JPS616627A - Production of electrochromic display element - Google Patents

Abstract

PURPOSE:To obtain an EC element which has good efficiency in working, permits continuous production, is suitable for mass production and is low in production cost by imposing a gel-like electrolyte soln. on the surface of the 1st substrate enclosed with a dam by a sealant and press-sticking the 2nd substrate onto said substrate from above under the reduced pressure to form a cell. CONSTITUTION:The surface of the 2nd substrate 7 presses first the gel-like electrolyte soln. 5 when the substrate 7 is successively pressed from above by a pressing device 9. The soln. 5 is then spread on the surface of the 1st substrate 1 and contacts with the dam 4 which is an outside frame, thus spreading further along the dam 4. The dam 4 is then pressed and compressed as the dam contacts with the surface of the 2nd substrate 7, by which the dam is press-stuck to the four circumferential sides of the substrates 2, 7 thereby forming the cell. The soln. 5 is packed into the cell formed in such a manner. The cell in such a state is held for several minutes in a vacuum vessel, by which the press sticking of the realant forming the dam 4 to both substrates 2, 7 is completed and the secure cell is obtd. The gaseous N2 is thereafter introduced into a vacuum vessel to maintain the state of 1atm therein. The cell is taken out of the vacuum vessel into the atm. The cell in which the electrolyte soln. is thoroughly packed and no foam exists is thus finished.

Description

[Detailed Description of the Invention] The present invention relates to an electrochromic device (hereinafter referred to as an “IO device”).
The present invention relates to a method for manufacturing a KO element (abbreviated as ), and particularly to a method for manufacturing a KO element using a gel electrolyte solution as an electrolyte solution.

Conventional electrolyte solutions for 11i0 elements are often solution-type solutions that use organic solvents such as propylene carbonate, and electrolytes such as lyticum iodide (BJ) or lithium perchlorate with ferrocene added. It has been used. However, the solution type is FiO
Accidents are likely to occur, such as when the electrolyte solution scatters if the element's substrate breaks, or when the substrate is pressed from the outside, opposing electrodes formed on the inner surface of the substrate come into contact with each other and cause a short circuit. It had the following drawback. Furthermore, as a manufacturing method for the [0 element] using a solution type, an injection hole is made in one of two substrates on which an EC material layer is formed on the electrode surface of at least one substrate. After forming a cell by placing these with the electrode side surfaces facing each other and sealing the periphery with a sealing material, or by making an injection hole in the sealing part in advance and forming a cell, pour the electrolyte solution through the injection hole into the cell. A method is usually used in which the injection hole is closed after filling the cell, but with this method, air bubbles remain in the cell, and the electrolyte solution tends to overflow from the injection hole. , remove this overflowing electrolyte solution after blocking the injection hole,
It also had the disadvantage of requiring cleaning.

For this reason, in recent years, EC devices have been studied that eliminate the above drawbacks by using an electrolyte solution that is made into a gel by adding an appropriate gelling agent to the solution type electrolyte solution. Even in the manufacturing method of the EC element, the problem is how to insert the electrolyte solution between the substrates.

That is, since the electrolyte solution is in the form of a gel, it is difficult to inject the gel-like electrolyte solution through the injection hole after forming the cell. For this reason, conventionally, a gel electrolyte solution is heated,
A method has been considered in which the viscosity is lowered and then injected into the cell of the FtO element through the injection hole, and then cooled and the viscosity increased again. However, this method has the drawback of poor work efficiency and the time required for injection, making it unsuitable for mass production. In addition, before applying a sealant to the substrates to form a cell, the gel electrolyte solution is sandwiched between the substrates and crushed, and after peeling off the electrolyte solution that has protruded to the outside, the surrounding area is cleaned and sealed with a sealant, and the cells are sealed. However, the form of the electrolyte solution that protrudes to the outside is not uniform, making it difficult to streamline the peeling process, and this method is not suitable for mass production. Moreover, the peripheral seal was incomplete and the durability was insufficient.

