KR880001970B1 - Ion exchange-electrolyte layer stiching method as electrochromic devices - Google Patents

Abstract

A layer of ion-exchange resin is applied as electrolyte layer in an electrochrome appts. by cutting a piece of suitable size and shape from a sheet of self-supporting film of the resin, using a die and a matrix, fixing the piece of film to the head of the same die as used for the cutting, applying the piece on the head of the die in such a way that it covers the electrochrome layer of the electrochrome appts., transferring the piece from the head of the die to the carrier, and pressing the piece firmly against the electrochrome layer on the carrier.

Description

Method for attaching ion exchange resin film as electrolyte layer of electrochromic device

1 is a side view of the punch.

2 is a bottom view of the punch.

3 is a vertical section of the die.

4 is a sectional view taken along line 4-4 of FIG.

5 is a bottom view of the die shown in FIG.

* Explanation of symbols for main parts of the drawings

1: Punch 2: Die

3: vertical hole 4: horizontal slot

5: groove 6: face of punch end

The present invention relates to an improved method of manufacturing an electrochromic device, and more particularly, to a method of attaching a polymer ion exchange resin film as an electrolyte layer in the production of laminated electrochromic devices.

The present invention is particularly useful for making electrochromic watch dials or other small electrochromic display devices.

The two layers of the persistent electrochromic layer and the electrolyte layer are configured to be ionically conductive in surface contact with each other, and means for reversibly imparting current between the electrodes to provide a reversible ion flow between the electrochromic layer and the electrolyte layer. Electrochromic devices are known that are disposed between two electrode surfaces having a diameter. By applying a current to such a device, a color image of the electrochromic layer can be expressed or disappeared along the direction of the current. When no current is applied, the electrochromic layer has a persistence no matter what state was last caused. Thus, by applying small current charges of appropriate polarity to the electrode leads, a digital color image can be formed, dissipated and changed at the field of view.

The material used to form the electrolyte layer in such an apparatus is a thin film of ion exchange resin, which must absorb and contain a small amount of water sufficient to activate the ion exchange function of the resin.

One conventional method of adhering such a resin layer to such an electrochromic device is to solvent coat a soluble resin layer on an electrochromic layer supported on an electrode substrate of a conductive glass plate or the like. Another method of forming an ion exchange resin film in an electrochromic device is to cut a self-supporting film of resin into pieces of uniform size and place it on an electrochromic layer on a support substrate. The present invention improves on this latter method. The problem with attaching a self-supporting film layer is that the contact surfaces are in electrical contact at all points. If air enters between the film and the substrate, the surface contact between the layers tends to be discontinuous. This discontinuity appears as spots in the finished device, where the electrochromic layer does not change color when current is applied.

The present invention provides a method of shearing and attaching an electrolyte layer to an electrochromic device using a freestanding ion exchange resin film as an electrolyte layer material. After the pieces of film are cut to the appropriate size by the bias and the die, the pieces of film are placed on the electrochromic layer on the supporting substrate in such a way that the cut film releases air between the film and the substrate when pressed against the substrate. Is attached to. The present invention can be easily applied to mass production.

The present invention will be described below with reference to the accompanying drawings, the most preferred example.

In FIG. 1, the punch 1 is a straight rod having a cross section of the same shape and size as the shape and size of the film piece to be cut by the punch and placed in the electrochromic device. For example, the cross section of the punch is a square with slightly rounded corners as can be seen in FIG. The face 6 of the punch end for cutting the film has a slightly rounded side shape. In a preferred example, the radius of curvature of such rounded face 6 is 2 inches (5.08 cm), the length of the punch is about 3.5 inches (8.08 cm), and the cross section size of the punch is 0.5 inches (about 1.27). Cm) square.

3, 4 and 5 show a die 2 for use with the punch 1 to cut out a piece of resin film and place it in an electrochromic device. That is, FIG. 3 shows a vertical cross section of the die 2, FIG. 4 shows a cross section along line 4-4 of FIG. 3, and FIG. 5 shows a bottom of the die.

A square vertical life 3 with rounded corners penetrates in the longitudinal direction of the die 2, and the punch 1 passes through this vertical hole 3. This vertical hole 3 is shaped to guide the passage of the punch in the longitudinal direction of the die. In other words, the vertical hole 23 has the same shape and size as the cross-sectional shape and size of the punch 1 as viewed from above. The horizontal slot 4 is orthogonal to the vertical hole 3 and is cut into the die from one vertical side of the die 2 via the vertical hole 3. The flat bottom of the horizontal slot 4 provides a stand on which the resin film is placed to be cut by a punch. In the drawings, resin films are not shown for the sake of clarity of the die. In operation, the resin film is inserted into the slot 4 and arranged so as to cover the vertical hole 3 on the flat bottom of the slot, and then the punch 1 is punched from above the die 2. 3) Put it inside and press down. As the end face 6 of the punch enters the resin film and continues to pass through the flat bottom of the slot and into the vertical hole 3, the resin film covering the hole 3 faces the end face 6 of the punch end. It is cut by the edge of and supported by the surface 6 of the punch end thereof and moved downward through the vertical hole 43 of the die 2. A groove 5 is formed at the bottom of the die 2 so as to form a jaw around the vertical hole 3, and the groove 5 allows the thin conductive glass substrate on which the resin film is to be attached to be placed in the groove. It is shaped.

