JP2013200373A - Electrochromic display device and manufacturing method for electrochromic display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrochromic display device that facilitates connection with wiring.SOLUTION: An electrochromic display device includes: a first substrate 10 that includes a first display electrode formed on a display substrate; a first electrochromic layer that is formed on the first display electrode; a second substrate 20 that includes a second display electrode formed on a porous film; a second electrochromic layer that is formed on the second display electrode; a counter substrate that includes a counter electrode formed on its surface; and an electrolyte that is put between the display electrode and the counter electrode. The first substrate 10 and the second substrate 20 are laminated, the first substrate 10 includes a first extraction electrode 12a that is extracted to a vicinity of one end of the first substrate 10 connected to the first display electrode, and the second substrate includes a second extraction electrode 22a that is extracted to a vicinity of one end of the second substrate connected to the second display electrode. Both the first extraction electrode 12a and the second extraction electrode 22a are exposed in a state of laminating the first substrate and the second substrate.

Description

  The present invention relates to an electrochromic display device and a method for manufacturing an electrochromic display device.

  In recent years, electronic paper has attracted attention as an electronic medium that replaces paper. Electronic paper is characterized in that a display device can be used like paper, and characteristics different from those of conventional display devices such as a CRT (Cathode Ray Tube) and a liquid crystal display are required. Specifically, electronic paper is a reflective display device, etc. that has a high white reflectance and a high contrast ratio, can display a high definition, and has a memory effect on display. There are demands for characteristics such as being able to be driven at a low voltage, being thin and light, and being inexpensive. Among these, in particular, as characteristics relating to display quality, there is a high demand for white reflectance equivalent to that of paper and the like and a high contrast ratio, and color display.

  So far, as a display device for electronic paper, for example, a method using a reflective liquid crystal, a method using electrophoresis, a method using toner migration, and the like have been proposed. However, in any of these methods, it is extremely difficult to perform multicolor display while ensuring a white reflectance and a high contrast ratio. In general, as a method of performing multicolor display, there is a method of providing a color filter. However, when a color filter is provided, the color filter absorbs light, so that the light reflectance is lowered. Further, when a color filter is used, since it is necessary to divide one pixel into red (R), green (G), and blue (B), the reflectance of the entire display device is lowered, and the contrast is increased accordingly. The ratio also decreases. As described above, when the white reflectance and the contrast ratio are significantly reduced, the visibility is extremely poor as compared with paper and the like, and it is difficult to use as electronic paper.

  On the other hand, as a promising method for realizing a reflective display device without providing the color filter as described above, there is a method using an electrochromic phenomenon. The electrochromic phenomenon is also called electrochromism, and means a phenomenon in which a redox reaction occurs reversibly and a color changes reversibly by applying a voltage. An electrochromic display device is a display device that utilizes the coloring and decoloring (hereinafter referred to as “decoloring and decoloring”) of an electrochromic compound that causes electrochromism. This electrochromic display device is a reflective display device, has a memory effect, can be driven at a low voltage, and so on, so that it can be used as an electronic paper. It is considered a strong candidate for technology.

  In addition, since the electrochromic display device performs color development / decoloration using an oxidation-reduction reaction, the response speed in color development / decoloration tends to be slow. Therefore, Patent Document 1 discloses a structure in which an electrochromic compound is fixed in the vicinity of an electrode to improve the response speed of color development and decoloration. In Patent Document 1, the time required for color development and decoloration, which was conventionally about several tens of seconds, can be improved to about 1 second for both the color development time from colorless to blue and the color erase time from blue to colorless. It states that it can be done. However, with respect to the response time of color development / decoloration, this is not sufficient, and further improvement in the response time of color development / decoloration is required.

  The electrochromic display device can produce various colors depending on the structure of the electrochromic compound, so multicolor display is possible, especially the colorless state and the color development state reversibly change. Therefore, a stacked multicolor configuration can be realized. In the color display in the stacked configuration, it is not necessary to divide one pixel into red (R), green (G), and blue (B) as in the prior art, so that the reflectance and contrast ratio of the display device are reduced. There is nothing.

  As a multicolor display device using such an electrochromic display device, for example, Patent Document 2 discloses a multicolor display device using an electrochromic compound in which fine particles of a plurality of types of electrochromic compounds are stacked. Yes. What is disclosed in Patent Document 2 is a multicolor display device using a multicolor display electrochromic compound in which a plurality of electrochromic compounds, which are polymer compounds having a plurality of functional functional groups having different voltages that exhibit color development, are stacked. is there.

  Further, Patent Document 3 discloses a display device in which a plurality of electrochromic layers are formed on an electrode, and multiple colors are developed using a difference in voltage value or current value necessary for the color development. What is disclosed in Patent Document 3 has a display layer formed by laminating or mixing a plurality of electrochromic compounds that develop different colors and have different threshold voltages for developing colors and different amounts of charge necessary for color development. It is a multicolor display device.

  Furthermore, Patent Document 4 discloses a multicolor display device having a structure in which a plurality of structural units in which an electrochromic layer and an electrolyte are formed between a pair of transparent electrodes. Further, Patent Document 5 discloses a multicolor display device corresponding to RGB three colors by forming a passive matrix panel and an active matrix panel using the structural units described in Patent Document 4.

  Further, in Patent Document 6, as a solution to the problems of the multicolor display devices described in Patent Documents 2 to 5, a plurality of display electrodes are provided separately from each other between the display substrate and the counter electrode, A multicolor electrochromic display device having a structure in which an electrochromic layer is formed corresponding to each display electrode is disclosed.

  By the way, the electrochromic display device is an electrochemical element using the Gretzel cell announced in 1991, and forms a nanoporous particle layer (nanoporous layer) having a large area and exhibits an electrochromic reaction on the surface thereof. A compound is bound or adsorbed. For this reason, when the compound binding or adsorption process on the surface of the nanoporous layer is not sufficiently performed, density unevenness occurs in the surface of the compound. After that, when a different layer is formed on the nanoporous layer by a wet process, in-plane density unevenness occurs on the nanoporous layer or in the nanoporous layer. Furthermore, in order to sufficiently advance the electrochromic reaction, it is necessary to sufficiently permeate the electrolyte into the nanoporous layer. However, since the nanoporous layer is used, there is a problem that the gas phase remains. Had.

  As a result, display unevenness, response speed unevenness, delay, and the like in the electrochromic display device are caused. This tends to occur as the device area increases, and when laminated to form a multicolor device, the thickness increases, so that the electrolyte does not penetrate immediately, and this problem Dots may appear prominently.

  In addition, in a multifunctional electrochemical device in which a plurality of electrochemical functional layers are stacked in one device, the electrolyte medium is sufficiently filled in the device and the ion transfer is performed in order to make each layer function. Must be done.

  On the other hand, such an electrochromic display device is used by being attached to an active matrix substrate such as a TFT, but when a plurality of electrochromic layers are formed, when connecting to wiring in the active matrix substrate, Simply, you cannot connect as it is.

  The present invention has been made in view of the above, and in an electrochromic display device in which a plurality of electrochromic layers are formed, an electrochromic display device and an electrochromic display device that can be easily connected to wiring in an active matrix substrate or the like. It is an object of the present invention to provide a method for manufacturing a chromic display device.

  The present invention relates to a first substrate in which a first display electrode is formed on a display substrate, a first electrochromic layer formed on the first display electrode, and a porous film. A second substrate on which a second display electrode is formed, a second electrochromic layer formed on the second display electrode, and a counter substrate on which a counter electrode is formed And an electrolyte placed between the display electrode and the counter electrode, wherein the first substrate and the second substrate are laminated, and the first substrate The substrate has a first extraction electrode formed in the vicinity of one end of the first substrate connected to the first display electrode, and the second substrate includes the first extraction electrode. The second drawn out in the vicinity of one end of the second substrate connected to the second display electrode An output electrode is formed, and in the state where the first substrate and the second substrate are stacked, the first extraction electrode and the second extraction electrode are both exposed. To do.

