JPS62286024A - Electrochromic display element - Google Patents

Abstract

PURPOSE:To prevent the blurring of a display and to improve a memory characteristic by forming an anisotropic conductive film of a conductive film having anisotropy in the thickness direction and forming an ion conductive film of a mosaic-shaped ion conductive film formed by dividing the film to n and m (n, m are positive integers) segments at the X-axis and Y-axis. CONSTITUTION:The anisotropic conductive film of the constitution laminated with a transparent conductive film, electrochromic film, ion conductive film, counter electrode and anisotropic conductive film is formed of the conductive film having the anisotropy in the thickness direction and the ion conductive film is formed of the mosaic-shaped ion conductive film formed by dividing the film to the n and m (where n, m are positive integer) segments at the X-axis and Y-axis. The mosaic-shaped ion conductive film refers to such a film formed by alternately arranging so-called electrolytic materials which permits the flow of ion current when impressed with a voltage to a mosaic shape with an inert matrix in-between and to such a film which allows the flow of the current in the thickness direction of the film but prohibits the flow of the current in the transverse direction. Such ion conductive film is not limited to a high-molecular ion exchange membrane and includes the film arranged with electrolyte parts contg. an inorg. salt, etc., to the mosaic shape.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an electrochromic display element (hereinafter abbreviated as an ECD element) that does not reversibly develop or fade color upon application of a voltage. 11), a surface-writing type ECD element with less bleeding, good memory performance, and clear display.
It is about providing.

(Prior art and problems to be solved by the invention) ECD
The device is a display device that utilizes the reversible color change that occurs in inorganic or organic materials when voltage is applied, and has features such as clear display and a memory function.

However, in general, ECD elements do not have threshold characteristics in their electrochromic film (hereinafter abbreviated as ECIIW) itself, making matrix driving difficult. Applications such as segment display were exclusive.

On the other hand, in Japanese Patent Publication No. 52-46098, E
A so-called surface writing type 0ECD element in which data is written from the surface of the CD element has been proposed.

This ECD element has the feature that since current flows only in the area touched by the pen electrode, it is possible to selectively color only that area, making it easy to draw letters and complex designs. However, in this ECD element, the EC film and the ion conductive layer are significantly deteriorated because the EC film is directly exposed to the atmosphere, and the EC film and the ion conductive layer are in direct contact with the EC film.
There were problems such as the film was easily damaged, the display was prone to smearing, and the memory performance was poor.

(Means for Solving the Problems) The present inventors have conducted extensive research to solve the above problems. As a result, by stacking and using a conductive film that has anisotropy in the thickness direction on the write electrode side, and stacking an ion conductive film divided into segments, we have been able to prevent display blurring and dramatically improve memory performance. Furthermore, by positioning the EC film on the transparent conductive film side opposite to the anisotropic conductive film, it is possible to improve the clarity of the display and improve the visibility. The present invention was completed based on this finding.

That is, the present invention is a transparent conductive film, ELEC!・In an electrochromic display element that has a laminated structure of a Rochromisoku film, an ion conductive film, a counter electrode, and an anisotropic conductive film, the anisotropic conductive film is a conductive film that has anisotropy in the thickness direction and is an ion conductive film. This is an electrochromic display element characterized in that it is a mosaic-like ion R electrical film that is divided into n and m (where n and m are positive integers) segments along the X and Y axes.

In the ECD element according to the present invention, a transparent conductive film, an EC film, an ion conductive film (hereinafter sometimes simply abbreviated as an Ic film), a counter electrode, and an anisotropic conductive film are generally laminated in this order. be.

