JPH0134366B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an electrochromic material (EC)
This relates to a light control body using.

Conventionally, blinds, curtains, and the like have been used as light control bodies for blocking light rays, but they are troublesome to open and close, and a light control body that allows finer adjustment is desired.

In recent years, liquid crystal display devices (LCD), electrochromic display devices (ECD), etc. have attracted attention as devices that perform display by electro-optically shielding light rays, and there are various ideas for using these devices as light control devices. Proposed.

Among these, the liquid crystal layer has the advantage of being thin, but the drawbacks of using a polarizing film include insufficient weather resistance and low transmittance during transmission, and the difficulty of keeping the gap between the substrates constant. Liquid crystals have disadvantages such as being sensitive to heat and ultraviolet light, so they have not yet been put into practical use.

ECD, which is a display that uses EC, has a slower response speed than LCD, and repeated coloring and decoloring causes problems such as decolorization and decolorization, and it has a lifespan of only about 10 ⁶ to ^{10 7} times, so it cannot be used as a watch. Because it has drawbacks such as not being able to display seconds,
Although it has the advantages of good contrast, coloring and decoloring, it consumes no power, and has memory properties, it has hardly been put into practical use at present.

However, the drawbacks of these ECDs do not pose much of a problem when used as a light control body that is not a display body. In other words, for a light control body, a response speed of a fraction of a second is essentially meaningless, and a response speed of several seconds to several minutes is usually sufficient, and the lifespan due to repeated coloring and decoloring is limited to 10 times a day. Approximately 40,000 times in 10 years since I deleted it, 10 ⁴ ~
10 It can withstand practical use after about ⁵ times, so there is no problem. Furthermore, the advantages of EC, such as good contrast and the fact that it does not require electricity for anything other than coloring and decoloring, can be utilized as is, and unlike liquid crystals, the gap between the substrates can be controlled as long as the EC and the counter electrode do not short-circuit. It is extremely easy to make and can be easily manufactured as a light control body.

Based on these findings, the present inventor has already made several proposals regarding the structure of a light control body.

However, in order to put EC dimmer into practical use,
It had to be much larger than the ECD, and a new big problem arose.

That is, in a light control body using EC, a large amount of power is temporarily consumed during coloring/decoloring, and a large current flows through the electrodes. For this reason, a high voltage is applied near the lead extraction part around the dimmer, but the voltage decreases as you move away from there, and as a result, the coloring sometimes appears shaded in parts.

The present invention was made with the aim of preventing such color unevenness, and provides a light control device in which a transparent substrate having an EC layer formed on a transparent electrode and a transparent substrate having a counter electrode formed thereon are laminated via an electrolyte. It is a light control body made by laminating low-resistance conductive wires on or below a transparent electrode.

Since the light control body of the present invention has a low-resistance conductive wire, there is almost no voltage drop at the transparent electrode, and even if the light control body has a large area, the entire density is almost uniform. The response speed of coloring/decoloring is also almost uniform and fast.

Further, it does not consume power except when coloring or decoloring, does not require precise gap control unlike liquid crystals, and is easy to manufacture as long as both electrodes are prevented from short-circuiting.

FIG. 1 is a cross-sectional view of a representative example of the light control body of the present invention, which includes a transparent substrate 4 on which a transparent electrode 2 and an EC layer 3 are formed on a conductive wire 1, and a transparent substrate on which a counter electrode 5 is formed. 6 are opposed to each other so as to sandwich the electrolyte 7, and the periphery thereof is sealed with a sealing material 8.

FIG. 2 and FIG. 3 show the conductive wire-like material 1 of the present invention.
1 is a plan view showing patterns Nos. 1 and 21, and the hatched portion in the figure is a conductive wire-like object;
In the figure, it is formed in a line shape, and in FIG. 3, it is formed in a grid shape. In both figures, the dashed line indicates the boundary between the sealing materials.

This conductive wire material may be used as long as it is stable against electrolytes such as gold, silver, copper, chromium, nickel, titanium, carbon, etc., and may be used for printing, vapor deposition, adhesion of wire or net materials, etching of metal layers, etc. The transparent electrode may be provided above or below the transparent electrode.
The cotton cloth of this conductive wire material can be from several tens of micrometers to several millimeters, and if you want it to be difficult to see, it should be about 50 to 200 micrometers. If it is clearly visible
It may be about 500 to 5000 μm. It is sufficient if the resistance is lower than that of a transparent electrode, but it may be appropriately set so that a difference in density between coloring and decoloring is unlikely to occur when a voltage is applied, and the thickness is also determined accordingly.