  The present invention also provides a first substrate on which a first display electrode is formed on a display substrate, a first electrochromic layer formed on the first display electrode, and a porous material. A second substrate having a second display electrode formed on the film; a second electrochromic layer formed on the second display electrode; and a counter electrode formed on the surface. In a method of manufacturing an electrochromic display device having a counter substrate and an electrolyte placed between the display electrode and the counter electrode, in the vicinity of an end portion of the surface of the second display electrode in the second substrate After the masking step of covering the surface by masking and the masking step, a first electrochromic layer is formed on the surface of the first display electrode, and a second electrochromic layer is formed on the surface of the second display electrode. After the electrochromic layer forming step to be formed and the electrochromic layer forming step, the masking removal step for removing the masking covering the surface of the second display electrode, and the second substrate are masked. Removing a part of the region, an extraction electrode forming step of forming a second extraction electrode, a surface of the first substrate on which the first electrochromic layer is formed, and the second substrate A bonding step of bonding the first substrate and the second substrate with the surface opposite to the surface on which the second electrochromic layer is formed facing each other. Features.

  The present invention also provides a first substrate on which a first display electrode is formed on a display substrate, a first electrochromic layer formed on the first display electrode, and a porous material. A second substrate having a second display electrode formed on the film; a second electrochromic layer formed on the second display electrode; and a counter electrode formed on the surface. In a method for manufacturing an electrochromic display device having a counter substrate and an electrolyte placed between the display electrode and the counter electrode, a bending step of bending the vicinity of an end of the second substrate; An electrochromic layer forming step of forming a first electrochromic layer on the surface of the first display electrode and forming a second electrochromic layer on the surface of the second display electrode after the bending step; The elect After the chromic layer forming step, the bent portion returning step for returning the bent portion of the second substrate, and removing a part of the bent region in the second substrate. The extraction electrode forming step of forming the second extraction electrode, the surface on which the first electrochromic layer is formed on the first substrate, and the second electrochromic layer on the second substrate A bonding step of bonding the first substrate and the second substrate with the surface opposite to the surface on which the surface is formed facing each other.

  According to the present invention, in an electrochromic display device in which a plurality of electrochromic layers are formed, an electrochromic display device that can be easily connected to a wiring and a method for manufacturing the electrochromic display device can be provided.

Structure diagram of electrochromic display device in this embodiment Explanatory drawing (1) of the extraction electrode of the electrochromic display apparatus in this Embodiment Explanatory drawing (2) of the extraction electrode of the electrochromic display apparatus in this Embodiment Explanatory drawing (3) of the extraction electrode of the electrochromic display apparatus in this Embodiment Explanatory drawing (4) of the extraction electrode of the electrochromic display apparatus in this Embodiment Explanatory drawing of the electrochromic display device in this embodiment Explanatory drawing (1) of the manufacturing method of the electrochromic display apparatus in this Embodiment Explanatory drawing (2) of the manufacturing method of the electrochromic display apparatus in this Embodiment Explanatory drawing (1) of the other manufacturing method of the electrochromic display device in this Embodiment. Explanatory drawing (2) of other manufacturing methods of the electrochromic display device in this Embodiment Explanatory drawing of the electrochromic display apparatus in a present Example

  The form for implementing this invention is demonstrated below. In addition, about the same member etc., the same code | symbol is attached | subjected and description is abbreviate | omitted.

(Electrochromic display device)
The electrochromic display device in the present embodiment will be described with reference to FIGS.

  The electrochromic display device in this embodiment includes a first substrate 10, a second substrate 20, a third substrate 30, and a fourth substrate 40, and the first substrate 10 and the second substrate 40. 20 and the third substrate 30 are laminated. The first substrate 10 is obtained by forming a first display electrode 12 on the surface of a display substrate 11, and a first electrochromic layer 13 is formed on the first display electrode 12. . The second substrate 20 has a second display electrode 22 formed on the surface of the first porous film 21, and a second electrochromic layer is formed on the second display electrode 22. 23 is formed. The third substrate 30 has a third display electrode 32 formed on the surface of the third insulating film 31, and a third electrochromic layer 33 is formed on the third display electrode 32. Has been. The first electrochromic layer 13, the second electrochromic layer 23, and the third electrochromic layer 33 each carry an electrochromic compound that is a portion that develops a color by an oxidation-reduction reaction, and supports and releases the electrochromic compound. And a metal oxide for performing coloration at high speed, and a single molecule of an electrochromic compound is adsorbed on the metal oxide. By having a metal oxide, electrons (or holes) can be transmitted from the first display electrode 12, the second display electrode 22, and the third display electrode 32 to the electrochromic compound through the metal oxide, It is possible to more efficiently develop and decolorize.

  The first electrochromic layer 13, the second electrochromic layer 23, and the third electrochromic layer 33 are fixed so that the electrochromic compound does not move, and electrons are exchanged with the redox of the electrochromic compound. As long as electrical connection is ensured so as not to be hindered, the electrochromic compound and the metal oxide may be mixed to form a single layer.

  The first electrochromic layer 13, the second electrochromic layer 23, and the third electrochromic layer 33 are formed of electrochromic materials that develop colors different from each other. The chromic layer 13 is colored magenta, the second electrochromic layer 23 is colored yellow, and the third electrochromic layer 33 is colored cyan. Accordingly, the electrochromic display device in this embodiment can perform full color display.

  In the fourth substrate 40, a counter electrode 42 is formed on the surface of the counter substrate 41, and a white reflective layer 43 is formed on the counter electrode 42. In the photochromic display device according to the present embodiment, the first substrate 10, the second substrate 20, and the third substrate 30 are stacked, and the fourth substrate 40 includes the third electrochromic layer 33. The white reflective layer 43 is pasted in a state of being opposed to each other, and a solution to be the electrolyte 50 is put in between.

  The first porous film 21 and the second porous film 31 are porous insulating films formed of an organic material, and the solution serving as the electrolyte 50 is the first porous film 21 and the second porous film. It can penetrate through the membrane 31. In addition, since the display substrate 11 and the counter substrate 41 form the outside of the photochromic display device in the present embodiment, they are formed of a material that is not porous.

  In the present embodiment, the first porous film 21, the second porous film 31, the display substrate 11, and the counter substrate 41 are formed of an organic material such as a resin film, are self-supporting, and In this application, the term “film” or “substrate” is used for convenience of explanation. The first display electrode 12, the second display electrode 22, the third display electrode 32, and the counter electrode 42 are formed of a transparent conductive film.

  Next, extraction electrodes provided on the first substrate 10, the second substrate 20, and the third substrate 30 in the electrochromic display device according to the present embodiment will be described. The electrochromic display device in this embodiment is formed by stacking a first substrate 10, a second substrate 20, and a third substrate 30. Therefore, the extraction electrodes provided on the first substrate 10, the second substrate 20, and the third substrate 30 are formed when the first substrate 10, the second substrate 20, and the third substrate 30 are stacked. , Are formed to be in different positions.

  Specifically, in the case shown in FIG. 2, as shown in FIG. 2A, the first substrate 10 has a first extraction electrode 12 a connected to the first display electrode 12 on the lower left portion. The second substrate 20 is provided with a second extraction electrode 22a connected to the second display electrode 22 in the central portion of the left end, and the third substrate 30 includes a third extraction electrode 22a. A third extraction electrode 32a connected to the display electrode 32 is provided in the upper left portion. As described above, the first substrate 10 provided with the first extraction electrode 12a, the second substrate 20 provided with the second extraction electrode 22a, and the first substrate provided with the third extraction electrode 32a. When the three substrates 30 are stacked, as shown in FIG. 2B, the surface of each of the first extraction electrode 12a, the second extraction electrode 22a, and the third extraction electrode 32a is formed at the left end portion. Exposed. Thus, when the 1st board | substrate 10, the 2nd board | substrate 20, and the 3rd board | substrate 30 are laminated | stacked, the 1st extraction electrode 12a, the 2nd extraction electrode 22a, and the 3rd extraction electrode 32a are the left end side. By forming each of the portions so as to be exposed at different positions, the connection between the first extraction electrode 12a, the second extraction electrode 22a, the third extraction electrode 32a, and a wiring (not shown) in the active matrix substrate or the like can be established. It can be done easily. That is, it is possible to easily connect a wiring (not shown) extending in the direction in which the first extraction electrode 12a, the second extraction electrode 22a, and the third extraction electrode 32a are arranged.