ECD elements themselves are known in various forms. The transparent conductive DI, EC film, IC film, and counter electrode in the present invention are not particularly limited, and known ones can be used. Typical examples of these that are most preferably used are as follows. For example, as for the transparent conductive film, publicly known ones can be used, such as indium oxide-tin oxide (IT
O), oxides such as zinc oxide, titanium oxide, cadmium oxide, and cadmium tin oxide, semiconductor coatings, or coatings of gold, silver, etc. having a thickness of 50 angstroms or less are preferably used. As for the EC membrane, known ones can be used.
For example, amorphous tungsten oxide is the most representative,
In addition, organic dyes, metal complexes, transition metal compounds, organic polymers, and the like, which have been recently studied as EC substances, may be appropriately employed. Examples include organic compounds such as Prussian blue, phthalocyanine, viologen, spiropyran, and phthalic acid derivatives, and polymer compounds containing these units. Furthermore, known counter electrodes can be used, such as indium oxide, indium oxide, tin oxide film (ITO film), metals, amorphous tungsten oxide, iron complexes, transition metal compounds such as manganese dioxide, etc. Examples include mixtures of the above compounds and carbon, etc. The counter electrode in the present invention includes, in addition to the known ones described in section 2, those that are composed of two layers of an EC film and a transparent conductive film and function as an electrode.

Furthermore, the IC film used in the present invention has n and m (
However, it is a mosaic-like ion conductive film divided into segments (n and m are positive integers).

The above-mentioned mosaic-like ion conductive film is a film in which so-called electrolyte materials through which ionic current can flow when a voltage is applied are arranged alternately in a mosaic pattern with an inert matrix in between. A membrane that allows current to flow, but not in the lateral direction. Examples of these mosaic ion conductive membranes include conventionally known mosaic ion exchange membranes, mosaic charged membranes, and the like.

In the present invention, these publicly known membranes can be suitably used, but the ion conductive membrane of the present invention is not limited to such polymer ion exchange membranes, and may include inorganic salts as described later. It also includes membranes in which electrolyte portions are arranged in a mosaic pattern.

Among these mosaic ion conductive membranes, those called mosaic ion exchange membranes or mosaic charged membranes are particularly preferably used as follows.

However, it is not particularly limited to what is described below. For example, a membrane-like material composed of an electrically neutral layer and a layer having an ion-exchange group, the layer having the ion-exchange group exists so as to penetrate through the thickness of the membrane-like material, and Each layer exists as a microscopic phase separation. In the above-mentioned ion exchange base layer, in the known mosaic charged membrane, a layer having a cation exchange group or an anion exchange group and a layer having an anion exchange group or a cation exchange group are separated by an electrically neutral layer. However, in the present invention, in addition to the membrane-shaped material described in 2, a layer having the same type of ion exchange group is present separated by an electrically neutral layer. are preferably used.

1. Microphase separation means that a layer with ion exchange groups exists in a manner that can be microscopically distinguished from an electrically neutral layer, and the layer with ion exchange groups is the same as the thickness of the ion conductive film. It suffices if it exists with a penetration of 1tfiL in the direction.

In addition, the above-mentioned electrically neutral layer means a layer that does not substantially conduct electricity during use, and even if ion exchange groups are present, the electrical resistance is 5 times higher than that of the layer having ion exchange groups. If the layer is larger than this, electricity will not substantially pass during use, so the layer can serve as an electrically neutral layer.

The IC film used in the present invention can be used without any particular limitations as long as it has the above-mentioned properties, and the manufacturing method thereof is also not particularly limited. Typical methods for manufacturing the IC film are as follows.

■ Binary or multi-component block copolymers, one in which ion-exchange groups can be introduced and the other in which ion-exchange groups cannot be introduced, are prepared by selecting an appropriate solvent and adjusting the temperature and temperature as film-forming conditions. Films are formed by means such as applying a gradient, and have ionic conductivity penetrating in the thickness direction of the film.More specifically, vinylpyridines and butadines are block copolymerized to cause phase separation as described above. The film is formed into a film and then subjected to an alkyl halide alkylation treatment to disperse the anion exchange group-containing part in the polystyrene phase.

■ A method in which a large number of ion conductive thin films and insulating thin films are laminated, fused or glued to form a block, and then this is cut into thin films in a direction perpendicular to the film surface.

■ A method in which a large number of ionically conductive fibers are consolidated with nonionically conductive polymers and then cut in a plane perpendicular to the length of the fibers.

■ A method in which ion-conductive fine particles with a particle size that matches the film thickness are uniformly dispersed in a non-ion-conductive polymer and molded.