The present invention was made to eliminate the drawbacks of the conventional FliO element manufacturing method, and provides a method for manufacturing EC elements that has good work efficiency, allows continuous production, is suitable for mass production, and has low production costs. The purpose is to provide

That is, the method for manufacturing an IC element according to the present invention includes the steps of forming a bank forming an outer frame using a sealing material at a peripheral position on the surface of the first electrode substrate on the side on which the electrode is formed; a step of placing a gel electrolyte solution on the surface of the first substrate; and a step of placing a gel electrolyte solution on the surface of the first substrate; placing the second substrate on the gel electrolyte solution so as to face the surface of the first substrate; and pressing the second substrate in the direction of the first substrate. The method is characterized in that the step of placing the second substrate on the gel electrolyte solution and the step of pressing the second substrate toward the first substrate are performed under reduced pressure.

Hereinafter, the method for manufacturing an EC element of the present invention will be explained in detail with reference to the drawings. FIGS. 1 to 12 are side views (partial top views) showing a typical method of the present invention. FIG. 1 shows a step of forming a bank 4 forming an outer frame using a sealing material on the first substrate 2, and FIG. 2 is a top view of the first substrate 2 on which the bank 4 is formed.

In the figure, an electrode (not shown) and an EC material layer (not shown) are formed on the surface of a first substrate 20 made of glass, plastic, etc. placed on a substrate mounting table 1. There is. A certain amount of sealing material is supplied onto the first substrate 2 by a sealing material supplying device 3 such as a dispenser or a screen printer, and the first substrate 20 is coated as shown in the top view of FIG. A bank 4 forming an outer frame having a predetermined width and thickness is formed at a peripheral position.

The embankment 4 may be placed with a frame-shaped film sheet, or with a plurality of thread-like polymeric materials twisted together, without depending on the sealing material supply device 3.

As the electrode, tin oxide (snow) or indium oxide/tin oxide (To) can be used, and when the MO element of the present invention is used as a light control mirror, a reflective metal such as titanium nitride can be used as the electrode. It's okay. As a BO substance,
Tungsten oxides (WOs), molybdenum oxides (MOOs)
2) etc. It is also convenient to bond solder to the end of the first substrate 2 and use it as a connection terminal for a power supply line that supplies voltage to the electrodes.

As a sealing material, it is a polymer that can be thermocompressed at 80°C to 200°C, has strong adhesive strength, and is suitable for gases (especially oxygen gas).
It is desired that the material has low permeability, good moisture and weather resistance, good chemical resistance, and has a dense composition that does not collapse and spread when the substrate 82 is pressed. The embankment 4 is formed by forming such a material into a film or thread form, or melting it and applying it onto the first substrate 2. Examples of materials with such characteristics include ethylene vinyl acetate (I
VA), polyethylene (PI!i), nylon, urethane, silicone, vinylidene chloride, ethylene ethyl acrylate, ethylene vinyl alcohol, ethylene acrylate J#
lil is preferred. Furthermore, if these materials are filled with a silane coupling agent, inorganic or organic filler, etc., better properties in terms of adhesive strength, gas permeability, etc. can be obtained. Furthermore, if the first substrate 2 is subjected to primer treatment in advance, more desirable characteristics can be obtained.

The optimum width of the embankment 4 varies depending on the size of the NC element, but for a normal small element, about 2 mm is appropriate, and the height of the embankment 4 (film thickness) is 50 μm to several inches. The degree is appropriate. More desirably, when the bank 4 is pressed and bonded with the second substrate on which the opposing electric conductor is formed, the film thickness is 5.
The height of the embankment 4 is preferably about 0 μm to 100 μm, and for this purpose, the height of the embankment 4 is preferably about 60 μm to 200 μm.

FIG. 3 shows the step of placing the gel electrolyte solution 5 on the surface of the first substrate 20 surrounded by the embankment 4, and FIGS. 4 to 10 show the first substrate after this step. FIG. 2 is a top view of the substrate 2. FIG.