Further, the line spacing may be about 1 cm for a thin cotton cloth and about several cm for a thick cotton cloth, and may be set as appropriate based on the resistance of the current value.

The conductive wire-like material can be formed into a variety of shapes such as a line shape, a lattice shape, a hexagonal shape, a wavy line shape, and others as described above.

The transparent substrate can be anything that is transparent and has sufficient strength, such as glass, plastic, or a laminate of these materials, and can be used as long as it is possible to form transparent electrodes and conductive wires on it. 1
A thickness of ~20mm is typically used.

This transparent electrode may be formed of In ₂ O ₃ , SnO ₂ , Au, or by a vapor deposition method, a printing method, a film pasting method, etc., and may be thin and colored blue, brown, gray, etc. It is also possible to form display segments that are not provided partially.

The EC layer can be a material such as WO ₃ , MoO ₃ , Ir ₂ O _3, etc., which can be used as long as it absorbs reversibly in the visible light range when a voltage is applied, and usually it can absorb over almost the entire visible light range. is used, but it causes absorption in a part of the visible light range, that is, it is colored in a specific color.
Further, it is also possible to use a material whose absorption light range changes, that is, whose color changes.

In addition, although a transparent electrode is normally used as the counter electrode, it is also possible to form an EC layer that is colored by applying a voltage opposite to the EC layer on the front side, or to provide it by forming carbon, manganese dioxide, or EC into a thin wire shape. be.

Various known sealing materials can be used, but
Epoxy resins, fluorine resins, silicone resins, and other materials that do not deteriorate with electrolytes and do not have an adverse effect on the electrolytes can be used, and the seal width can be much wider than that of ordinary ECDs. Material selection criteria are relatively undemanding.

The electrolyte may be any electrolyte as long as it can color or erase the color of the EC layer, and usually an organic solvent to which various additives are added is used.

Specifically, 0.005M of a chelating agent such as acetylacetone, ethylenediamine, thiosalicylic acid, etc. is added to a proton-supplying organic solvent such as an alcohol having 3 or more carbon atoms, an amide solvent, or propylene carbonate, as necessary, to improve responsiveness. /that's all,
A mixture of 0.005M or more of an iodine-containing compound such as monoiodine acetic acid or lithium iodide to improve color erasing properties, or 0.005M or more of trichloroacetic acid or benzenesulfonic acid to improve responsiveness during coloring is used. Ru.

Alternatively, a Redox system capable of performing a Redox reaction at the counter electrode may be simply added to a solution containing H ⁺ or L ⁺ ions.

In addition, polymeric monomers with polar groups such as polyacrylic acid, polyvinyl alcohol, polyvinyl acetal, and polyvinyl acetate that give adhesiveness and stickiness to these electrolytes can be added instead of the organic solvent. When a substance is used, the electrolyte has the advantage of being easy to seal because leakage is less likely to occur.

4 to 6 are cross-sectional views of embodiments of the present invention, all of which are exaggerated for clarity.

FIG. 4 is the most basic example, in which conductive wires are formed only on the front substrate, with conductive wires 31 on a transparent substrate 34, transparent electrodes 32 on top of that, and an EC layer. 33 is shown.

FIG. 5 shows an example in which conductive wires are formed on both the front substrate and the counter electrode side substrate.
A transparent electrode 42 is placed on a transparent substrate 44, and a conductive wire 41 and an EC layer 43 are placed on top of the transparent electrode 42, and
On the counter electrode side, a conductive wire 48 is placed on a transparent substrate 46, and a transparent counter electrode 45 is placed on top of the conductive wire 48.
The figure shows a light control body formed with a .

By forming conductive wires on both substrates as in this example, it is preferable to more easily achieve uniformity in coloring density.

FIG. 6 shows yet another example in which conductive wires 51, 58 are provided on both substrates, transparent electrodes 52, 55, and an EC layer 53 are provided at positions corresponding to the conductive wires. An in-plane sealing material 59 is used to maintain a constant distance between the two substrates.
Furthermore, a reinforcing wire such as a nylon cord or a fluororesin-coated steel wire may be embedded in this in-plane sealing material to prevent fragments from scattering even if the transparent substrate is damaged.