Although some examples are given below, the present invention is not limited to these means, and the layer having an ion exchange group of the membrane does not penetrate in a two-dimensional direction, and the layer having the ion exchange group There is no particular limitation as long as there is a method for making an IC film that penetrates through the film in its thickness direction.

The ion exchange group constituting the rc membrane of the present invention is not particularly limited, and any known ion exchange group can be used. Examples of typical ion exchange groups include sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphorous acid groups, sulfate ester groups, phosphoric ester groups, phenolic hydroxyl groups, thiol groups, and metals. Any complex having a negative charge in an aqueous solution is effective, and hydrogen ions, ammonium ions, metal ions, and other organic ammonium bases are preferably used as counter ions. Examples of anion exchange groups include primary, secondary, and tertiary amines, quaternary ammonium bases, tertiary sulfonium bases, quaternary phosphonium bases, and cobaltidinium bases, all of which have a positive charge in an aqueous solution. It is valid. Counter ions include halogen ions, sulfate ions, nitrate ions, hydroxide ions,
Inorganic ions such as nitrite ions, sulfite ions, phosphate ions, phosphite ions, hydroxide ions, hypochlorite ions, and negatively charged anions such as carboxylic acid groups and sulfonic acid groups are all effective. be.

Furthermore, the cation exchange groups and anion exchange groups of the IC membrane used in the present invention as described above do not need to be ion exchange groups in advance, but may be functional groups that can become ion exchange groups under the conditions of use, such as -8O□. X, -COX, -CN, C
oR, 502R, (however, X is a halogen atom, R is an alkyl group), a functional group that can become a cation exchange group under usage conditions, and a functional group that can become an anion exchange group under usage conditions, such as an epoxy group, a benzyl halide group, etc. It may be.

The materials constituting the IC membrane of the present invention may be inorganic or organic materials without particular limitation, but polymers having ion exchange groups are most preferred. Examples of polymers having cation exchange groups include styrene sulfonic acid polymers and their salts, or polyvinyl compounds and polyallyl compounds that form a crosslinked structure with the monomer and divinylbenzene, etc.
Copolymerized polymethallyl compounds, etc. (crosslinked polymers)
; Acrylic acid, methacrylic acid polymers and their salts, crosslinked polymers of these monomers, copolymers with other copolymerizable monomers, perfluoroalkyl vinyl ether sulfonyl fluoride and tetrafluoride; Hydrolyzed with a copolymer of ethylene to give a sulfonic acid group, or its salts: Hydrolyzed with a copolymer of barfluoroalkyl vinyl ether carboxylic acid methyl ester and tetrafluoroethylene to give a carboxylic acid group and salts.

In addition, examples of polymers having anion exchange groups include:
Polymers and copolymers of vinylpyridine, N-alkylated products of these polymers, and aminated polymers and copolymers of chloromethylstyrene are used. It also includes copolymers (crosslinked polymers) of polyvinyl compounds, polyallyl compounds, polymethallyl compounds, etc. that form a crosslinked structure such as divinylbenzene.

When the layer having the ion-exchanging IA group is present in the electrically neutral layer with microphase separation, the size of the layer having the ion-exchanging group is as small as possible, for example, 200 μm or less, preferably 501 μm or less. It is preferable that it is less than m.

Further, the IC film constituting the ECD element of the present invention is
By dividing the display into segments n and m (where n and m are positive integers) along the axis, it is possible to prevent blurring of the display of the ECD element and to dramatically improve memory performance. became.

Methods of dividing the above IC film into segments include coating the ion-conducting part and insulating part in two coats by screen printing, etc., and applying light to the ion-conducting part and insulating part after assembling the ECD element. I of the part that is not in contact with the membrane
A method of curing or cross-linking the C membrane to reduce its ion conductivity, a method of applying an ion exchange membrane capable of introducing a polymer membrane to the EC membrane and then introducing an ion exchange group only to the portion where conductivity is desired, etc. There is.

The number of divisions of the segment 1. is not particularly limited and may be determined as necessary, but in general, m is a positive integer), the n and m range from several to several hundred
The value may be selected from 50,000 to 5,000,000, for example.