In the figure, a predetermined amount of the gel electrolyte solution is placed on the surface of the first substrate 2 surrounded by the bank 4 by an electrolyte solution supply device 6 such as a dispenser. The gel electrolyte solution 5 is prepared by printing, transfer, knife coating, etc.
It may be applied uniformly over the entire surface surrounded by the bank 4 on the first substrate 2, but in this case, when the second substrate is placed, air bubbles (as described later) Since the process is carried out in a vacuum with a slight amount of N2 gas present, N2 gas bubbles (N2 gas bubbles) tend to remain. Therefore, as shown in FIGS. 3 to 11, it is desirable to swell the electrolyte solution 5 at the center of the upper surface of the first substrate 2 and spread the electrolyte solution at the center with the second substrate. . At this time, the electrolyte solution 5 can be placed on the surface of the first substrate 20 by placing it uniformly in a rectangular shape as shown in FIG. , those that are placed uniformly in dotted shapes, those that are placed uniformly in a circular or manual shape as shown in Figures 6 to 8, and those that are placed uniformly in a circular or manual shape as shown in Figures 9 and 10. Various methods of placement are possible, such as placing it in a relatively large block at the center and placing it in smaller blocks at the periphery.
It is better to have a relatively large lump in the center and provide small lumps near the four corners to compensate for the lack of spreading of the lump-like electrolyte solution, so that no air bubbles remain. Therefore, in the above-described mounting methods shown in FIGS. 4 to 10, the mounting method with the larger figure number (i.e.,
The mounting method shown in FIG. 10) is more preferable than the mounting method shown in FIG. 4 because air bubbles are less likely to remain. In addition, at this time, the electrolyte solution 5
The electrolyte solution 5 is placed on the first substrate 2 in a nitrogen gas atmosphere to prevent oxidation.The viscosity of the electrolyte solution 5 is desirably from s, oOOOPB to 5o, ooooopsa, and the viscosity is adjusted by heating or heating the electrolyte solution 5. This is done by cooling or diluting with a solvent.

The material for the electrolyte solution is γ-butyrolactone (γ-
BIJ), propylene carbonate, butyl alcohol, etc., resins that dissolve in the organic solvent and form a gel, such as urethane resins, acrylic acid resins, oxidized resins, and other resins, and needless to say are not limited to these.

FIG. 11 shows the step of placing the second substrate 7 on which electrodes are formed on the gel electrolyte solution 5 with the electrode surface facing the electrode surface of the first substrate 2. As shown in FIG. The second substrate 7 is placed in a substrate holder 8 under a gas atmosphere, and it is desirable to maintain the residual nitrogen gas pressure at about 10 Torr to 60 Torr. Further, the temperature of the substrate mounting table is preferably about 50°C. If the degree of vacuum is too high or the temperature is too high, the solvent in the electrolyte solution 5 will vaporize and begin to foam; if the degree of vacuum is too low, bubbles will form in the cells when pressing the second substrate 7 to form the cells. This is because there is a higher possibility that the remaining particles will remain.

As with the electrodes on the first substrate 2, the electrodes formed on the second substrate 7 are made of metal such as 8nO* or TiN. Furthermore, if the mC material layer is not formed on the electrode of the first substrate 2, a W layer is formed on the electrode of the second substrate 7.
A BO material layer such as on is formed. Note that, like the first substrate 2, both the electrode and the EO material layer are not shown.

In FIG. 12, the second substrate 7 is pressed against the first substrate 2 in a vacuum with an N8 gas pressure of 10 Torr to 60 Torr, and the second substrate 7 is pressed against the first substrate 2 using a known pressing device 9. The pressure to press the second substrate 7 to the first substrate 2 around the four peripheries of both difference plates should be approximately IK4/at to 7 Kf/- to prevent the spread of the electrolyte solution and the sealing material on each substrate. 2.7 Desirable on edge crimp.

When the second substrate 7 is pressed from above by the pressing device 9, the surface of the substrate 7 first presses the gel-like electrolyte solution 5, and the electrolyte solution 5 is spread on the surface of the first substrate 10. death,
It comes into contact with the embankment 4 that serves as the outer frame, and further extends along the front area 4. Next, the embankment 4 comes into contact with the surface of the second substrate 70, is compressed, and is pressed to the four peripheries of the substrates 2 and 7 to form a cell. A gap-shaped electrolyte solution 5 between the first and second substrates 2 and 7
regulated by the amount of Thus, the first. Second board 2
．． 7 and the embankment 4 to create a state of differential pressure between the sealing material forming the embankment 4, and by taking out the cell from the vacuum 1 into the atmosphere, even if air bubbles remain in the cell, the air bubbles are removed. is quenched by atmospheric pressure, leaving a cell completely filled with electrolyte solution and free of air bubbles.

