JPH04295832A - Manufacturing method of electrochromic device - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Description: TECHNICAL FIELD The present invention relates to a method of manufacturing an electrochromic device. [0002] When a voltage is applied, a reversible electrolytic oxidation or reduction reaction occurs, and the phenomenon of reversible coloring (coloring) is called electrochromism. A thin film of an electrochromic (hereinafter abbreviated as EC) substance that exhibits this phenomenon is sandwiched between a pair of transparent or opaque electrode layers,
A device that changes color or fades by controlling the voltage applied between the electrode layers is called an EC element. For example, an ECD (see Japanese Patent Publication No. 52-46098) in which a transparent electrode film (cathode), a tungsten trioxide thin film, an insulating film such as silicon dioxide, and an electrode film (anode) are sequentially laminated on a glass substrate. is known as an all-solid-state ECD. When a voltage is applied to this ECD, the tungsten trioxide (WO3) thin film is colored blue. [0004] Thereafter, when a reverse voltage is applied to this ECD, the blue color of the WO3 thin film disappears and it becomes colorless. Although the mechanism of coloring and decoloring has not been elucidated in detail, WO3
It is understood that a small amount of water contained in the thin film and insulating film (ion conductive layer) controls the coloring and decoloring of WO3. The reaction formula for coloring is estimated as follows. [0005] H2 O → H+ +OH− (WO3
Membrane = cathode side) WO3 +nH+ +ne- → H
nWO3
Colorless and transparent
Blue (insulating film = anode side) OH- → 1/2H2
O+1/4O2 ↑+1/2e- 0006] This E
Attempts have been made for more than 20 years to utilize C elements in light quantity control elements (for example, anti-glare mirrors) and numeric display elements using seven segments. [0007] By the way, at least one of the pair of electrode layers that directly or indirectly sandwich the EC layer must be transparent in order to show the coloring and decoloring of the EC layer to the outside. Particularly in the case of a transmissive ECD, both must be transparent. At present, S is used as a transparent electrode material.
nO2, In2 O3, ITO (SnO2 and In
2O3 (mixtures with
For example, the ECD is usually formed on a glass plate, a plastic plate, etc.), and the element is sealed with resin between the substrate on which the ECD is formed and a protective substrate to protect it from physical and chemical effects. ing. An example of the structure of such an ECD is shown below. FIG. 2 is a schematic cross-sectional view showing the structure of an ECD in which an element is sealed together with a resin between two substrates, and FIG. 3 is a schematic cross-sectional view of the ECD before sealing. In Figure 2, ITO is applied to the entire surface of the rectangular glass element substrate (1).
Form an electrode layer with
7) A groove was formed between the lower electrode (2) and the lower electrode (2). Incidentally, patterns of the lead-out portion (7) and the lower electrode (2) are also directly formed by vapor-depositing ITO using a mask. Next, a reversible electrolytic oxidation layer (3) made of a mixture of iridium oxide and tin oxide, an ion conductive layer (4) made of tantalum oxide, and a reductively colored EC layer (5) made of tungsten oxide. were formed in sequence. Finally, ITO was deposited as an upper electrode (6) to produce an ECD. At this time, the ITO was formed so that one end was in contact with the extraction part (7) already formed on the element substrate (1). Here, two conductive clips (8) made of phosphor bronze and having a U-shaped cross section were prepared as electrode contacts. Attach two of these clips (8) to the edge sides of the element board (1), and thereby the clips (8)
Crimp the upper and lower electrode extraction parts,
ECD formed on the element substrate (1) shown in FIG. 3
I got it. The ECD formed on the element substrate (1) shown in FIG. cover with a sealing board (9), and sealing resin (1
0) was sealed. The shape and dimensions of the conductive clip (8) were set so that the sealing substrate (9) could be positioned and the non-display area around the ECD could be masked. [0013] Basically, an ECD is constructed only by the laminated structure of the lower electrode (2) to the upper electrode (6). That is, the lead-out portions (7) of the lower electrode (2) and the upper electrode (6) are each electrically connected to the clip (8), and furthermore, external wiring (11) and (12) are connected to the driving power source, respectively. As mentioned above, the ECD is colored and erased by voltage manipulation. [0014] However, if the amount of sealing resin held between the element substrate (1) and the protective sealing substrate (9) is too small, the element surface may not be fully covered. is not sealed. In addition, if the amount is too large, the sealing resin that protrudes from the outer periphery of the two substrates will wrap around the substrate surface and harden and adhere in lumps, so after curing, it is necessary to remove the sealant that has adhered to the substrate surfaces and end faces. However, this removal process takes time, and in some cases, the device may be damaged during the process, which is a problem. [0015] The present invention prevents the sealing resin protruding from the periphery of the substrate during sealing from wrapping around the substrate surface, thereby eliminating the need to remove the cured resin from the substrate surface and thereby preventing damage to the substrate surface. It is an object of the present invention to provide a method for manufacturing an EC element. Means for Solving the Problems In the method for manufacturing an EC element according to the present invention, an electrochromic element formed on a first substrate is sealed together with a resin between the first substrate and the second substrate. In the method for manufacturing an electrochromic device, the electrochromic device on the first substrate and the second electrochromic device are