The anisotropic conductive film used in the present invention itself is well known, and these known films can be used in the present invention without particular limitation. Typical examples of the anisotropic conductive film include polymer films made by electrolytically polymerizing aromatic compounds such as pyrroles and thiophenes in a pattern in a polymer matrix to make them conductive. The manufacturing method of the above-mentioned polymer film is not particularly limited.
The manufacturing method and the resulting anisotropic M conductive film described in Japanese Patent No. 60-107210 and the like are preferably used. The anisotropic conductive film used in the present invention is not limited to the film-like material obtained by the above-mentioned electrolytic polymerization, but is made by mixing a conductive filler such as carbon or metal powder into a thermoplastic resin and forming it into a film. It is also possible to use a film in which thin metal wires are embedded in a direction perpendicular to the film surface.

The thickness of each of the above-mentioned film-like materials constituting the F and CD elements of the present invention is not particularly limited, but in general, the thickness of the transparent conductive film is 100 to 5,000 μm, the EC film is 1 μm, and the thickness of OO μm to 5 μm.
Preferably, the number of electrodes is 3,000 to 6,000, the IC film is 1,000 to 200μ, and the counter electrode force is preferably selected from the range of 1 to 80μ, and the anisotropic conductive film is 5 to 100μ.The ECD element of the present invention is configured. Transparent conductive film, EC film, IC
The method of laminating the film-like materials of the membrane counter electrode and the anisotropic conductive film is not particularly limited, and any known physical or chemical method may be used to laminate them. Examples of representative methods that are generally preferably adopted are as follows.

A transparent conductive film is deposited on a transparent substrate such as glass or a polymer film such as polyethylene terephthalate by vacuum evaporation, sputtering, ion blating, or CV.
Lamination can be easily performed using a thin film forming technique such as the D method. Generally, a transparent electroconductive film is laminated on a transparent substrate, and an EC film is laminated on the opposite side of the substrate.

An EC film can generally be easily laminated on a transparent conductive film by a thin film forming technique such as a vacuum evaporation method, a sputtering method, or a CVD method. The above method is particularly suitable when the EC film material is an inorganic material.

On the other hand, if the EC film material is an organic material, there are cases where the laminating means described in (11) cannot be used. In this case, a binder may be mixed and laminated using spin coating, screen printing, or the like.

In addition, the method for laminating the ion conductive film is as follows:
EC film of a laminate with a C film = Alternatively, the solution is laminated on the counter electrode of a laminate of an anisotropic conductive film and a counter electrode by a subif coating method or screen printing method, or the solution is applied with a roller or a roller. After coating, an ion conductive film can be formed by scattering the solvent.

Also suitable is a method in which the laminate of the transparent conductive film and the EC film and the laminate of the anisotropic conductive film and the counter electrode are laminated together via an ion conductive film. The means for gluing the three parts together is pressurizing them with a pressure of 1 to 1000 kg/c+ to bring them into close contact, or simultaneously applying heat or ultrasonic vibration to improve the adhesion. Also preferred is a means for further enhancing the effect.

In addition, it is preferable that the OECD element of the present invention is used as a so-called reflective type in order to obtain a contrast between coloring and fading. In this case, it is preferable that the IC film is white.

For this purpose, TiOz and Al are used as white pigments in TCp.
Oxides such as 2O2, Tames, etc. and antimonic acid c
sbzo,, ・nH20), di-D-ium phosphate (Zr (HP 04)2 ・n H2O), titanium phosphate (TI (II P 0a)z' n H
zO) or polytetrafluoroethylene powder in an amount of 5 to 80% by weight, preferably 10 to 80% by weight, based on the IC film.
It is preferable to add 40% by weight and mix well.

Furthermore, as for the method of laminating the counter electrode, the above-mentioned method is appropriately adopted depending on the material of the counter electrode. That is, a vacuum evaporation method, a sputtering method, a CVD method, a screen printing method, etc. are preferably employed. Alternatively, the material for the counter electrode may be mixed with a binder, processed into a sheet, and then laminated in close contact with the anisotropic conductive film 2 by means of pressure bonding, fusing, or the like. Alternatively, a method of plating a counter electrode material on the anisotropic conductive film by electroplating, electroless plating, or the like may also be adopted. In addition, when a redox substance is mixed into the IC film, it may be sufficient to use only the anisotropic conductive film without using a counter electrode. Furthermore, when electrolytically polymerized films of pyrrole, thiophene, or the like are used as anisotropic conductive films, these electrolytically polymerized films themselves may act as counter electrodes.