Note that the cell of the IC element is completed through the above steps, and sufficient durability can be obtained with only the barrier 4 made of sealing material.
As shown in the cross-sectional view in the figure, if a secondary sealing material layer 10 is further formed on the outside of the sealing material bank 4, the cells become stronger and the durability increases. The secondary sealing material 10 is butyl rubber.

It may be formed using a material such as fluororesin, vinylidene chloride resin, or epoxy by a method such as fusion bonding.

Note that the reference numeral 11 in FIG. 13 indicates a solder layer, and the first and second
It is formed at the end of the substrate 2.7 and is used to solder a power supply line connected to an external power source.

Hereinafter, the method for manufacturing an EO element of the present invention will be explained in more detail by showing specific examples.

Example Deoxygenated and dehydrated 0°75MLi, dehydrated polyvinyl butylar/gamma-butyrolactone solution 50 ml
I/25f was dissolved in an N2 gas atmosphere to prepare a gel electrolyte solution. 1. A substrate formed by depositing only a To film as an electrode on a 10 crn square glass substrate. T.T.O.
A WOa layer is further formed as an EC material layer on the film by a vapor deposition method to prepare a substrate, and solder that can be welded to glass is adhered to the edge of each substrate to form a solder layer 11 as shown in FIG.
was formed. At this time, the sheet resistance of the TO film is 10Ω, and the WOs
The thickness of the layer is 5. It was set as ooaX.

Next, an EVA film having a thickness of 100 μm was used as a sealing material, and as shown in FIG. 14, it was shaped into a rectangular frame with a hole in the center having the same size as the substrate. At this time, the width d of the frame portion was set to 2〒.

The frame of this IVA film was used as the first film on which the TO film was formed.
It was placed on a substrate and used as an embankment.

Next, 0.55 f of the gel electrolyte solution was applied from a dispenser onto the surface of the first substrate surrounded by the bank in the pattern shown in FIG. 8. This step was performed under an inert atmosphere filled with N2 gas in a vacuum chamber.

Next, the N2 gas was degassed to 30 Torr, and the first
The WON layer forming surface of the second substrate on which the WTO film and the Won layer were formed is opposed to the WTO film forming surface of the first substrate, and the WON layer forming surface of the second substrate is placed on the mass of the gel electrolyte solution. Place it,
It was pressed from behind using a suppression device. The pressing force at this time is 5
Kg/cd, and pressurized for 3 minutes while heating the sealing material part in the vacuum tank to 11 o'C.

After that, N2 gas was introduced and the pressure in the vacuum chamber was set to atmospheric pressure.
It was left as it was to cool and the sealing material was fixed to the inner board.

A power supply line for external source connection was soldered to the solder layer on the end face of the board, and as shown in Fig. 13, the end face was sealed with epoxy adhesive as a secondary sealing material 1o to create an EC element. .

Example 2 In the same manner as in Example 1, a gel electrolyte solution was prepared, and in the same manner as in Example 1, a To film alone or an ITO film and a WOs layer were evaporated on the surface, and a solder layer was formed at the t7 end. Two glass substrates were prepared, and hot melt type FiVA was applied with a dispenser to a thickness of 100 μm and a width of 2 cm on the four peripheries of the surface on which the To film was formed on one of the substrates to form a bank.

The substrate with the bank formed therein is placed in a vacuum chamber, and the gelled electrolyte solution is heated to reduce its viscosity, and then applied to the surface of the substrate surrounded by the bank using a dispenser as shown in FIG. Electrolyte vinegar solution was applied in a similar pattern. By lowering the viscosity in this way, the electrolyte solution could be easily applied onto the first substrate.

In the same manner as in Example 1, another glass substrate was placed and pressed in a straight-walled state on the gel electrolyte bath solution and held at atmospheric pressure, and then a power supply line was soldered to the end.

Next, the peripheral portion was secondarily sealed with hot melt type butyl rubber to produce an EC element.