A resin is placed on one of the substrates, the first substrate and the second substrate are engaged, and the two substrates to be engaged are rotated to connect the first substrate and the second substrate. Excess resin is discharged from the engaging edge portion. [Operation] In the present invention, during sealing, the sealing substrate and the element substrate are rotated together, and the centrifugal force causes the sealing resin protruding from between the substrates to be scattered around, so that the resin is not deposited on the substrate surface. Also, resin does not adhere in lumps to the end surface of the substrate. [0018] The rotation speed of the sealing substrate and the element substrate can be varied depending on the size of the substrate and the viscosity of the sealing resin, but the rotation speed must be such that at least the sealing resin used is scattered. be. Although there are no restrictions on the direction of rotation of the substrate, it is better to rotate the substrate vertically, since gravity is added to the centrifugal force, resulting in better resin scattering. In the embodiments described later, ECD is described as a preferable example, but the laminated structure of ECD is as follows.
Although not particularly limited, the structure of solid-state ECD includes, for example: ■4-layer structure such as electrode layer/EC layer/ion conductive layer/electrode layer; ■electrode layer/reduction colored EC
A five-layer structure such as layer/ion conductive layer/reversible electrolytic oxidation layer/electrode layer is mentioned. [0020] As the material of the transparent electrode, for example, SnO
2, In2O3, ITO, etc. are used. Such an electrode layer is generally formed by vacuum thin film forming techniques such as vacuum evaporation, ion plating, and sputtering. (Reduction colorability) EC layer is generally WO3, M0
O3 etc. are 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. Although thin films of these materials are insulators with respect to electrons due to the manufacturing method, they also contain protons (H+) and hydroxy ions (OH-
) is a good conductor. Cations are required for the coloring and decoloring reaction of the EC layer, and it is necessary to contain H+ ions and Li+ ions in the EC layer and other parts. The H+ ions do not have to be ions from the beginning, but only H+ ions are generated when a voltage is applied. Therefore, water may be included instead of the H+ ions. Very little of this water is sufficient, and often even moisture that naturally enters from the atmosphere will discolor. [0022] The EC layer and the ion conductive layer may be placed either on top or on the bottom. Further, a reversible electrolytic oxidation layer or a catalyst layer may be provided to the EC layer with an ion conductive layer sandwiched 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, and the like. These substances may be dispersed in the ion conductive layer or the transparent electrode, or may be dispersed therein. The opaque electrode layer may also serve as a reflective layer, such as gold, silver, aluminum, chromium, tin, zinc, nickel,
Metals such as ruthenium, rhodium, and stainless steel are used. [Embodiment] An embodiment of the present invention will be described below. The upper electrode (6) of the ECD formed on the element substrate (1) shown in FIG. 3 is covered with a protective sealing substrate (9), and a sealing resin (10) is sealed in between. Note that the same reference numerals as those described above indicate the same or corresponding parts. FIG. 1 is a sectional view showing a state in which an element substrate and a protective sealing substrate are engaged and rotated. As shown in FIG. 1, a smaller rectangular glass element substrate (1) shown in FIG. A sealing substrate (9') was placed and adsorbed. In addition, a suction cup (13
) is smaller than the sealing substrate (9'). and,
A liquid sealing resin (10) made of epoxy resin was applied onto the sealing substrate (9'). Furthermore, the element substrate (1) on which the ECD shown in FIG. 3 was formed was placed on top of this. Here, the element substrate (1) is attached to another substrate holder (14).
It is in a state where it is sucked by the suction cup (13). Further, the size of the suction cup (13) is smaller than the element substrate (1). Next, each substrate (
1) (9') and each board (1) (
9') were put together vertically and rotated at high speed. The sealing resin (10) protruding from each substrate (1) (9') will be scattered in the circumferential direction from the edge surface of the substrate due to centrifugal force, and the sealing resin (10) protruding from the edge surface of the substrate (1) (9') will be scattered in the circumferential direction from the edge surface of the substrate. (10) did not wrap around to the substrate surface side. The sealing resin (10) will harden if left at room temperature or slightly heated, so after confirming the hardening, stop the rotation of the substrate and remove the sealed element substrate from the substrate holder (14). When removed, an element is obtained in which the sealing resin does not wrap around the surface of the substrate. At this point, connect the external wiring (
11) When (12) is bonded, the EC of this example is
D is completed. This ECD is supplied with a coloring voltage (+
1.35V), the wavelength 63
The transmittance decreased to 20% for 3 nm light (after 10 seconds), and this transmittance was maintained for a while even after the voltage application was stopped. This time, when a decoloring voltage (-1.35 V) was applied, the transmittance similarly recovered to 70% (after 10 seconds). As described above, according to the present invention, the sealing substrate and the element substrate are rotated together during sealing, and the sealing resin protruding from between the substrates is scattered around. Since the resin does not adhere to the substrate surface and the resin does not adhere in lumps to the end face of the substrate, a process for removing the cured resin is no longer necessary. This also has the effect of eliminating damage to the substrate.

[Brief explanation of the drawing]

FIG. 1 is a sectional view showing a state in which an element substrate and a protective sealing substrate are engaged and rotated.

[Figure 2] E with an element sealed with resin between two substrates
FIG. 2 is a schematic cross-sectional view showing the configuration of a CD.

FIG. 3 is a schematic cross-sectional view of the ECD before sealing.

[Explanation of symbols]

Claims (1)

[Claims] 1. A method for manufacturing an electrochromic device, in which an electrochromic device formed on a first substrate is sealed together with a resin between the first substrate and a second substrate, wherein the electrochromic device formed on the first substrate is sealed with a resin. Resin is placed on either the element or the second substrate, the first substrate and the second substrate are engaged, and the two engaging substrates are rotated to connect the first substrate and the second substrate. A method for manufacturing an electrochromic device, characterized in that excess resin is discharged from an edge portion that engages with two substrates.