In addition, in the 0ECD element of the present invention, the counter electrode is I
Segmenting to match the ion conductive portion of the C film is an extremely important technique for preventing smearing of the display of the device and improving memory performance.

In the OECD element of the present invention, there are cases where the ion conductive film also comes into contact with the atmosphere on the side surface of the laminate, so in this case, it is preferable to seal it with a sealant.

Generally, anisotropic conductive films, EC films, ion conductive films, and counter electrodes are often solid film-like materials, but F, C films, and IC films may be made of liquid materials to the above-mentioned thickness as necessary. It is often a good embodiment to form the film into a film.

Furthermore, in the ECD element of the present invention, interposing a transparent conductive film between the anisotropic conductive film and the counter electrode is one of the highly desirable embodiments in order to improve the response speed of the ECD element. . As the transparent conductive film, conventionally known ones can be used without any restrictions, such as oxides such as indium oxide, indium oxide-tin oxide (ITO), tin oxide, zinc oxide, titanium oxide, cadmium oxide, and cadmium tin oxide. , semiconductor thin films, or metal thin films such as gold, silver, palladium, and platinum are preferably used.

(Effects) The ECr) element of the present invention, which is obtained in a similar manner, uses an anisotropic conductive film on the writing electrode side, so it has the characteristic that it can freely draw any characters or designs. In addition, the IC film is located on the X axis and Y axis with n and m (n and m are 5
By dividing the image into segments of up to 5,000,000,000,000, it is possible to prevent display blurring and improve memory performance.

Further, in the ECD element of the present invention, since the EC film is located on the side of the transparent conductive film opposite to the side of the writing electrode, the display can be made extremely clear and easy to see.

(Examples) The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

Example] A piece of I'l"0 glass with a resistance of 10 Ω/hole was cut into a 5C angle, and the I
F soI patterns with a diameter of 100 μrn were made regularly in the vertical and horizontal directions with a space of 200 II m in the resist on the O,, JZ. On top of this, apply approximately 30% SiO over the entire surface.
After vacuum evaporation to a thickness of m, the resist and the remaining SiO were removed to obtain an ITO electrode with a pattern of 100xlrn in diameter. A solution of polyvinyl chloride in tetrahydrofuran was applied to the ITO electrode l- and gradually dried to form a 30 μm polyvinyl chloride film.

This ITO electrode-polyvinyl chloride integrated product contains 0.3 mol of virol, zM,...! Using a PT plate as an acetonitrile electrode containing 0.075 mol/p of TeI-laethylammonium chlorate, at a constant voltage of 2 ■ for about 90 minutes,
Electrolytic polymerization was performed using the I T'O electrode as a positive electrode.

After the electrolytic polymerization was completed, the ITO electrode was taken out from the electrolytic solution, the polyvinyl chloride film was peeled off from the ITO electrode, and the electrode was thoroughly washed with al-ni-l. The polyvinyl chloride film made in this way has a polypyrrole dot pattern similar to the doso pattern of the IT○ electrode mentioned above, and in the direction perpendicular to the film surface. A so-called anisotropic conductive film was obtained which had conductivity but showed no conductivity in the plane direction. Next, the anisotropic conductive film was temporarily attached to a smooth stainless steel plate, and then a square with a side of 600 μm was attached to the copper plate with a thickness of 80 ttm.
After attaching a mask with regular holes made with a space of 7+m, place it in the vacuum chamber, and then turn the inside of the -E vacuum chamber into I
After evacuation to below X 1 0''' Torr, oxygen was introduced and .WO3 was deposited to a thickness of about 11 tm at a vacuum level of 5 X ] O-' Torr to form a counter electrode.

Next, on a square polyethylene terenaphthalate film having a thickness of 100 μm and a side of 50 mm, DOFO was sputtered to a thickness of about 2000 mm as a transparent conductive film.

On the entire surface of the transparent conductive film, WO was deposited to a thickness of about 5,000 mm under the above conditions to obtain an EC film.

