JPH04107427A - Production of transmission type electrochromic element - Google Patents

Abstract

PURPOSE:To allow the production of the transmission type electrochromic element (ECD) which obviates the intrusion of air bubbles by dropping a sealing resin having <=1,000cP viscosity onto a sealing substrate and pressing an element substrate on which the ECD is previously formed thereon, then curing the sealing resin. CONSTITUTION:The curable sealing resin R having <=1,000cP viscosity is dropped onto the transparent sealing substrate G. The transmission type ECD of a fully solid thin film type formed on the transparent element substrate S is pressed to the sealing resin R on the sealing substrate G, by which nearly the entire surface of the element is coated with the sealing resin R. The sealing resin R is then cured. The intrusion of the air bubbles is substantially prevented by using the sealing resin R of the viscosity as low as <=1,000cP in such a manner. The workability at the time of sealing is improved in this way and the resin layer free from the intrusion of the air bubbles is formed. The element having the good appearance and reliability is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method of manufacturing a transmission type electrochromic device.

[Conventional technology]

Electrochromism is a phenomenon in which electrolytic oxidation or reduction reactions occur reversibly when a voltage is applied, resulting in reversible coloring. Using an electrochromic (hereinafter abbreviated as EC) substance that exhibits such a phenomenon, we create an EC element (hereinafter abbreviated as ECD) that changes color and fades by voltage manipulation.
Attempts have been made for more than 20 years to utilize CDs as light amount control elements (for example, anti-glare mirrors) and numeric display elements using seven segments. For example, a transparent electrode film (cathode), a tungsten trioxide thin film,
An ECI (ECI) (see Japanese Patent Publication No. 52-46098), which is formed by sequentially laminating an insulating film such as silicon dioxide and an electrode film (anode), is known as an all-solid-state ECD.

When voltage is applied to this ECD, tungsten dioxide (
WO3) The thin film is colored blue. After that, when a reverse voltage is applied to this ECD, the blue color of the WOa thin film disappears and becomes colorless. The mechanism of coloring and decoloring has not been elucidated in detail.) ■03 Thin film and insulating film (ion conductive layer)
It is understood that the small amount of water contained therein controls the coloring and decoloring of 1■03. The reaction formula for coloring is estimated as follows.

・H20→H"+0H (W03 film = cathode side) ・ (Insulating film = anode side) OH--1/2 H2O+1/40.2↑10eBy the way, a pair of electrodes that directly or indirectly sandwich the EC layer The layer is EC
At least one of the layers must be transparent so that the coloring and fading of the layers is visible to the outside. Particularly in the case of a transmissive ECD, both must be transparent. Currently, transparent electrode materials include SnO□, In2O5, and ITO (Sn
02 and In2O+), ZnO, etc., but these materials have relatively poor transparency and must be made thin, and for this and other reasons, ECDs are made of glass plates, plastic plates, etc. It is common to form on a substrate. An example of the structure of such an ECD is shown in FIG.

In Figure 1, (A) is the upper transparent electrode, (B) is the lower transparent electrode, and (E) is the reduction coloring EC layer (for example, WO2).
, (D) is an ion conductive layer, (C) is a reversible electrolytic oxidation layer (
For example, iridium oxide or iridium hydroxide), and basically the laminated structure of (A) to (B) alone constitutes an ECD, but as mentioned above, these ECDs are mounted on the element substrate (S). It is formed. Furthermore, in order to retain a small amount of moisture contained in the EC layer and the ion conductive layer, the laminated structure is sealed with a non-moisture curing resin, and the sealing substrate is bonded to the resin before the sealing resin is cured. be.

(R) is a sealing resin for the ECD, such as an epoxy resin, and (G) is a sealing substrate.

[Problem to be solved by the invention]

However, in the conventional method of manufacturing a transmission type ECD, there is a problem in that air bubbles are likely to be mixed in when applying the sealing resin to the element substrate.

An object of the present invention is to produce a transmission type ECD without inclusion of air bubbles.

[Means to solve problems]

In order to solve the above problems, in the present invention, the viscosity is 1000
Drop the sealing resin of centipoise or less onto the sealing substrate,
An element substrate on which an ECD was previously formed was pressed onto it, and then the sealing resin was cured.

[Effect]

In the present invention, since a sealing resin with a low viscosity of 1000 centipoise or less is used, air bubbles are difficult to enter, and the EC
It has been found that coating the sealing resin on the sealing substrate causes less air bubbles than the conventional manufacturing method in which the sealing resin is coated on the sealing substrate. Furthermore, since the state of the sealing resin can be seen through the transparent element substrate, workability during sealing is improved.

The laminated structure of the ECD in the present invention is not particularly limited; for example, it may have a four-layer structure such as (1) electrode layer ZEC layer/ion conductive layer/electrode layer.

