JPS6273237A - Ion conductive material for electrochromic display element - Google Patents

Abstract

PURPOSE:To obtain an ECD element having a non-linear relation between the voltage and current to be impressed between an EC film and counter electrode of an ECD element by selecting an ion conductive material. CONSTITUTION:This ion conductive material for the electrochromic display element consists of the ionic high-polymer material which is the ionic high- polymer material of >=3,000mol.wt. having an ion exchange group or a functional group to change the ion exchange group under use conditions and into which an ionic low-polymer material of <=1,000mol.wt. to dissociate to ions under the use conditions is incorporated at max. 1,000ppm. The skeleton of the ionic high-polymer material is adequately a polymer or copolymer of hydrocarbons, polymer or copolymer of halogen-contg. hydrocarbons of chlorine, iodine, bromine, fluorine, etc., polymer or copolymer of perfluorocarbon polymer or copolymer bound and incorporated with metals or elements such as silicon into the main chain of the above-mentioned polymers, etc. The functional group of the ionic high-polymer to be used is the ion exchange group or the functional group which change to the ion exchange group under the use conditions.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides a novel ion conductive material for an electrochromic display (hereinafter sometimes simply abbreviated as ECD) element.

[Prior art and problems to be solved by the invention] ECD
The device is a display device that utilizes a reversible color change that occurs in an inorganic or organic material by applying a voltage. The ECD element is superior in viewability because it has no viewing angle dependence compared to a liquid crystal, and has special features such as having a memory function and being able to be driven at a low voltage. However, the ECD devices that are currently being proposed for development are still a step forward in terms of practical life, response speed, and contrast ratio, and the reality is that future development is awaited.

An ECD element is generally assembled with a main structure in which a transparent conductive film, an electrochromic film (hereinafter simply referred to as an EC film), an ion conductive material, and a counter electrode are laminated.

The inventors of the present invention have confirmed that the life span, response speed, and contrast ratio of the ECD element depend not only on the material of the EC film but also on the materials of the entire ion conductive material.

The inventors of the present invention have conducted extensive research to solve the various problems mentioned above, have already made numerous proposals, and have succeeded in manufacturing a stable ECD element. When ECD elements are put into practical use, it is necessary to divide the display element into many segments in order to display fine details such as characters and images, and if the separation between the divided segments is not sufficient. It is difficult to display clear characters, images, etc. - In order to display the above clear characters and images, if there is a non-linear relationship between the voltage and current applied between the electrochromic film and the counter electrode, the current value between the segment to be displayed and the adjacent segment must be It is markedly different and can display clear credit information.

Therefore, the current issue in ECD device development is that there is a nonlinear relationship between the voltage and current applied between the Ec film and the counter electrode. This is the development of an ECD element in which a current flows through.

[Means to solve all problems]

As a result of careful consideration to solve the above technical problem, the present inventors decided to select an ion conductive material, and found that there is a nonlinear relationship between the voltage and current applied between the EC film and the counter electrode in the ECD element. It was discovered that a related ECU element could be used, and the present invention was completed.

That is, the present invention is an ionic polymer with a molecular weight of 3,000 or more that contains an ion exchange group or has a functional group that converts into an ion exchange group under the conditions of use, and an ionic polymer with a molecular weight of 1,000 or less that dissociates into ions under the conditions of use. Up to 100 low molecular weight substances
This is an ion conductive material for electrochromic display elements made of an ionic polymer containing 0 ppm.

The ion conductive material of the present invention is a molecule i-30 that has an ion exchange group or a functional group that converts into an ion exchange group under usage conditions.
00 or more, preferably H5000 or more. The skeleton of the ionic polymer has a molecular weight of 3000.
Any polymer or copolymer containing hydrocarbons such as chlorine, iodine, bromine, fluorine, etc. may be used as long as it is preferably 5000 or more and is stable. Polymers or copolymers; 9-fluorocarpoy-based polymers or copolymers; polymers or copolymers containing elements such as metal or silicon bonded to the main chain of these polymers, etc. is preferable, and the copolymer contains the above-mentioned hydrocarbon monomer, rodan-containing hydrocarbon monomer, or perfluorocarbon monomer as one component, and their mutual or Copolymers with other copolymerizable monomers can be used without particular limitation. Specific examples of these monomers and copolymers will be described later, but conventionally known ionic polymers, ion exchange resins, ion exchange resin membranes, etc. may be used as they are or those soluble in solvents. It can be used by dissolving it in a solvent if necessary.