Next, on the EC film, an ion conductive material was regularly printed on the EC film in a square shape with a side of 600 μm at intervals of 300 μm in length and width using a screen printer. The ionic conductive substance includes 5 parts by weight of lithium perchlorate 45 parts by weight of propylene carbonate 30 parts by weight of TiO□ Average molecular g
A mixture of 20 parts by weight of polyethylene oxy F 400 and 20 parts by weight was used.

On the other hand, a photocurable insulating pentad resin was printed using a screen printer in the grid-like spaces of the counter electrode formed in a pattern on the anisotropic conductive film.

As the photocurable insulating resin, photocurable resin 302
1 (manufactured by Three Bond Co., Ltd.) 70 parts by weight, Ti0.3
A mixture of 3 parts by weight was used.

Next, the mosaic-like ion conductive part and the grid-like insulating part are pasted together so that their unevenness matches, and then UV rays are irradiated for about 2 minutes using a high-pressure mercury lamp to remove the resin in the insulating part. hardened. Furthermore, after lead wires were taken out to the outside of the transparent conductive film of the -l- arrangement element, the outer periphery was sealed with a silicone adhesive to form an ECD element.

-1- ECI) Between the transparent conductive film of the element and each dot of the polypicolol of the anisotropic conductive film, there is a positive or negative 2 to 3
The voltage (2) was applied for several seconds, and the coloring/decoloring properties, memory properties, etc. of the ECD element were observed and investigated from the transparent conductive film side. As a result, it was confirmed that coloring and fading occurred extremely quickly, and the display color also showed a beautiful blue color. Some more doso]
When the coloring was left as it was and the memory property was examined, the coloring state was maintained at the same level as the initial state after at least 10 hours, and the memory property was also good.

Example 2 A laminate of polyethylene terephthalate, ITO and WO8 obtained in the same manner as in Example 1 was placed in a plasma polymerization apparatus, 0.2 Torr of ethylene gas was introduced as a monomer gas, and high frequency power of 35 W was applied to the apparatus. A polyethylene film with a thickness of 2 μm was formed over the entire surface of the Wo3 film.

Next, a water-soluble tri-film photoresist, 7
? - Cover the sample with LR1,0 (trademark: manufactured by Hercules), expose and develop using a predetermined mask to form a resist i.
The length and width are 300. A space of +1m was opened and left regularly. This was installed in a high frequency sultta device, and SiO□
A film of about 1 .mu.m thick was laminated onto the sample-1- using Target Sol I.

Next, this sample was immersed in a 3% KOH aqueous solution at 50° C. to remove the remaining photoresist and the Sin deposited thereon. This sample was placed in a flow-through reaction tank made of transparent quartz glass, and SO□ gas and C
Ultraviolet rays were irradiated for about 1 hour while flowing a glass mixture of e2 gas at an equivalent ratio of 2=1. This causes Sin
, only on the parts of the polyethylene membrane that are not covered with -so
, cg group has been introduced.

Furthermore, this sample was taken out from the reaction tank and 5%], i0
-so, cg groups were immersed in H aqueous solution for 10 minutes to form -3O3
It was converted into a 1,i group, and further immersed in a 0.5 M -HCff aqueous solution to be converted into a -3O3H group.

The sample was then thoroughly washed with water and then immersed in glycerin for equilibration.

Next, an anisotropic conductive film of polypyrrole obtained in the same manner as in Example 1 was attached to a smooth stainless steel plate, and on top of that, a square with a side of 600 x 1 m was placed on a copper plate with a thickness of 80 μm, with a length and width of 30,017 m. A mask with regular holes cut out at regular intervals was attached.

Next, the sample was placed in a sputtering apparatus, and reactive sputtering was performed in an oxygen atmosphere of 5 mT and orr using a Tr gold metal target, and an iridium oxide film was deposited on the sample to a thickness of about 500 mm.

Next, the above polyethylene terephthalate, ITO1W
03. The laminate of the mosaic ion conductive film, the anisotropic conductive film, and the IreX laminate are glued together so that the positions of the ion conductive part and the TrOx pattern part match, and EC is applied.
It was used as a D element.