  In the case shown in FIG. 3, as shown in FIG. 3A, the first substrate 10 is provided with the first extraction electrode 12 b connected to the first display electrode 12 on the entire left end side. The second substrate 20 is provided with a second extraction electrode 22b connected to the second display electrode 22 in the central portion at the left end, and the third substrate 30 has the third display electrode 32 and A third extraction electrode 32b to be connected is provided at the upper left portion. In this way, the first substrate 10 provided with the first extraction electrode 12b, the second substrate 20 provided with the second extraction electrode 22b, and the first substrate provided with the third extraction electrode 32b. When the three substrates 30 are stacked, as shown in FIG. 3B, the surface of each of the first extraction electrode 12b, the second extraction electrode 22b, and the third extraction electrode 32b is formed at the left end portion. Exposed. Thus, when the first substrate 10, the second substrate 20, and the third substrate 30 are stacked, the first extraction electrode 12b, the second extraction electrode 22b, and the third extraction electrode 32b are on the left end side. By forming so as to be exposed at different positions, it is easy to connect the first extraction electrode 12b, the second extraction electrode 22b, the third extraction electrode 32b, and a wiring (not shown) on the active matrix substrate or the like. Can be done. That is, it is possible to easily connect a wiring (not shown) extending in the direction in which the first extraction electrode 12b, the second extraction electrode 22b, and the third extraction electrode 32b are arranged.

  In the case shown in FIG. 4, as shown in FIG. 4A, the first substrate 10 has first extraction electrodes 12 c and 12 d connected to the first display electrode 12 on the lower left end portion and The second extraction electrode 22c and 22d connected to the second display electrode 22 are provided in the left end central portion and the right end central portion on the second substrate 20 and provided on the right end upper portion. The substrate 30 is provided with third extraction electrodes 32c and 32d connected to the third display electrode 32 in the upper left portion and the lower right portion. As described above, the first substrate 10 provided with the first extraction electrodes 12c and 12d, the second substrate 20 provided with the second extraction electrodes 22c and 22d, and the third extraction electrodes 32c and 32d. When the third substrate 30 provided with is laminated, as shown in FIG. 4B, the first extraction electrode 12c, the second extraction electrode 22c, and the third extraction electrode are provided at the left end side portion. Each surface of 32c is exposed, and the surface of each of the first extraction electrode 12d, the second extraction electrode 22d, and the third extraction electrode 32d is exposed in the right end portion. Therefore, it is possible to easily connect the first extraction electrodes 12c and 12d, the second extraction electrodes 22c and 22d, the third extraction electrodes 32c and 32d, and a wiring (not shown) on the active matrix substrate. That is, a wiring (not shown) extending in the direction in which the first extraction electrode 12c, the second extraction electrode 22c, and the third extraction electrode 32c are arranged can be easily connected, and the first extraction electrode 12d. Wiring (not shown) extending in the direction in which the second extraction electrode 22d and the third extraction electrode 32d are arranged can be easily connected.

  In the case shown in FIG. 5, as shown in FIG. 5A, the first extraction electrodes 12e, 12f, 12g and 12h connected to the first display electrode 12 are provided on the first substrate 10 at the left end. The second extraction electrodes 22e, 22f, 22g, and 22h connected to the second display electrode 22 are provided on the left end portion and the right end portion. The third substrate 30 is provided with third extraction electrodes 32e, 32f, 32g and 32h connected to the third display electrode 32 at the left end portion and the right end portion. The first extraction electrodes 12e, 12f, 12g, and 12h, the second extraction electrodes 22e, 22f, 22g, and 22h, and the third extraction electrodes 32e, 32f, 32g, and 32h are the first substrate 10, When the substrate 20 and the third substrate 30 are stacked, as shown in FIG. 5B, the first extraction electrodes 12e and 12f, the second extraction electrodes 22e and 22f, and the third extraction electrode are formed at the left end portion. The surface of each of the lead electrodes 32e and 32f is exposed, and the surface of each of the first lead electrodes 12g and 12h, the second lead electrodes 22g and 22h, and the third lead electrodes 32g and 32h is exposed at the right end portion. Is exposed. Therefore, the first extraction electrodes 12e, 12f, 12g and 12h, the second extraction electrodes 22e, 22f, 22g and 22h, the third extraction electrodes 32e, 32f, 32g and 32h, and the wiring (not shown) on the active matrix substrate Can be easily connected. That is, it is possible to easily connect a wiring (not shown) extending in the direction in which the first extraction electrodes 12e and 12f, the second extraction electrodes 22e and 22f, and the third extraction electrodes 32e and 32f are arranged, Wiring (not shown) extending in the direction in which the first extraction electrodes 12g and 12h, the second extraction electrodes 22g and 22h, and the third extraction electrodes 32g and 32h are arranged can be easily connected.

  Next, the electrochromic display device will be described in more detail based on FIG. 1 and FIG. In the electrochromic display device, the electrolyte layer includes the first display electrode 12 on the first substrate 10, the second display electrode 22 on the second substrate 20, the third display electrode 32 on the third substrate, and the fourth display electrode. It is provided so as to be sandwiched between the counter electrodes 42 in the substrate 40. The electrolyte layer contains an electrolyte 50 and a solvent or a solid electrolyte, and the first electrochromic layer 13, the second electrochromic layer 23, and the third electrochromic layer 33 are the first display electrode 12, the second electrochromic layer 33, respectively. The display electrode 22 and the third display electrode 32 generate and decolorize by an oxidation-reduction reaction by transfer of charges. In addition, each of the components on the counter electrode 43 side of the first electrochromic layer 13, the second electrochromic layer 23, and the third electrochromic layer 33 has a white reflection function so that a reflective type can be obtained. A display element can also be used.

  A transparent sealing layer may be provided on the porous film instead of the display substrate 11. By providing the sealing layer, the effect of preventing leakage of the electrolyte layer can be obtained. In addition, entry of moisture and the like from the outside can be prevented, and deterioration of element characteristics can be prevented. The sealing layer preferably has a gas barrier property, and a polymer coat layer using a gas barrier sealing material or the like is suitable. As the material of the sealing layer, an acrylic resin, an epoxy resin, a mixture thereof or a material to which an appropriate filler is added, an ethylene-vinyl alcohol copolymer, vinylidene chloride, a cyclic olefin copolymer, or the like is used. be able to. When the sealing layer is not provided, the display substrate functions as a transparent sealing layer that seals the electrolyte layer.

  The electric resistance between each of the first display electrode 12, the second display electrode 22, and the third display electrode 32 is determined by the first electrochromic layer 13, the second electrochromic layer 23, and the third electrochromic. It depends on the film thickness of the layer 33 and the like. When insulation cannot be obtained between each of the first display electrode 12, the second display electrode 22, and the third display electrode 32, it is between the first electrochromic layer 13 and the second display electrode 22. It is preferable to form an insulating layer on one or both of the second electrochromic layer 23 and the third display electrode 32. In the present embodiment, a first porous film 21 having a function as an insulating film is provided between the first electrochromic layer 13 and the second display electrode 22. A second porous film 31 having a function as an insulating film is provided between the second electrochromic layer 23 and the third display electrode 32.

  Furthermore, in each of the first electrochromic layer 13, the second electrochromic layer 23, and the third electrochromic layer 33, a protective layer made of an organic polymer material is in contact with the surface opposite to the display substrate 11. By forming, the adhesiveness with each adjacent layer of the 1st electrochromic layer 13, the 2nd electrochromic layer 23, and the 3rd electrochromic layer 33, the dissolution resistance with respect to a solvent, the display electrode ( The insulation between the first display electrode 12, the second display electrode 22, and the third display electrode 32) can be improved, and the durability of the electrochromic display device can be improved.