The ion conductive material of the present invention needs to have a molecular weight of 3,000 or more, preferably 5,000 or more.

The upper limit of the molecular weight varies depending on its usage, but is generally limited to industrial production, and in the case of solid materials, especially film-like materials, the entire film-like material has a single molecular weight (high molecular weight). (500,000 to 1,000,000 for a single mouse) Preferably, the amount is about 1,000,000, and when used in the form of a liquid, it is preferably about 500,000.

Further, the functional group of the ionic polymer used in the present invention is an ion exchange group or a functional group that converts into an ion exchange group under the conditions of use. As the ion exchange group, known cation exchange groups and anion exchange groups can be used without particular limitation. Examples of particularly preferably used cation exchange groups include sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, and phosphorous acid groups.

These include sulfate ester groups, phosphate ester groups, sulfite ester groups, thiol groups, phenolic hydroxyl groups, negatively charged gold F5 complexes, and -COH.

F3 also has ion exchange groups such as primary amines, secondary amines, tertiary amines, quaternary ammonium bases, tertiary sulfonium bases, quaternary sulfonium bases, cobaltidinium bases, and wire mesh complex salts. These include things that have a positive charge.

Furthermore, the functional group that converts into an ion exchange group under the conditions of use is not particularly limited and can be selected from known functional groups, but examples of functional groups that are generally suitably used are cation exchange groups -802X, - COX, -CN.

When -CORl -802R (X hahaloP 7 atoms, R is an alkyl group) is an acyl or anion exchange group, examples include epoxy 7 group and pendyl halide group.

The bonding of the ion exchange group or the functional group that converts into an ion exchange group under usage conditions to the skeleton is not particularly limited, and may be bonded to either the side chain or the main chain. Further, the amount of bonded ion exchange groups is not particularly limited as long as the ECD element operates in the usage mode. Generally, the ion exchange group used is 0.2 meq/g dry resin or more and 12 meq/g dry resin or less. Preferably, 0.5 milliequivalents/gram dry resin or more and 8 milliequivalents/gram dry resin are used.

In the present invention, the most preferably used ionic polymers are styrene sulfonic acid homopolymers or copolymers containing styrene sulfonic acid as one component (hereinafter referred to as polymerizable monopolymers). A copolymer having one component thereof is simply referred to as a copolymer); a homopolymer or a copolymer of acrylic acid, methacrylic acid, vinyl sulfonic acid, etc.; Hydrolyzate of copolymer of 3,6-nokif-4-)f-7-octensulfonyl fluoride) and tetrafluoroethylene; polyvinylvinonium bases; polyethyleneimine; polybenzyltrimethylammonium bases etc.

Examples of the ionic polymer 1, ion exchange resin, ion exchange resin membrane, etc. are water n products, seawater concentration and desalination, 6-salt electrolysis,! This is a well-known type used in the field of semi-four-fathom ponds. These known ionic polymers contain the necessary monotons, catalysts, and plasticizers.

It is commercially available after mixing with a solvent and polymerizing it into a membrane-like particle shape or a fibrous ring shape as required. Therefore, it is generally possible to easily obtain a material having the required physical properties and the required shape. Generally, attempts to use ion exchange membranes as ion conductive materials in ECD elements have already been made, and as mentioned above, the lifespan of ion exchange membranes has been limited according to conventional proposals.

The speed change and contrast ratio were unsatisfactory, and it was difficult to display a single stroke of clear text. had concluded that the above-mentioned defects were fatal, but surprisingly, an ionic polymer was developed in which the ionic low-molecular substances contained in the ionic polymer were removed to a specific amount or less. EC when the body is used as an ion conductive material for ECD elements
It was discovered that a non-linear conduction relationship was observed between the voltage and current applied between the membrane and the counter electrode. That is, there is nonlinearity between the applied voltage and the amount of charge injection. That is, the ionic polymer used in the present invention contains at most 10 ionic low-molecular substances with a molecular weight of 1000 or less that dissociates into ions under the conditions of use.
00 ppm, preferably 500 pprn, and more preferably 100 ppm.