When the characteristics of the above ECD element were investigated in the same manner as in Example 1, it was found that this element operated well, although the appearance of the display was inferior to that in Example 1 because the ion conductive film did not contain white pigment. I made sure to do it.

The memory properties were as good as in Example 1, and the colored state remained almost the same as the initial state for 50 hours or more.

Example 3 1 Distilled in Completely Dehydrated Tetrahydrofuran
Dissolve one mole of styrene, add butyl lithium in a nitrogen stream to perform living synion polymerization, then add butadiene four times the mole of styrene to perform block copolymerization, and then add one mole of styrene. Furthermore, 4 moles of butadiene was added to form a quaternary block copolymer, and methanol was added to this to terminate the polymerization reaction. The resulting polymer solution was added to a large amount of methanol to obtain a precipitate, which was then dissolved in tetrahydrofuran and poured into methanol for purification, which was repeated to obtain a highly pure block copolymer.

This was then dissolved in a solvent, cast on a polytetrafluoroethylene sheet, and dried to form a film.

This was immersed in 95% sulfuric acid at 30° C. for 48 hours to cause a crosslinking reaction at the polybutadiene portion and introduce a sulfonic acid group into the polystyrene portion. This was immersed in ethylene glycol to achieve equilibrium, and a mosaic-like ion conductive film was obtained.

Next, the mosaic-like ion conductive film was placed between the polyethylene terephthalate, transparent conductive film, and WO3 laminate obtained in the same manner as in Example 1, and the commercial conductive film, Ire, and laminate obtained in the same manner as in Example 2. They were pasted together and brought into close contact under pressure to form an ECD element.

-F The characteristics of the ECD element were examined in the same manner as in Example 1, and there was almost no uneven coloring or color bleeding, and the response of coloring and decoloring was fast. Moreover, the memory property was also good at 10 hours or more.

Example 4 In the same manner as in Example 1, ITO and WO8 were laminated on polyethylene terephthalate.

In addition, in the same manner as in Example 1, the anisotropic conductive film and the counter electrode (
A laminate of WO3) was obtained.

Next, a photopolymerizable ion conductive substance was printed on the EC film and the counter electrode by screen printing, and the two were bonded together.

The photopolymerizable ionically conductive substances include 15 parts by weight of polyester acrylate, 20 parts by weight of 1,3-butanediol diacrylate, 2 parts by weight of benzoin, and N,N.
- 2 parts by weight of dimethylaniline, 2-aldylamido-2-methyl propanesulfonic acid monomer of l i type 2
A mixture of 0 parts by weight, 0.5 parts by weight of lithium perchlorate, 8 parts by weight of ethylene glycol, and 32.5 parts by weight of antimonic acid powder was used.

Next, the bonded structure was irradiated with ultraviolet light with a wavelength of around 280 nm from a metal halide lamp from above the anisotropic conductive film at a power of 100 W/cm for 10 seconds. At this time, since the WO3 used for the counter electrode absorbs light with two wavelengths, the ion conductive film below it does not polymerize, but polymerization occurs in other parts, significantly reducing the ionic conductivity. .

When the characteristics of the device were examined in the same manner as in Example 1, it was found that there was no smearing of the display and it had a memory property of 4 hours or more.

Example 5 Polyethylene terephthalate, I
A TO1WO3 laminate was obtained. Next, by screen printing, 60 lines of 300 ml of insulating material were printed vertically and horizontally.
It was printed in a grid pattern arranged at intervals of 0 μm.

As an insulating substance, TiO was added to 70 parts by weight of a commercially available epoxy adhesive (Epoxy E Set 11, manufactured by Konishi Co., Ltd.).
A mixture of 30 parts by weight of ZZ was used. Next, the epoxy adhesive was printed and heat treated at 100° C. for 1 hour to harden the epoxy.