The conductive wires of the present invention are usually gathered near the peripheral seal and taken out to the outside, for example, they are welded to a band-shaped metal plate outside the seal, soldered, etc., and connected from the band-shaped metal plate to the outside. , a plurality of conductive wires are grouped together and connected to the outside with pins. From the viewpoint of ease of attaching the control light, it is preferable that the external connection terminal has a structure that allows connection and removal with a single touch, such as a pin or plug.

Also, if the conductive wire is led outside in a straight line across the seal, if the seal width is narrow, it will likely cause negative effects such as liquid leakage and moisture permeation, so the seal width should be widened only in this part. , it is preferable to form the conductive wire into a zigzag shape. Alternatively, a through hole may be provided in the substrate to take it out to the outside, or an inter-substrate transfer may be provided within the seal.

In addition, in the present invention, a time display section is provided in a part of the light control body, an ultraviolet cut film or a color film is attached, the light control body is divided into a plurality of sections, and the light control operation is performed for each section. It can also be used for a variety of purposes, including building windows and partitions.

Next, an explanation will be given based on examples.

Example 1 Chromium was deposited on a 30 cm square glass substrate using a metal mask at 10 mm intervals to a width of 100 μm and a thickness of 200 Å to form a conductive wire, and on top of this, an In ₂ O ₃ −SnO ₂ transparent electrode was placed over the entire surface. Using a substrate deposited to a thickness of 2000 Å, WO ₃ was formed to a thickness of 7000 Å on the front substrate. This 2
Place the two boards facing each other and cover the periphery with epoxy resin.
Seal with a width of mm, and internally contain 0.1M of LiClO ₄ in propylene carbonate and 0.1M of LiI as electrolytes.
was injected, and the injection port was sealed with epoxy resin to create a light control body. Note that this conductive wire has a width of 2 mm at one end of the board as shown in Figure 2.
It was designed to form a band-like body from which it was connected to the outside.

When a voltage of 1V was applied to this dimmer for 2 minutes, the light transmittance was approximately 30%, and the difference in light transmittance between the center and the periphery was 5% or less. Moreover, this chrome was so thin that it was hardly noticed.

On the other hand, in a light control body using a conventional substrate with only a transparent electrode of In ₂ O ₃ −SnO ₂ without using chromium conductive wires, the light transmittance is about 20% in the peripheral area.
However, the difference in the center area was more than 40%, and the difference was more than 20%.

Example 2 Chromium was placed on a 90cm x 60cm glass substrate at 20mm intervals 1
A light control body was formed in the same manner as in Example 1 except that it was deposited to a width of 500 Å in mm and a thickness of 500 Å.

When a voltage of 1.5V was applied to this dimmer for 2 minutes, the light transmittance was approximately 35%, and the difference in light transmittance between the center and the periphery was less than 10%.

In contrast, a simple method that does not use chromium conductive wires
In a light control body using a conventional substrate with only a transparent electrode of In ₂ O ₃ -SnO ₂ , the light transmittance was about 10% at the periphery, but it was over 50% at the center, a difference of 40%. %, which was even more remarkable than the difference in Example 1.

The light control body of Example 2 has a chrome line width of 1 mm.
Although it was visible to the naked eye, it was only visible as a thin line in the window, so the appearance did not deteriorate much.

As described above, the light control body of the present invention can quickly obtain uniform coloring density, and the effect is particularly large when used in a large light control body, making it suitable for various applications. is possible.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional explanatory diagram of a basic example of the present invention. Second
3 and 3 are front views showing examples of patterns of conductive wires of the present invention. 4 to 6 are cross-sectional explanatory views of examples of the present invention. Transparent substrate: 4, 6, 34, 44, 46, Transparent electrode: 2, 5, 32, 42, 45, 52, 55, Conductive wire: 1, 11, 21, 31, 41, 48,
51,58.

Claims (1)

[Claims] 1. A light control body in which a transparent substrate on which an electrochromic material layer is formed on a transparent electrode and a transparent substrate on which a counter electrode is formed are laminated via an electrolyte,
A light control body made by laminating low-resistance conductive wires on or below a transparent electrode.