In the example shown in the figure, this groove 5 is a square 3/4 inch square with rounded corners and concentric with the vertical hole 3. In other words, the groove 5 is in the form of a countersink at the bottom of the vertical hole 3. A square substrate is placed in the groove 5, and then the die is placed so that the bottom of the die 2 is placed on a firm and flat surface. Then, the punch 1 is pushed downward through the vertical hole 3 The film in the slot 4 is cut by the face 6 of the punch end, and then the punch 1 is lowered in the slot 4 with the cut piece of film slightly attached to the face of the punch end. Continued downward through the vertical hole 3, the punch 1 presses the cut piece of film against the substrate when the punch tip reaches the substrate. Since the face 6 of the punch tip is slightly curved, the film piece is first pressed against the flat substrate surface along the centerline by such curved face 6. The film piece is then transferred by adhesion from the face 6 of the punch end toward the substrate, and then the punch 1 is withdrawn from the vertical hole 3 of the vertical 2.

Another punch (not shown) having the same shape as the punch 1 described above, but having a rounded surface of the same shape and size as the face 6 of the punch tip, instead of the punch tip for cutting the film. By inserting into the vertical lifespan 3, the piece of film disposed on the substrate can be more firmly pressed into place as described above. When the elastic rounded surface of another punch comes into contact with the film on the substrate, the elastic rounded surface first presses the film against the substrate along the centerline where the film is first attached to the substrate, and then applies more force to the punch. When pressed, the elastic rounded surface of the punch is pushed outward from the centerline, gradually pushing the film against the substrate from the center outwards, and as the film is pressed gradually over the substrate surface, the air beneath the film Will be pushed outward. In this way, the substrate having the attached electrolyte resin layer (film) is separated from the die 2, and then assembled into a electrochromic display device by a known method.

Some particularly preferred polymeric ion exchange resins useful for preparing electrochromic devices according to the invention include homopolymers of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) with AMPS and vinylsulfonic acid (VAS). Copolymers. Homopolymers of VAS, AMPS or VAS or other vinyl monomers (with acid components) and other vinyl monomers, polystyrene sulfonic acids, and other copolymers of such may also be used.

The resin selected should be one capable of forming a self-supporting resin film when used in the present invention. Films suitable for this use can be made by casting (casting), molding (moulding) or other suitable film forming method. It is advisable to use a resin film with some surface adhesion to assist in the transfer of the film as described above, and such adhesion is most resin film when the resin film has the amount of absorbed moisture that it should have for use as an electrolyte. Can be obtained from The film may also contain pigments, conventional humectants or other functional additives.

As a variant of the invention, instead of using a punch with elastic ends to press the film against the substrate, the substrate is removed from the die after the film is attached by the above-described cutting punch, and then the film is rolled, It can be more firmly attached to the substrate by pressing or other suitable means. Assembly of the electrochromic device is completed by adding a counter-electrode to the side of the ion conductive film opposite the electrochromic electrode and sealing the assembly at its corners.

Particular embodiments embodying the present invention using the apparatus and method described above are described in detail below.

Example 1

An electrochromic image layer of tungsten oxide is deposited on a substrate of NESA glass with a conductive surface layer of tin oxide by a vacuum deposition method through a stencil mask. 2.7 g of polyethylene oxide with a molecular weight of 100,000, 3 g of TiO ₂ pigment and 27 g of polyacrylamido methyl propane sulfonic acid were added to 37 g of water to form a mixture. The mixture is cast in a silicone rubber film mold and then dried in a nitrogen containing atmosphere with a relative humidity of 50-55% and a temperature of 22 ° C. The cast and dried film sheets are 0.7 mm thick. The film sheet is taken out of the mold and wetted in a nitrogen atmosphere with a relative humidity of 60% to improve the plasticity and surface adhesion of the film sheet. Using the above-described punch-die apparatus and method, the film is placed in a horizontal slot of the die and a conductive glass substrate having an image layer of tungsten oxide is placed in the groove on the bottom of the die, and then the punch is passed through the die. The film in the horizontal slot is cut and the cut piece of resin film is attached to the punch end and the punch continues out below the surface of the substrate. As the punch tip reaches the substrate, the cut film piece at the punch tip is disposed to cover the electrochromic layer on the substrate and is pressed against the substrate along the contact line between the curved and flat substrate surface of the punch tip. You lose. The punch is removed leaving the cut piece of film on the substrate. Next, another knitting piece having the same shape as the above cutting punch but having an elastic curved surface at the end is pressed against the cut film piece on the substrate through the die. The pressing force at this time should be sufficient to deform the curved surface and press the film against the substrate surface gradually outward from the center line. The film is adhesive enough to adhere securely to the substrate.

The substrate to which the cut film is attached as described above is conditioned in a nitrogen atmosphere at 65% relative humidity for at least 24 hours to improve the ion conductivity of the resin layer. After this treatment, the electrode layer is pressed onto the resin layer and adhered to the resin layer, and the electrochromic device thus produced is sealed to complete the electrochromic device.

Claims (5)

Punch a film piece of a predetermined size and shape by a punch from a film sheet of ion exchange resin disposed in the die, and continue to advance the punch in the die while the cut film piece is attached to the end of the punch, Placing the cut film piece of the punch end on the electrochromic layer on the support substrate for the electrochromic layer of the electrochromic device disposed at the bottom of the cut and the cut from the punch end to the electrochromic layer on the support substrate. A method of attaching an ion exchange resin film as an electrolyte of an electrochromic device, comprising transferring a piece of film and then pressing the film piece to firmly adhere the film piece to an electrical generating layer on a supporting substrate. 2. The method of claim 1, wherein the film sheet is moisturized before cutting the piece of film so that the surface of the film sheet is slightly adhesive. The said ion exchange resin film sticking method of Claim 1 which formed the surface of the punch tip slightly curved. According to claim 1, in which the ion exchange resin film attaching method containing Ti0 ₂ pigment to the film sheet. The said ion exchange resin film sticking method of Claim 1 which contained the any one of the usual moisture absorbents in the said film sheet.

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