  Since the electrochromic display device has the above-described structure, it can easily perform multicolor display. The potential of the first display electrode 12 with respect to the counter electrode 42, the potential of the second display electrode 22 with respect to the counter electrode 42, and the potential of the third display electrode 32 with respect to the counter electrode 42 can be controlled independently. As a result, the first electrochromic layer 13 provided in contact with the first display electrode 12, the second electrochromic layer 23 provided in contact with the second display electrode 22, and the third display electrode 32 are provided. The third electrochromic layer 33 provided in contact therewith can be independently developed and decolored.

  Since the first electrochromic layer 13, the second electrochromic layer 23, and the third electrochromic layer 33 are provided on the display substrate 11 side, the first electrochromic layer 13, the second electrochromic layer 13, and the second electrochromic layer 33 are provided. Color development of only the first electrochromic layer 13, color development of only the second electrochromic layer 23, only the third electrochromic layer 33, depending on the color development / decoloration pattern of the electrochromic layer 23 and the third electrochromic layer 33 Color development by two layers of the first electrochromic layer 13 and the second electrochromic layer 23, Color development by two layers of the first electrochromic layer 13 and the third electrochromic layer 33, Second electrochromic Color development by the two layers of the layer 23 and the third electrochromic layer 33, the first It is possible to color development by three layers of the electrochromic layer 13 and the second electrochromic layer 23 and the third electrochromic layer 33, it is possible multicolor display.

  In addition, as described above, the first electrochromic layer 13, the second electrochromic layer 23, and the third electrochromic layer 33 are electrochromic layers that color yellow, magenta, and cyan. Full-color display is possible by independently controlling the potentials of the display electrode 12, the second display electrode 2, and the third display electrode 32.

(Method for manufacturing electrochromic display device)
Next, a method for manufacturing the electrochromic display device in the present embodiment will be described. 7 and 8 are schematic views showing a method for manufacturing the electrochromic display device in the present embodiment. FIG. 8 shows the case of the third substrate 30, but the same applies to the first substrate 10 and the second substrate 20. First, as shown in FIG. 7, the first substrate 10, the second substrate 20, and the third substrate 30 are prepared in advance. The substrate 10 has a display substrate 11 on which a first display electrode 12 is formed. The second substrate 20 is a film-like first porous film 21 on which a second display electrode 22 is formed. The third substrate 30 is a film-like third insulation. A third display electrode 32 is formed on the surface of the film 31.

  Next, masking is performed in the masking units 110a, 110b, and 110c. Specifically, the masking portion 110a masks the surface near the side surface of the first substrate 10, the masking portion 110b masks the surface near the side surface of the second substrate 20, and the masking portion 110c performs third masking. Masking is performed on the surface near the side surface of the substrate 30. The masking may be performed, for example, in a region where the first extraction electrode 12a or the like in the first substrate 10 is formed, a region where the second extraction electrode 22a or the like in the second substrate 20 is formed, This is performed by applying a masking tape in a region where the third extraction electrode 32a and the like are formed on the substrate 30.

Next, a porous electrode material made of a metal oxide such as TiO _{2 is} applied in the porous electrode material application portions 111a, 111b, and 111c. Specifically, a porous electrode material is applied to the first substrate 10 in the porous electrode material application part 111a, and a porous electrode material is applied to the second substrate 20 in the porous electrode material application part 111b. The porous electrode material is applied to the third substrate 30 in the porous electrode material application part 111c.

  Next, in the heating units 112a, 112b, and 112c, a porous electrode is formed by baking. Specifically, a porous electrode is formed by baking the first substrate 10 in the heating unit 112a, and a porous electrode is formed by baking the second substrate 20 in the heating unit 112b. A porous electrode is formed by baking the third substrate 30 in the portion 112c.

  Next, an electrochromic material is applied in the electrochromic material application portions 113a, 113b, and 113c. Specifically, an electrochromic material for forming the first electrochromic layer 13 is applied to the surface of the first substrate 10 in the electrochromic material application unit 113a, and the second substrate is formed in the electrochromic material application unit 113b. An electrochromic material for forming the second electrochromic layer 23 is applied to the surface of the substrate 20, and the third electrochromic layer 33 is formed on the surface of the third substrate 30 in the electrochromic material application portion 113c. Apply electrochromic material.

  Next, baking is performed in the heating units 114a, 114b, and 114c. Specifically, the first substrate 10 is baked in the heating unit 114a, the second substrate 20 is baked in the heating unit 114b, and the third substrate 30 is baked in the heating unit 114c.

  Next, rinsing is performed in the rinse portions 115a, 115b, and 115c. Specifically, the first electrochromic layer 13 is formed by rinsing the first substrate 10 in the rinse portion 115a, and the second substrate 20 is rinsed in the rinse portion 115b. The second electrochromic layer 23 is formed, and the third substrate 30 is rinsed in the rinse portion 115c, whereby the third electrochromic layer 33 is formed.

  Next, baking is performed in the heating units 116a, 116b, and 116c. Specifically, the first substrate 10 is baked in the heating unit 116a, the second substrate 20 is baked in the heating unit 116b, and the third substrate 30 is baked in the heating unit 116c.

  Next, an adhesive layer is formed in the adhesive layer forming portions 117a, 117b, and 117c. Specifically, the adhesive layer forming unit 117a forms an adhesive layer by applying an adhesive to the first substrate 10, and the adhesive layer forming unit 117b applies the adhesive to the second substrate 20. Then, the adhesive layer is formed by applying an adhesive to the third substrate 30 in the adhesive layer forming portion 117c. The adhesive layer formed on each substrate is an adhesive layer having ion conductivity, and a general solid electrolyte or the like can be used. Furthermore, by sticking a film having a through hole without an electrochemical function layer thereon, the risk of direct contact with each electrochromic layer can be avoided and the handling becomes easy.

  Next, the masking tape stretched at the mask peeler portions 118a, 118b, and 118c is removed. Specifically, in the mask peeler portion 118a, the masking tape stretched on the first substrate 10 in the masking portion 110a is removed, and in the mask peeler portion 118b, the masking stretched on the second substrate 20 in the masking portion 110b. The tape is removed, and the masking tape attached to the third substrate 30 at the masking portion 110c is removed at the mask peeler portion 118c. As a result, a region where the first extraction electrode 12a is formed is exposed in the first substrate 10, and a region where the second extraction electrode 22a is formed is exposed in the second substrate 20, and the third substrate 30 is exposed. Then, the region where the third extraction electrode 32a is formed is exposed.

  Next, in the pattern cutter portions 119b and 119c, the extraction electrode is cut into a desired shape. Specifically, the second lead electrode 22a having a desired shape is formed on the second substrate 20 in the pattern cutter portion 119b, and the third shape 30 having a desired shape is formed on the third substrate 30 in the pattern cutter portion 119c. The extraction electrode 32a and the like are formed.

  Next, in the bonding unit 120, the first substrate 10, the second substrate 20, the third substrate 30, and the fourth substrate 40 are bonded.

  Next, the cutting unit 121 cuts the first substrate 10, the second substrate 20, the third substrate 30, and the fourth substrate 40 bonded to each other with a desired size.

  As described above, the electrochromic display device in this embodiment having the structure shown in FIG. 2B or the like can be manufactured by roll-to-roll.

  The manufacturing method described above is a manufacturing method in which a masking tape is applied to the masking portions 110a, 110b, and 110c, and the masking tape stretched on the mask peeler portions 118a, 118b, and 118c is removed. However, as shown in FIG. 9, first, in the portions corresponding to the masking portions 110a, 110b, 110c, the vicinity of the side surfaces on both sides of the first substrate 10, the second substrate 20, and the third substrate 30 is folded. In the part corresponding to the bent and mask peeler portions 118a, 118b, and 118c, the bent portion may be returned to the original manufacturing method. Even with this method, the electrochromic display device in the present embodiment having the structure shown in FIG.