Ionic low-molecular substances with a molecular weight of less than 3000 that dissociates into ions under usage conditions are contained in large amounts in ordinary ionic polymers, and generally vary by about 2% by weight up to 5%.
There were even things that were related to it. The fact that such a large amount of ionic low-molecular substances are contained is surprising in itself, and furthermore, it is a phenomenon that such contained ionic low-molecular substances have an adverse effect on the use of the present invention as an ion conductive material for an ECD element. is a completely unexpected phenomenon. However, the mechanism by which the ionic low-molecular-weight substance exerts an adverse effect is not necessarily clear.

By removing these ionic low-molecular substances, the present inventors established a linear conduction relationship between the voltage and current applied between the electrochroic membrane and the counter electrode, as will be clear from the examples described later. Since what was shown shows a nonlinear conduction relationship, these ionic low-molecular substances dissociate into ions under the conditions of use and cause electricity to be carried, resulting in EEC.
It is assumed that the characters on the D-column and the display of one of the cars were working without any hesitation. While this phenomenon is completely unexpected as described above, it is also a surprising phenomenon.

The ionic low-molecular substances described above exist in various forms and types depending on the manufacturing method of the ionic polymer, but the following are representative examples of the substances contained in general commercially available ionic polymers: be.

(1) A low molecular weight polymer that has an ion exchange group or a functional group that converts into an ion exchange group under the conditions of use.

(11) Ionic monomeric substances that have ion exchange groups or have functional groups that convert into ion exchange groups under the conditions of use.

011) Compounds such as inorganic salts, inorganic acids, and inorganic bases that dissociate into ions under usage condition 1.

The above (1) and (+r) Vi are mainly oligomers contained in the ionic polymer in a state where the degree of polymerization is suppressed to a low level or is not polymerized or copolymerized for some reason during the production of the ionic polymer, These include altered substances of monomer (monomer substances) solvents, decomposition products of catalysts, etc.

Moreover, the above (ill) contains catalysts, solvents, hydrolyzing agents, etc. used when producing the ionic polymer, attached or adsorbed to the ionic polymer.

The means for removing the contained ionic low-molecular substance from the ionic polymer is not particularly limited, and any means may be used. The following are examples of representative means that are generally suitably adopted industrially.

If the ionic polymer is in a solid state, the ionic polymer may be mixed with a nonionic solvent such as a polar solvent such as nooxane, trimethylformand, trimethylsulfoxide, water, or alcohols, or benzene or toluene. , by immersing it in a non-polar solvent such as hexane and eluting the ionic low-molecular substance until it reaches the specified amount, or by placing an anode and a cathode in the solvent and applying electricity to move and remove the ionic low-molecular substance. The following methods are suitable. In addition, solid ionic polymers such as water, ethylene glycol, f-robylene glycol, glycerin, trimethyl sulfoxide,
In the case of liquids obtained by dissolving in nooxane, dimethylformamide, trimethylacetamide, diethylacetamide, etc. or mixed solvents containing these as components, and those in which the ionic polymer is a liquid, these liquids Preferably, a method is used for dialysis-purifying the substance using a dialysis membrane made of cellophane paper or the like, by applying an electric current, or by using only a concentration difference without applying an Ff current. In addition, it is also effective to purify a polymer by repeatedly dissolving it in a good solvent (2) and injecting it into a poor solvent and causing precipitation, which is a common method for purifying polymers.

The amount of the ionic low-molecular substance having a molecular weight of 1000 or less contained in the ionic polymer as the ion-conducting material of the present invention is a very important factor in the use of the ion-conducting material. In the present invention, the content of the ionic low molecular weight substance must be reduced to a maximum of 1000 ppm, preferably 500 ppm, and more preferably 100 ppm. If the content of the ionic low-molecular substance exceeds the above value, it becomes difficult to provide a clear display such as two strokes of characters on the ECD element.

