial erasing. There is a feature that is possible. The entire screen can be erased by the techniques of the fourth to seventh embodiments. If an electrochromic material that changes color depending on the voltage is used, multicoloring is possible. In addition, the touch-type / pen-type device can be erased with a shape like an eraser in addition to a rod-shaped drawing tool.

(2) Regarding the electronic whiteboard, a clean electronic whiteboard can be realized without using a chalk or whiteboard marker by using the touch-type or pen-type electrochromic device according to the present invention. In the touch electrochromic device having the transparent film 26 and the upper transparent conductive film 24 as in the first to seventh embodiments, it is possible to draw with any shape of material, such as a finger or a stick, regardless of conductivity or non-conductivity. It can be used as a whiteboard. The pen type as in the eighth to eleventh embodiments can be used as a whiteboard by using a conductive pen. The electrochromic device of the present invention is characterized in that it can be colored, bright, and partially erased. Further, the entire screen can be erased by the techniques of the fourth to seventh embodiments. If an electrochromic material that changes color depending on the voltage is used, multicoloring is possible. In addition, the touch-type / pen-type device has a shape like a whiteboard eraser in addition to a rod-like drawing tool, and can be erased. Further, a complicated and expensive system such as a combination of a whiteboard, a projector, hardware, and software is not required as in a conventional electronic whiteboard, and it can be manufactured at a low cost with a simple structure.

(3) Regarding dimming glass and electronic curtains, electrochromic materials have been used as dimming glass and electronic curtains by using them for window glass of automobiles, aircrafts, rooms, etc., from the prior art. However, the conventional electrochromic light control glass and electronic curtain only change the color of the entire glass (coloring, light control, decoloring, and discoloration), and color change in some places cannot be obtained. In the present invention, since the coloring of a part of the glass can be changed by touching with a finger or an object, light control or a curtain of only a part of the window glass is possible. Therefore, for example, in the window glass of automobiles, aircraft, and rooms, only the direct sunlight part is darkened to shield it from direct sunlight, and only the part of the glass where you want to enjoy the scenery is partially erased to make the scenery different. You can shield direct sunlight while watching.

(4) Regarding anti-glare mirrors, conventional electrochromic anti-glare mirrors only adjust the brightness of the entire mirror or only a limited part. On the other hand, when the electrochromic device according to the present invention is used, the color can be changed by directly touching only the reflective part of the mirror part irradiated with bright incident light from sunlight or light. It is possible to obtain a clear reflected image while providing a part of the antiglare function.

(5) Regarding the sunglasses, the conventional electrochromic sunglasses only dimmed the entire sunglasses, but when the electrochromic device of the present invention is used, the color of the touched part can be changed, and a part of the sunglasses. It is possible to block light.

(6) Regarding the fusion with the display, when a display device such as a liquid crystal display is arranged on the back of the electrochromic device of the present invention, it is possible to freely draw and erase pictures and characters on the display. . As a result, a device for displaying notes and memos on the display can be realized.

(7) Regarding an information input terminal device by fusion with a touch screen (touch panel) device, a touch position reading device such as a touch screen (touch panel) is disposed on the front surface (touch surface) of the electrochromic device of the present invention. You can also. In this case, it is also possible to input information using position information by the display device and the touch screen according to the present invention. In this case, when a display device such as a display is further arranged on the back surface, an information terminal device combining the touch screen and the display device or light control device of the present invention can be realized.

DESCRIPTION OF SYMBOLS 10 ... Board |

substrate

12, 12A, 12B ... Lower conductive film 14 ... Electrochromic material 16 ...

Electrolyte

18, 18C, 18D ... Conductive film 20 ... Insulator 22 ... Spacer 24 ... Upper transparent conductive film 26 ...

Transparent film

28, 54 ... Power source 30 ... Finger 32 ... Erasing power source 34 ...

Common power source

36, 42 ... Erasing electrode 44 ... Insulating layer 48 ... Hand 50 ... Drawer (pen)
50A: Conductor part of the paint 52 ... Wiring

Claims

A substrate,
A lower conductive film disposed on the substrate;
An electrochromic material and an electrolyte disposed on the lower conductive film;
An upper transparent conductive film disposed on the electrochromic material and the electrolyte via an insulating spacer;
A transparent film disposed on the upper transparent conductive film;
Means for applying a voltage between the lower conductive film and the upper transparent conductive film,
When the transparent film is pushed from the upper surface, the transparent film is curved and there is no gap formed by the spacer, and the upper transparent conductive film and the electrochromic material or electrolyte therebelow are in electrical contact with each other. An electrochromic drawing / display apparatus characterized in that an electric field is applied to only the electrochromic material immediately below the contact point and the color of the electrochromic material is locally changed.
A substrate,
A lower conductive film disposed on the substrate;
An electrochromic material and an electrolyte disposed on the lower conductive film;
With conductor paint,
Means for applying a voltage between the drawing tool and the electrochromic material and the electrolyte;
When the drawing tool is brought into contact with the electrochromic material and the electrolyte, the contact point is locally energized, and an electric field is applied only to the electrochromic material immediately below the contact point, and the color of the electrochromic material changes locally. An electrochromic drawing / display device characterized by the above.
The electrochromic drawing / display device according to claim 1, wherein the electrochromic material is disposed under or on the electrolyte.
4. The electrochromic drawing / display device according to claim 1, wherein a conductive film is disposed on the electrochromic material and the electrolyte.
The electrochromic drawing / display device according to any one of claims 1 to 4, wherein the electrochromic material is a metallo supramolecular polymer or a conductive polymer compound.
6. The electrochromic drawing / display device according to claim 5, wherein carbon nanotubes are mixed in the electrochromic material.
7. The electrochromic drawing / display apparatus according to claim 2, wherein a power source is built in the drawing tool.
8. The electrochromic drawing / display device according to claim 1, wherein local erasure and discoloration are possible by changing the magnitude and polarity of the voltage.
5. The electrochromic drawing / writing according to claim 4, further comprising means for applying a voltage between the electrochromic material and the conductive film on the electrolyte and the lower conductive film so that the entire erasing is possible. Display device.
10. The electrochromic drawing / display device according to claim 9, wherein an erasing electrode is disposed on the electrochromic material and the electrolyte or conductive film.
11. The electrochromic drawing / display device according to claim 10, wherein a higher voltage is applied as the distance increases, according to a distance from an erasing electrode disposed on the conductive film. .