  Further, in the method of manufacturing the electrochromic display device in the present embodiment, as shown in FIGS. 8 and 9, the first substrate 10, the second substrate 20, and the third substrate 30 are one-dimensionally arranged. In addition to the manufacturing method in which the first substrate 10, the second substrate 20, and the third substrate 30 are two-dimensionally aligned, the manufacturing method may be a method of manufacturing the first substrate 10, the second substrate 20, and the third substrate 30. FIG. 10 illustrates a manufacturing method in which the first substrate 10, the second substrate 20, and the third substrate 30 are two-dimensionally arranged. FIG. 10 (a) illustrates masking. FIG. 10B shows a state where the extraction electrodes are cut into a desired shape in the pattern cutter portions 119b and 119c. FIG. 10B shows a state where the portions 110a, 110b and 110c are masked.

  The above description shows an example of the structure of the electrochromic display device or the method of manufacturing the electrochromic display device in the present embodiment, and is not limited to the above structure or method. For example, the structure of the electrochromic display device can be freely changed from the viewpoint of suppressing light loss due to light scattering of the porous film and the simplicity of the manufacturing process. Moreover, the number of layers of the electrochromic layer which is an electrochemical functional layer can be changed depending on the number of functions desired to be expressed.

(Element member of electrochromic display device)
Next, element members and the like forming the electrochromic display device in the present embodiment will be described in detail.

  As the display substrate 11, for example, a substrate made of a transparent material such as a glass substrate or a plastic substrate is used. As the plastic substrate, for example, polycarbonate, polyethylene, polystyrene, or the like, or polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, or the like that is polyester can be used. In addition, when a plastic film is used as the display substrate 11, a lightweight and flexible electrochromic display device can be manufactured.

  The material for forming the first display electrode 12, the second display electrode 22, and the third display electrode 32 is not particularly limited as long as it is a conductive material, but ensures light transmission. Therefore, a transparent conductive material that is transparent and excellent in conductivity is used. Thereby, the visibility of the color to develop can be improved more.

Transparent conductive materials include inorganic materials such as tin-doped indium oxide (hereinafter referred to as ITO), fluorine-doped tin oxide (hereinafter referred to as FTO), and antimony-doped tin oxide (hereinafter referred to as ATO). In particular, indium oxide (hereinafter referred to as In oxide), tin oxide (hereinafter referred to as Sn oxide) or zinc oxide (hereinafter referred to as Zn oxide) formed by vacuum film formation can be used. It is preferable that it is an inorganic material containing any one of these. In oxides, Sn oxides, and Zn oxides are materials that can be easily formed by sputtering, and can provide good transparency and electrical conductivity. Of these, particularly preferred materials are InSnO, GaZnO, SnO, In ₂ O ₃ , ZnO and the like.

  The material for forming the counter substrate 41 is not particularly limited, and the material for the counter electrode 42 is not particularly limited as long as it is a conductive material. When a glass substrate or a plastic film is used as the counter substrate 41, a transparent conductive film such as ITO, FTO, or zinc oxide, or a conductive metal film such as zinc or platinum, or carbon is used as a material for the counter electrode. It is done. The counter electrode made of these transparent conductive film or conductive metal is used by being coated on the counter substrate 42. On the other hand, when a metal plate such as zinc is used as the counter electrode 42, the counter substrate 41 also serves as the counter electrode 42.

  In addition, when the material of the counter electrode 42 is a material that causes a reverse reaction opposite to the oxidation-reduction reaction caused by the first electrochromic layer 13, the second electrochromic layer 23, and the third electrochromic layer 33, It is possible to perform color erasing. That is, when the first electrochromic layer 13, the second electrochromic layer 23, and the third electrochromic layer 33 are colored by oxidation, a reduction reaction occurs, and the first electrochromic layer 13 and the second electrochromic layer 13 are generated. When the layer 23 and the third electrochromic layer 33 are colored by reduction, if a material that causes an oxidation reaction is used as the counter electrode 42, the first electrochromic layer 13, the second electrochromic layer 23, and the third electrochromic layer 33 are used. The reaction of color development / decoloration in the chromic layer 33 becomes more stable.

  For the first electrochromic layer 13, the second electrochromic layer 23, and the third electrochromic layer 33, a material that causes a color change by oxidation and reduction is used. As such a material, a known electrochromic compound such as a polymer, a dye, a metal complex, or a metal oxide is used.

  Specifically, polymer-based and dye-based electrochromic compounds include azobenzene, anthraquinone, diarylethene, dihydroprene, styryl, styryl spiropyran, spirooxazine, spirothiopyran, thioindigo, tetrathiafulvalene, Terephthalic acid, triphenylmethane, triphenylamine, naphthopyran, viologen, pyrazoline, phenazine, phenylenediamine, phenoxazine, phenothiazine, phthalocyanine, fluoran, fulgide, benzopyran, metallocene Low molecular organic electrochromic compounds such as polyaniline, and conductive polymer compounds such as polyaniline and polythiophene are used.

Among those described above, it is particularly preferable to include a dipyridine-based compound represented by the following chemical formula 1 (general formula). Since these materials have a low color development / discoloration potential, even when an electrochromic display device having a plurality of display electrodes is configured, a good color value is exhibited by the reduction potential.

In the general formula shown in Chemical Formula 1, R1 and R2 each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group which may have a substituent, and at least one of R1 and R2 is: It has a substituent selected from COOH, PO (OH) ₂ , and Si (OC _k H _{2k + 1} ) ₃ . X represents a monovalent anion. n represents 0, 1 or 2. k represents 0, 1 or 2. A represents an alkyl group having 1 to 20 carbon atoms, an aryl group, or a heterocyclic group which may have a substituent.

  These compounds are formed in contact with the electrode. Particularly preferably, the electrochromic compound is adsorbed or bonded to the nanostructured semiconductor material and is in contact with the electrode. The electrochromic compound is fixed so that the electrochromic compound does not move, and it is sufficient that electrical connection is ensured so as not to prevent the transfer of electrons accompanying the oxidation and reduction of the electrochromic compound. And the nanostructured semiconductor material may be mixed into a single layer.

  The material of the nanostructure semiconductor material is not particularly limited, but titanium oxide, zinc oxide, tin oxide, aluminum oxide (hereinafter referred to as alumina), zirconium oxide, cerium oxide, silicon oxide (hereinafter referred to as silica), yttrium oxide, Oxygen boron, magnesium oxide, strontium titanate, potassium titanate, barium titanate, calcium titanate, calcium oxide, ferrite, hafnium oxide, tungsten oxide, iron oxide, copper oxide, nickel oxide, cobalt oxide, barium oxide, strontium oxide Metal oxides mainly composed of vanadium oxide, aluminosilicate, calcium phosphate, aluminosilicate and the like are used.

  Moreover, these metal oxides may be used independently and 2 or more types may be mixed and used. In view of electrical properties such as electrical conductivity and physical properties such as optical properties, it is selected from titanium oxide, zinc oxide, tin oxide, alumina, zirconium oxide, iron oxide, magnesium oxide, indium oxide, and tungsten oxide. When one kind or a mixture thereof is used, multicolor display excellent in response speed of color development and decoloration is possible. The shape of the nanostructured semiconductor material is not particularly limited, but a shape having a large surface area per unit volume (hereinafter referred to as a specific surface area) is used in order to efficiently carry the electrochromic compound. . By having a large specific surface area, the electrochromic compound is efficiently supported, and a display excellent in display contrast ratio of color development and decoloration is possible.

  A preferable film thickness range of each of the first electrochromic layer 13, the second electrochromic layer 23, and the third electrochromic layer 33 is 0.2 to 5.0 μm. When the film thickness is thinner than this range, it is difficult to obtain the color density. Moreover, when the film thickness is thicker than this range, the manufacturing cost increases, and the visibility is likely to deteriorate due to coloring.

  The interelectrode resistance between each of the first display electrode 12, the second display electrode 22, and the third display electrode 32 is the potential of one display electrode with respect to the counter electrode 42 and the other display electrode with respect to the counter electrode 42. The resistance of the display electrode must be large enough to be controlled independently of the potential of the first display electrode 12, at least one of the first display electrode 12, the second display electrode 22, and the third display electrode 32. It must be formed to be greater than the sheet resistance.