Furthermore, on top of that, an ion conductive material made by Kojukin was printed in a pattern opposite to the previously printed insulating material.
Photopolymerization was performed by irradiating ultraviolet rays for about 10 seconds using a high-pressure mercury lamp to harden the seion conductive material. The photopolymerizable ion conductive substance includes polyethylene glycol 400 diacrylate 20 parts by weight Li-type 2-acrylamido-2-methylpropanesulfonic acid 3o heavy Ji parts benzoin
2 parts by weight ethylene glycol
3 parts by weight of lithium fluoride 0.
5 parts by weight Probylene carbonate 1-6 parts by weight Methanol 3.5 parts by weight Ti
A mixture containing 35 parts by weight of 0z was used.

Next, a counter electrode material was screen printed on the pattern of the ion conductive portion of the ion conductive film.

As the counter electrode material, carbon paste (Dotai 1
A mixture of 80 parts by weight of -FC-404 (manufactured by Fujikura Kasei ■) and 20 parts by weight of manganese dioxide was used. This was cured by heating at 80'C for 1 hour.

Next, the epoxy adhesive (Epoxy E Set L, manufactured by Konishi Co., Ltd.) was printed on the grid portion where the counter electrode material was not printed, and heat treated at 100° C. for 1 hour to harden it. Furthermore, a low-resistance conductive resin (Dotite I)-550, manufactured by Fujikura Kasei Ltd.) was screen-printed in the same pattern on the above-mentioned counter electrode, and cured by heat treatment at 50°C for 11 hours. It was made into a conductive film.

When the characteristics of the above device were examined in the same manner as in Example 1, it was found that there was no smearing of the display and the device had a memory property of 10 hours or more.

Example 6 Polyethylene terephthalate, I
A TO, WO2 laminated film was obtained.

Next, fine powder of zirconium phosphate, which is an inorganic ion exchanger, was made into a spherical shape with a diameter of 30 μm using a molding machine. This was uniformly dispersed in polyvinyl chloride dissolved in tetrahydrofuran.

This was uniformly cast on the WO3 film and tetrahydrofuran was scattered to form a polyvinyl chloride film in which spherical zirconium phosphate was uniformly dispersed on the WOx.

Next, in the same manner as in Example 5, a counter electrode and an anisotropic conductive film were screen printed to obtain an ECD element.

When the characteristics of the above ECD element were investigated in the same manner as in Example 1, the response speed of coloring/decoloring was slightly slower than that of Examples 1 and 2, but there was no smearing of the display, and the memory property was longer than 10 hours. showed that.

Example 7 When evaporating WO's as an EC film, a mask with regularly drilled holes in a square with a side of 600 μm and a space of 300 μm in length and width was attached to a copper plate with a thickness of 80 μm, and further EC was applied. ECD was carried out in the same manner as in Example 1, except that when screen printing the ion conductive substance on the membrane, the printing was done so that it matched the pattern of the patterned WO3 membrane.
We tested the element and investigated its characteristics.

As a result, the coloring and fading properties were good. Furthermore, the memory property was 15 hours or more.

Comparative Example 1 An ECD element was produced in the same manner as in Example 1 except that the ion conductive resin was printed over the entire surface and the insulating resin was not printed at all.

When the characteristics of the ECD element described in Example 2 were investigated in the same manner as in Example 1, it was found that although the response of coloring and decoloring was quick, the colored area gradually spread over a period of several minutes to several tens of minutes, and the initial coloring The coloring density of the parts became thinner, and the memory properties were not good.

Comparative Example 2 An ECD element was produced in the same manner as in Example 1 except that the thickness of the WO3 film deposited as a counter electrode was 5000 mm.
We investigated its characteristics. However, in this case, the display characteristics of the ECD element were observed from the anisotropic conductive film side. As a result, the response speed and memory properties were almost the same as in Example 1, but although the anisotropic conductive film appeared almost entirely transparent, there were still black dots, so the display was poorer than in Example 1. It was clearly inferior in terms of clarity or ease of viewing.

Claims (1)

[Claims] Transparent conductive film, electrochromic film, ion conductive film,
In an electrochromic display element having a structure in which a counter electrode and an anisotropic conductive film are laminated, the anisotropic conductive film is a conductive film having anisotropy in the thickness direction, and the ion conductive film is a conductive film having anisotropy in the thickness direction, and An electrochromic display element characterized in that it is a mosaic-like ion conductive film divided into n and m segments (where n and m are positive integers).