(2) A five-layer structure such as electrode layer/reduction colored EC layer/ion conductive layer/reversible electrolytic oxidation layer/electrode layer is preferred.

Examples of the material for the transparent electrode include SnO□, In2
O*, ITO, etc. are used. Such an electrode layer is generally formed by a vacuum thin film forming technique such as vacuum evaporation, ion blasting, or sputtering. (Reduction colorability) As the EC layer, 1v03, Mo5s, etc. are generally used.

As the ion conductive layer, for example, silicon oxide, tantalum oxide, titanium oxide, aluminum oxide, niobium oxide, zirconium oxide, hafnium oxide, lanthanum oxide, magnesium fluoride, etc. are used. Thin films of these materials are insulators for electrons due to the manufacturing method, but are good conductors for protons (H+) and hydroxy ions (OH-). Cations are required for the coloring and decoloring reaction of the EC layer, and H+ ions and L! It is necessary to contain + ions in the EC layer and other parts. The H''' ions do not need to be ions from the beginning, but only as long as H+ ions are generated when a voltage is applied. Therefore, water may be included instead of H+ ions.

The EC layer and the ion conductive layer may be placed either side up or down. Further, a reversible electrolytic oxidation layer or a catalyst layer may be provided to the EC layer with an ion conductive layer interposed therebetween (which may also serve as an oxidative coloring EC layer in some cases). Such layers include, for example, iridium oxide or hydroxide, nickel, chromium, vanadium, ruthenium, rhodium. These substances may be dispersed in the ion conductive layer or the transparent electrode, or may be dispersed therein.

〔Example〕

An ITO electrode layer is formed on the entire surface of a rectangular glass element substrate (S), and then photoetching or laser cutting is performed to form an ITO electrode layer between the lead-out part (F) for the upper electrode (A) and the lower electrode (B). A groove was formed. As a result, a take-out portion (F) and a rectangular lower electrode (B) isolated from the take-out portion (F) were formed. Note that these patterns may be directly formed by depositing ITO using a mask. Next, a reversible electrolytic oxidation layer (C
), tantalum oxide layer (D) and tungsten oxide layer (E
) were formed in sequence. Finally, as a bipartite electrode (A), [T
ECD was fabricated by evaporating O.

At this time, the ITO was formed so that one end was in contact with the extraction part (F) already formed on the substrate (S).

First step: Prepare a sealing jig (I). Then, a liquid sealing tree 1 made of epoxy resin is placed on the sealing substrate (G).
ff(R) in a circular shape (see Figure 2a) or in a narrow strip shape (second
After discarding the cloth in the cloth (see figure b), place it on the sealing jig (I).

2nd step: The all-solid thin film type transmission type ECD element formed on the transparent element substrate is slowly placed on the sealing resin so that it contacts the sealing resin at a point (Figure 3b) or in a straight line ( (FIG. 3c), the entire element surface was covered with a sealing resin. (No. 3
(See figure d) 3rd step: The liquid sealing resin hardens when left at room temperature or slightly heated, so after confirming that it has hardened, remove it from the jig and apply it to the upper and lower electrodes respectively. , and the external wirings LA and LB are bonded to complete the ECD of this embodiment. In this ECD,
When a coloring voltage (+1.35V) is applied from the drive power supply (Su), the transmittance for incident light with a wavelength of 633 nm decreases to 20% (after 10 seconds).This transmittance remains for a while even after the voltage application is stopped. It was kept. This time, the decoloring voltage (-1, 3
5V), the transmittance recovered to 70%.

(After 10 seconds) This ECD is useful as a light control glass that can electrically control the amount of transmitted light.

〔Effect of the invention〕

As described above, according to the present invention, workability during sealing is improved, a resin layer without air bubbles can be formed, and an element with good appearance and reliability can be obtained.

[Brief explanation of the drawing]

FIG. 1 is a schematic vertical sectional view showing an example of an ECD. FIGS. 2a and 2b are schematic plan views showing the application shape of the sealing resin in the example. Figures 3a to 3d are schematic vertical sectional views showing the sealing process in the example. [Explanation of symbols of main parts] ECD...Electrochromic device S...Element substrate G...Sealing substrate R...Sealing (in liquid form or after hardening) Resin I
・・・・・・Sealing jig

Claims (1)

[Claims] First step: Dropping a curable sealing resin with a viscosity of 1000 centipoise or less onto a transparent sealing substrate; Second step: Dropping a curable sealing resin having a viscosity of 1000 centipoise or less onto a transparent sealing substrate; a step of pressing a solid thin film type transmission electrochromic element onto the sealing resin on the sealing substrate, thereby covering almost the entire surface of the element with the sealing resin; and a third step: the sealing A method for manufacturing a transmission type electrochromic element, comprising: curing a stopper resin.