  The interelectrode resistance between each of the first display electrode 12, the second display electrode 22 and the third display electrode 32 is such that the first display electrode 12, the second display electrode 22 and the third display electrode 32. When the voltage is lower than the sheet resistance of any one of the display electrodes, when a voltage is applied to any one of the first display electrode 12, the second display electrode 22, and the third display electrode 32, the same voltage is applied. Is also applied to the other display electrode, and the electrochromic layer corresponding to each display electrode cannot be erased independently. The interelectrode resistance between each of the first display electrode 12, the second display electrode 22, and the third display electrode 32 is the first display electrode 12, the second display electrode 22, and the third display electrode 32. The sheet resistance is preferably 500 times or more. In order to ensure the resistance value, it is preferable to form an insulating layer.

As the material for the insulating layer which is a porous film, it is particularly preferable if it is porous, but it is not limited to this, and a material excellent in insulation, durability and film formability can be used. A material containing at least ZnS can be used. ZnS has a feature that it can be deposited at high speed by sputtering without damaging the electrochromic layer. Furthermore, ZnO—SiO ₂ , ZnS—SiC, ZnS—Si, ZnS—Ge, or the like can be used as a material containing ZnS as a main component.

Here, the ZnS content is preferably about 50 to 90 mol% in order to maintain good crystallinity when the insulating layer is formed. Thus, particularly preferred _{materials, ZnS-SiO 2 (8/2)} , ZnS-SiO 2 (7/3), ZnS, ZnS-ZnO-In2O 3 -Ga 2 O 3 in (60/23/10/7) is there. By using such an insulating layer material, a good insulating effect can be obtained with a thin film, and a decrease in film strength (that is, peeling of the film) due to multilayering can be prevented.

  On the other hand, forming the insulating layer into a porous film can be performed by forming the insulating layer as a particle film. In particular, when ZnS or the like is formed by sputtering, a porous film such as ZnS can be formed by previously forming a particle film as an undercoat layer. In this case, the nanostructured semiconductor material can be formed as a particle film, but a porous particle film containing silica, alumina, or the like can be formed as a part of the insulating layer. By making the insulating layer porous by using such a method, the electrolyte layer can penetrate into the insulating layer, so that the movement of charges as ions in the electrolyte layer accompanying the oxidation-reduction reaction is easy. Thus, multicolor display with excellent response speed of color development / erasure is possible. Furthermore, the insulating layer can be laminated and / or mixed with the thin film polymer layer.

  In addition, the film thickness of the insulating layer which is a porous film can be 20-500 nm, More preferably, it can be set as the range of 20-150 nm. When the film thickness is thinner than this range, it is difficult to obtain insulation. Moreover, when a film thickness is thicker than this range, while manufacturing cost increases, visibility will fall by coloring.

As the electrolyte layer, a layer in which a supporting salt is dissolved in a solvent is used. For this reason, ionic conductivity is high. As a material of the electrolyte layer, for example, an inorganic ion salt such as an alkali metal salt or an alkaline earth metal salt, a quaternary ammonium salt, an acid, or an alkali support salt can be used as the support salt. Specifically, LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ COO, KCl, NaClO ₃ , NaCl, NaBF ₄ , NaSCN, KBF ₄ , Mg (ClO ₄ ) ₂ , Mg (BF ₄ ) ₂ , tetrabutylammonium perchlorate, etc. can be used.

  Examples of the solvent include propylene carbonate, acetonitrile, γ-butyrolactone, ethylene carbonate, sulfolane, dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, and polyethylene glycol. , Alcohols are used. In addition, since it is not particularly limited to a liquid electrolyte in which a supporting salt is dissolved in a solvent, a gel electrolyte or a solid electrolyte such as a polymer electrolyte is also used.

  The electrolyte layer is preferably formed in a gel or solid form in order to improve element strength, improve reliability, and prevent color diffusion. As a solidification method, it is preferable to hold the electrolyte and the solvent in the polymer resin. This is because high ionic conductivity and solid strength can be obtained. Further, the polymer resin is preferably a photocurable resin. This is because the device can be manufactured at a low temperature and in a short time compared to thermal polymerization or a method of thinning the film by evaporating the solvent.

  Examples of the resin include, but are not limited to, polymers such as urethane, ethylene glycol, prene glycol, vinyl alcohol, acrylic, and epoxy. Moreover, the function of a white reflective layer can also be given by disperse | distributing white pigment particle | grains in an electrolyte layer. Although it does not specifically limit as a white pigment particle, Metal oxides, such as a titanium oxide, an aluminum oxide, a zinc oxide, a silicon oxide, a cesium oxide, an yttrium oxide, are mentioned. When the electrolyte layer is cured with a photo-curing resin, if the amount of the white pigment is increased, light is shielded, which tends to cause poor curing. Although depending on the thickness of the electrolyte layer, the preferred content is 10 to 50 wt%. The thickness of the electrolyte layer can be in the range of 0.1 to 200 μm. Preferably it is 1-50 micrometers. This is because if the electrolyte layer 16 is thicker than this, electric charges are easily diffused, and if it is thinner than this, it is difficult to hold the electrolyte.

  The first porous film 21, the second porous film 31 and the like may be any materials that are inert to the electrolyte and transparent, and are not particularly limited in mechanical strength. , Polycarbonate, polyester, polymethacrylate, polyacetal, polyvinylidene chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyurethane and the like. Among these, it is preferable to use polyolefin, polyvinylidene fluoride, polytetrafluoroethylene, or the like from the viewpoint of chemical stability and electrical insulation.

  The first porous film 21, the second porous film 31, and the like are films having a large number of through holes. As the first porous film 21, the second porous film 31, and the like, for example, a general nonwoven fabric or a self-supporting film in which a large number of through holes are formed in a plastic substrate or the like with a heavy ion beam can be used. The through-holes of the porous film in the present embodiment are mainly formed in the thickness direction of the film rather than being formed in various directions such as the thickness direction, the surface direction, and the diagonal direction of the film as in a general porous film. It is preferable to be formed. This is to realize the roles and effects described below. That is, the through-hole (pore part) of the porous membrane plays a role of releasing the gas phase when the electrolyte is infiltrated into the electrochromic layer that is the nanoporous layer. By allowing the gas phase to escape through the through-holes (pores) of the porous film, it is possible to prevent the occurrence of display unevenness, response speed unevenness, delay, etc. of the electrochromic display device due to the residual gas phase. In addition, since electrolyte ions are easily transmitted through the through-holes (pores), it is possible to cause an electrochemical reaction even when a plurality of porous films are stacked. In addition, by using a self-supporting film, a multi-functional electrochemical device can be easily manufactured because a process of sequentially stacking is not required in the production of a multi-functional electrochemical device in which a plurality of electrochemical functional layers are stacked with one device. can do.

  The nonwoven fabric is not necessarily limited, but the thickness is 5 to 500 μm, more preferably 10 to 150 μm, the fiber diameter is 0.2 to 15 μm, more preferably 0.5 to 5 μm, and the porosity is It is preferably a microporous homogeneous non-woven fabric composed of ultrafine fibers of 40 to 90%, more preferably 60 to 80%. When the thickness exceeds 500 μm, the responsiveness of the electrochromic element is lowered, and when it is 5 μm or less, the strength is weak and handling and workability become difficult. When the fiber diameter exceeds 15 μm, the porosity is lowered, and when the fiber diameter is 0.2 μm or less, the strength is lowered. When the porosity is 90% or more, the strength is reduced, and when the porosity is 40% or less, the ionic conductivity of the electrolyte layer is lowered.