Example 3 The hot melt type BVA of Example 2 was replaced with tetrahydrofuran (THF), butyl acetate, and cyclohexane. FiVA was dissolved in a solvent such as dichloroethane, xylene, and carbon tetracarbon, and a silane coupling material was added thereto. The sealing material prepared in this way had stronger adhesive strength than hot melt type KVA.

Example 4 Instead of the hot melt type mv material of Example 2, a sealing material made by blending hot melt type IVA with polyvinylidene chloride was used.

This sealing material showed excellent properties in terms of moisture resistance and oxygen permeation resistance.

Example 5 A gel electrolyte solution and a glass substrate were prepared in the same manner as in Example 2, and hot melt type butyl rubber was applied using a dispenser onto one of the four peripheries of the glass substrate as shown in FIG. A second outer frame 13 was formed by applying hot-melt type BVA to the inside of the first outer frame 12 using a dispenser, thereby forming a double bank. After this, an me element was manufactured in the same manner as in Example 2, except that no secondary sealing was applied to the outside of the first and second substrates.

In this example, by forming a double bank, high sealing performance was obtained without applying a secondary seal to the outer end surface of the substrate.

As explained above, in the method for manufacturing an EC element of the present invention, a bank forming an outer frame is formed using a sealing material at a peripheral position on the surface of the first substrate, and the first substrate surrounded by the front surface is A gel electrolyte solution is placed on the surface, and a second
Since the cell is formed by pressing the substrates together under reduced pressure, the electrolyte solution does not protrude outside the cell, so there is no need to remove and clean the protruding electrolyte solution. There is no need to heat the solution to lower its viscosity before injecting it into the cell, making it extremely efficient. Furthermore, no air bubbles remain in the cell, and therefore, the electrolyte or redox agent is oxidized by the remaining air bubbles, causing deterioration of the EC element. Yotsu℃
, it has excellent continuous productivity and is suitable for mass production, resulting in lower production costs.

[Brief explanation of the drawing]

1 to 12 are side (partially top) views showing a typical example of the method for manufacturing an EC element of the present invention, FIG. 13 is a sectional view showing a state in which the secondary sealant is applied, and FIG. 14 15 is a top view showing one embodiment of the embankment, and FIG. 15 is a top view showing another embodiment of the embankment. DESCRIPTION OF SYMBOLS 1... Substrate mounting stand, 2, 7... Substrate, 3... Seal material supply device, 4... Bank, 5... Gel-like electrolyte solution, 6... Electrolyte solution supply device, 8 ... Substrate holder, 9... Pressing device, 10... Secondary sealing material layer, 11
...Solder layer. Above is Figure 1 Frequency 27 Figure 3
Fig. 47 Fig. 5 Fig. 6 Fig. 7 Miyabi 8 Fig. 9 Fig. 10 Embroidery 12 Fig. Yoi 14 Fig. 15

Claims (2)

[Claims] (1) Further forming an EC material layer on at least one electrode surface of the first and second substrates having electrodes formed thereon;
, in the method for manufacturing an electrochromic device, in which the surface of the second substrate on which the electrode is formed is placed inside and sealed by sandwiching a gel electrolyte therebetween, the surface of the first substrate on the side on which the electrode is formed; forming a bank forming an outer frame using a sealing material at a peripheral position above the bank; placing a gel electrolyte solution on the surface of the first substrate surrounded by the bank; and a step of placing a gel electrolyte solution on the surface of the first substrate surrounded by the bank. on the gel electrolyte solution so that the surface of the second substrate on which the electrode is formed faces the surface of the first substrate on which the electrode is formed; pressing the substrate toward the first substrate; placing the second substrate on the gel electrolyte solution; and pressing the second substrate toward the first substrate. A method for manufacturing an electrochromic device, characterized in that the step is performed under reduced pressure. (2) The step of forming a bank forming an outer frame using a sealing material at a peripheral position on the surface of the first substrate on the side where the electrodes are formed is a step of forming a bank forming an outer frame with a sealing material around the surface of the first substrate on the side where the electrodes are formed. The electrochromic device according to claim 1, which is a step of forming a double bank by a first outer frame formed on a position and a second outer frame formed inside the first outer frame. Method of manufacturing elements.