  The diameter of the through hole formed in the plastic substrate or the like is preferably about 0.01 to 100 μm, for example. If the diameter of the through hole is 0.01 μm or less, the through hole may not completely penetrate the porous film, or when the display electrode is formed, the through hole is blocked with a transparent conductive film having poor ion permeability such as ITO. May end up. In addition, when the diameter of the through hole is 100 μm or more, it is a level that can be visually observed (the size of one pixel electrode in a normal display), and a display electrode cannot be formed immediately above the through hole. There is. In order to completely avoid such a problem, it is more preferable that the diameter of the through hole is about 0.1 to 5 μm. In addition, when a display electrode is formed on such a porous film, it is easy to form a display electrode with good conductivity because the surface flatness is good, and an electrochromic display device with good display performance is manufactured. Can do.

  The ratio of the area of the through holes to the total area of the first porous film 21 and the second porous film 31 can be set as appropriate, and can be set to about 0.01 to 30%, for example. . If the ratio of the area of the through-holes to the entire area of the porous film 15 or the like is too large, the area without the display electrode is widened, so that a problem occurs in the color development response (current flow) and a problem may occur in the color development / decoloration display. There is. Further, if the ratio of the area of the through hole to the entire area of the porous film 15 or the like is too small, the permeability of the electrolyte ions is deteriorated, so that there is a possibility that a problem occurs in the color development / decoloration display.

  The first porous film 21, the second porous film 31, and the like include a part of the material constituting the electrochromic layer (electrochromic compound and metal oxide carrying the electrochromic compound). For example, when a film of titanium oxide fine particles constituting an electrochromic layer is to be formed on the first porous film 21, the second porous film 31, etc., the first porous film 21, the second porous film 21, One of the materials in which the titanium oxide fine particles enter into the through-holes (pores) of the two porous membranes 31 and the like, and the first porous membrane 21 and the second porous membrane 31 constitute the electrochromic layer. The part is included. By including at least a part of the electrochromic layer in the through-holes (pores) of the first porous film 21 and the second porous film 31 in which the electrolyte is held, the color is efficiently developed and decolored. be able to.

  Thus, according to the present embodiment, the porous film (film having a large number of through holes) is formed on either the display electrode side or the electrochromic layer side of the laminate of the display electrode and the electrochromic layer. By providing it, it is possible to create a gas phase escape when the electrolyte is infiltrated into the electrochromic layer, which is a nanoporous layer, and the electrolyte can be sufficiently infiltrated into the electrochromic layer. As a result, it is possible to prevent occurrence of display unevenness, response speed unevenness, delay, and the like of the electrochromic display device.

  In addition, since the electrolyte permeates immediately into the electrochromic layer, a remarkable effect is exerted particularly in an electrochromic display device in which a plurality of electrochromic layers are stacked to form a multicolor coloring element.

(Formation of display electrode and electrochromic layer)
First, a 40 mm × 40 mm glass substrate is prepared, a 40 mm × 40 mm polycarbonate substrate as the display substrate 11 is fixed on the prepared glass substrate using a tape, and an ITO film is sputtered on the entire upper surface by sputtering to a thickness of about 100 nm. The first display electrode 12 was formed by forming a film so as to have a thickness of 1 mm. When the sheet resistance between the electrode end portions of the first display electrode 12 was measured, it was about 200Ω.

  Next, after a tape such as a masking tape is applied to a part of the side surface of the first display electrode 12, SP210 (commercial product) is formed as a titanium oxide nanoparticle dispersion on the glass substrate on which the first display electrode 12 is formed. (Name: Showa Titanium Co., Ltd.) was applied by spin coating and annealed at 120 ° C. for 15 minutes to form a titanium oxide particle film, followed by 4,4 ′-(1-phenyl-1H -pyrrole-2,5-diyl) bis (1- (4- (phosphonomethyl) benzyl) pyridinium) Spinning with 1 wt% 2,2,3,3-tetrafluoropropanol solution of viologen compound represented by bromide as coating solution Coat, anneal at 120 ° C. for 10 minutes, rinse with 2,2,3,3-tetrafluoropropanol, and anneal at 120 ° C. for 5 minutes to form titanium oxide particles and electrochromic To form a first electrochromic layer 13 composed of compound. Thereafter, the display substrate 11 on which the first display electrode 12 and the first electrochromic layer 13 were formed was peeled from the glass substrate. The first electrochromic layer 13 exhibits magenta color by applying a voltage or the like.

  Next, a 40 mm × 40 mm glass substrate is prepared separately, and a tape is used on the prepared glass substrate, and the first porous film 21 is a polyethylene porous film of 40 mm × 40 mm which is the first porous film. (Sunmap LC series, Nitto Denko Corporation) was fixed, and the second display electrode 22 was formed by depositing an ITO film to a thickness of about 100 nm on the entire upper surface by sputtering. . When the sheet resistance between the electrode ends of the second display electrode 22 was measured, it was about 200Ω.

  Next, after a tape such as a masking tape is applied to a part of the side surface of the second display electrode 22, SP210 (commercial product) as a titanium oxide nanoparticle dispersion is formed on the glass substrate on which the second display electrode 22 is formed. (Name: Showa Titanium Co., Ltd.) was applied by spin coating and annealed at 120 ° C for 15 minutes to form a titanium oxide particle film, followed by 4,4 '-(4,4'- 1 wt% of a viologen compound represented by (1,3,4-oxadiazole-2,5-diyl) bis (4,1-phenylene)) bis (1- (8-phosphonooctyl) pyridinium) bromide 2,2,3 , 3-tetrafluoropropanol solution is spin-coated as a coating solution, annealed at 120 ° C. for 10 minutes, rinsed with 2,2,3,3-tetrafluoropropanol, and annealed at 120 ° C. for 5 minutes. By performing titanium oxide particles and A second electrochromic layer 23 made of a romic compound was formed. Then, the 1st porous film 21 in which the 2nd display electrode 22 and the 2nd electrochromic layer 23 were formed was peeled from the glass substrate. The second electrochromic layer 23 exhibits yellow color by applying a voltage or the like.

  Next, another 40 mm × 40 mm glass substrate is prepared, and a tape is used on the prepared glass substrate, and the second porous film 31 is a polyethylene porous film of 40 mm × 40 mm which is the second porous film. A third display electrode 32 is formed by fixing a film (Sunmap LC series, Nitto Denko Corporation) and depositing an ITO film to a thickness of about 100 nm on the entire upper surface by sputtering. did. When the sheet resistance between the electrode ends of the third display electrode 32 was measured, it was about 200Ω.

  Next, after a tape such as a masking tape is applied to a part of the side surface of the third display electrode 32, SP210 (commercial product) as a titanium oxide nanoparticle dispersion is formed on the glass substrate on which the third display electrode 32 is formed. Name: Showa Titanium Co., Ltd.) was applied by spin coating and annealed at 120 ° C. for 15 minutes to form a titanium oxide particle film, followed by 4,4 ′-(isoxazole-3,5 -diyl) bis (1- (2-phosphonoethyl) pyridinium) bromide 1 wt% 2,2,3,3-tetrafluoropropanol solution of viologen compound is spin coated as coating solution and annealed at 120 ° C for 10 minutes Treatment, rinsing with 2,2,3,3-tetrafluoropropanol, and annealing at 120 ° C. for 5 minutes, so that the titanium oxide particles and the electrochromic compound are made. To form a third electrochromic layer 33. Then, the 2nd porous film 31 in which the 3rd display electrode 32 and the 3rd electrochromic layer 33 were formed was peeled from the glass substrate. The third electrochromic layer 33 exhibits cyan color by applying a voltage or the like.

(Formation of display electrode extraction part)
After peeling the tape such as masking tape stretched on the first display electrode 12, the second display electrode 22, and the third display electrode 32 to expose the display electrode, the first porous film 21 and By cutting the second porous film 31 into the shape shown in FIG. 3, the first extraction electrode 12 b is formed on the first substrate 10, the second extraction electrode 22 b is formed on the second substrate 20, and the third substrate 30 is formed. A third extraction electrode 32b was formed.

(Formation of counter electrode)
Apart from the glass substrate used when the first to third display electrodes 12, 22, 32, etc. are formed, a 40 mm × 40 mm glass substrate is prepared, and a counter substrate 41 using a tape on the prepared glass substrate. A 40 mm × 40 mm polycarbonate substrate is fixed, and an ITO film is formed in a region of 30 mm × 8 mm at three locations on the upper surface by sputtering so as to have a thickness of about 100 nm, thereby forming a counter electrode 42. did. When the sheet resistance between the electrode ends of the counter electrode 42 was measured, it was about 200Ω.

(Production of electrochromic display device)
On the side of the surface on which the counter electrode 42 of the fourth substrate 41 is formed, a laminated body of the third electrochromic layer 33, the third display electrode 32, and the second porous film 31, A laminate of the electrochromic layer 23, the second display electrode 22 and the first porous film 21 was placed on top of each other, and then tetrabutylammonium perchlorate was dissolved in dimethyl sulfoxide at 0.1 M to prepare. After the electrolyte solution was dropped from above, an electrochromic display device was fabricated by bonding and encapsulating the first electrochromic layer 13, the first display electrode 12, and the display substrate 11.

  The electrochromic display device manufactured in this example includes a display substrate 11, a first display electrode 12, a first electrochromic layer 13, a first porous film 21, a second display electrode 22, and a second display electrode. The electrochromic layer 23, the second porous film 31, the third display electrode 32, and the third electrochromic layer 33 are stacked. The shape and the like of each extraction electrode are the same as those shown in FIG.

(Color development test)
A voltage was applied to the electrochromic display device manufactured in this example, and color development was evaluated. The applied voltage was 3.0 V and the application time was 2 seconds. The display electrode 12 was connected to the negative electrode, and the counter electrode 41 was connected to the positive electrode.

  As shown in FIG. 11, magenta is developed by applying a voltage between the first display electrode 12 and the counter electrode 42, and a voltage is applied between the second display electrode 22 and the counter electrode 42. Thus, yellow can be developed, and cyan can be developed by applying a voltage between the third display electrode 32 and the counter electrode 42. The electrochromic display device in this example was able to independently develop magenta, yellow, and cyan, and could stably maintain the color once independently developed.

  As mentioned above, although the form which concerns on implementation of this invention was demonstrated, the said content does not limit the content of invention.

DESCRIPTION OF SYMBOLS 10 1st board | substrate 11 Display board | substrate 12 1st display electrode 12a-12g 1st extraction electrode 13 1st electrochromic layer 20 2nd board | substrate 21 1st porous film 22 2nd display electrode 22a-22g Second extraction electrode 23 Second electrochromic layer 30 Third substrate 31 Second porous film 32 Third display electrodes 32a to 32g Third extraction electrode 33 Third electrochromic layer 40 Fourth substrate 41 counter substrate 42 counter electrode 43 white reflective layer 50 electrolyte

Special table 2001-510590 gazette JP 2003-121883 A JP 2006-106669 A JP 2003-270671 A JP 2004-151265 A JP 2009-163005 A

Claims (10)

A first substrate having a first display electrode formed on the display substrate;
A first electrochromic layer formed on the first display electrode;
A second substrate on which a second display electrode is formed on the porous film;
A second electrochromic layer formed on the second display electrode;
A counter substrate having a counter electrode formed on the surface;
An electrolyte placed between the display electrode and the counter electrode;
Have
The first substrate and the second substrate are laminated,
The first substrate is formed with a first extraction electrode that is extracted in the vicinity of one end of the first substrate that is connected to the first display electrode,
The second substrate is formed with a second extraction electrode that is extracted in the vicinity of one end of the second substrate connected to the second display electrode,
The electrochromic display device, wherein the first extraction electrode and the second extraction electrode are both exposed in a state where the first substrate and the second substrate are stacked.   2. The first extraction electrode and the second extraction electrode are also formed in the vicinity of the other end of the first substrate and the second substrate, respectively. The electrochromic display device described in 1. The porous membrane is a first porous membrane,
A third substrate on which a third display electrode is formed on the second porous film;
A third electrochromic layer formed on the third display electrode;
Have
The first substrate, the second substrate, and the third substrate are laminated,
A third extraction electrode is formed on the third substrate and is extracted near one end of the third substrate connected to the third display electrode.
In the state where the first substrate, the second substrate, and the third substrate are laminated, the first extraction electrode, the second extraction electrode, and the third extraction electrode are all exposed. The electrochromic display device according to claim 1 or 2.   The first extraction electrode, the second extraction electrode, and the third extraction electrode are also formed in the vicinity of the other end of the first substrate, the second substrate, and the third substrate, respectively. The electrochromic display device according to claim 3, wherein the electrochromic display device is provided. A plurality of the first extraction electrodes are formed,
The electrochromic display device according to any one of claims 1 to 4, wherein a plurality of the second extraction electrodes are formed. A white reflective film is formed on the counter electrode,
The surface on which the first electrochromic layer or the second electrochromic layer is formed and the surface on which the white reflective film is formed are opposed to each other. The electrochromic display device according to any one of 5. A first substrate on which a first display electrode is formed on a display substrate, a first electrochromic layer formed on the first display electrode, and a second on a porous film A second substrate on which the display electrode is formed, a second electrochromic layer formed on the second display electrode, a counter substrate on which a counter electrode is formed, and the display In a method of manufacturing an electrochromic display device having an electrode and an electrolyte placed between the counter electrode,
A masking step of covering the vicinity of the edge of the surface of the second display electrode on the second substrate by masking;
After the masking step, an electrochromic layer forming step of forming a first electrochromic layer on the surface of the first display electrode and forming a second electrochromic layer on the surface of the second display electrode;
After the electrochromic layer forming step, a masking removing step for removing the masking covering the surface of the second display electrode;
An extraction electrode forming step of forming a second extraction electrode by removing a part of the masked region in the second substrate;
The surface of the first substrate on which the first electrochromic layer is formed is opposed to the surface of the second substrate opposite to the surface on which the second electrochromic layer is formed. A bonding step of bonding the first substrate and the second substrate;
A method of manufacturing an electrochromic display device, comprising: The porous membrane is a first porous membrane,
A third substrate on which a third display electrode is formed on the second porous film, and a third electrochromic layer formed on the third display electrode,
In the masking step, the vicinity of the edge of the surface of the third display electrode on the third substrate is covered by masking,
In the electrochromic layer forming step, a third electrochromic layer is formed on the surface of the third display electrode,
In the masking removal step, the masking covering the surface of the third display electrode is removed,
8. The method of manufacturing an electrochromic display device according to claim 7, wherein in the extraction electrode forming step, a part of the masked region is removed from the third substrate. A first substrate on which a first display electrode is formed on a display substrate, a first electrochromic layer formed on the first display electrode, and a second on a porous film A second substrate on which the display electrode is formed, a second electrochromic layer formed on the second display electrode, a counter substrate on which a counter electrode is formed, and the display In a method of manufacturing an electrochromic display device having an electrode and an electrolyte placed between the counter electrode,
A bending step of bending the vicinity of the end of the second substrate;
An electrochromic layer forming step of forming a first electrochromic layer on the surface of the first display electrode and forming a second electrochromic layer on the surface of the second display electrode after the bending step; ,
After the electrochromic layer forming step, a bent portion return step for returning the bent portion of the second substrate,
An extraction electrode forming step of forming a second extraction electrode by removing a part of the bent region in the second substrate;
The surface of the first substrate on which the first electrochromic layer is formed is opposed to the surface of the second substrate opposite to the surface on which the second electrochromic layer is formed. A bonding step of bonding the first substrate and the second substrate;
A method of manufacturing an electrochromic display device, comprising: The porous membrane is a first porous membrane,
A third substrate on which a third display electrode is formed on the second porous film, and a third electrochromic layer formed on the third display electrode,
In the bending step, the vicinity of the end of the third substrate is bent,
In the electrochromic layer forming step, a third electrochromic layer is formed on the surface of the third display electrode,
In the bent part return step, the bent part of the second substrate is restored,
The third extraction electrode is formed by removing a part of the bent region in the third substrate in the extraction electrode forming step. Manufacturing method of electrochromic display device.