The manner of use of the ion conductive material of the present invention is not particularly limited, and the manner of use of known ion conductive materials can be adopted as is. Examples of generally preferred embodiments are as follows.

A cationic polymer having a cation exchange group or a functional group that becomes a cation exchange group under the usage conditions, and an anionic polymer having an anion exchange group or a functional group that becomes an anion exchange group under the usage conditions. An ion conductive material in which at least two or more layers of ionic polymers are laminated is one preferred form.

In this case, the number of layers to be laminated is not particularly limited, and any one of the above ionic polymers may be used, but industrially, 2 to 7 layers, preferably 3 to 5 layers, are laminated. It is preferable to do so. In addition, the order in which the upper layer is laminated should be such that at least one set of laminates is in contact with a cationic polymer and an anionic polymer, but in general, different types of ionic polymers are laminated alternately. Preferably. In the above-mentioned lamination mode, it is preferable that at least one of the laminated materials is a liquid ionic polymer. In addition to the embodiment in which the ionic polymer itself is used as a liquid or dissolved in a nonionic solvent, the liquid material may also be used in which a solid ionic polymer is dissolved or swollen in a nonionic solvent. Any mode may be used. When the above-mentioned liquid ionic polymer is laminated onto a solid material, particularly a layered (membrane-like) ionic polymer to form the ionic 24 electric material of the present invention, the pores of the solid material are It is preferable to have a size that does not allow the ionic polymer to pass through.

Further, in the composite laminate, it is desirable that the layers are in close contact with each other, and the means for preventing the close contact may be appropriately selected from known means as necessary.

The ion conductive material of the present invention exhibits extremely good strength properties as an ion conductive material for ECD elements. Therefore, the conventionally known EC
The ion conductive material may be used as it is as the ion conductive material of the D element. The configuration of a typical ECD element will be explained as follows. For example, an ECD element is generally constructed of a transparent conductive film, an EC film, an ion conductive material, and a counter electrode in this order. As the transparent conductive film, the EC film and the counter electrode, conventionally known ones can be arbitrarily employed. For example, as for the transparent conductive film, known ones can be used, such as oxide semiconductor thin films such as indium oxide-tin oxide (ITO), tin oxide, zinc oxide, titanium oxide, cadmium oxide, and cadmium tin oxide, or 50% thick oxide semiconductor thin films.
A thin film of gold, silver, etc. with a thickness of angstrom or less is preferably used. In addition, for the EC film, known materials can be used, such as amorphous tungsten oxide, which is the most representative, but other materials that have recently been studied as EC materials, such as organic dyes, metal complexes, transition metal compounds, organic polymers, etc. will be adopted as appropriate. Further, as for the counter electrode, known ones can be used, such as iridium oxide, indium oxide-tin oxide film (ITO film), metal, amorphous tungsten oxide, iron complex, transition metal oxide-cargen sintered body, and Examples include manganese oxide and others.

Note that in this specification, the counter electrode refers to a single electrode, as well as a single electrode.
It is synonymous with electrodes of laminated structure such as EC film and metal electrode or EC film and I'rO film, and is an ECD with a breaker sandwich structure having opposing electrodes of these laminated structures.
The devices generally have good contrast ratios, response speeds, and lifetimes.

〔effect〕

An ECD element using the ion conductive material of the present invention, that is, a transparent conductive film, an EC film, an ion conductive material, and a counter electrode, are constructed in this order.
However, when divided into segments (n and m are positive integers ranging from 2 to 3 to several hundred minutes), for example, if a signal is sent to segments n-2 in the X-axis direction and m-3 in the Y-axis direction, (n -2,m
Only the segments 3) are activated, and the segments adjacent to these are not activated. Therefore, the characters, images, etc. displayed on the KECD element can be displayed clearly, and the contribution of the present invention is immeasurable.

The number of segments described above naturally depends on the size of the EC film and cannot be specified unconditionally. Generally, n and m are appropriately selected from several to several million values. The method of dividing the IC film into segments is not particularly limited, and any known method can be used as is. Typical examples of methods are as follows. When the segment unit is large, it is recommended to form a lattice-shaped barrier layer on a transparent conductive film such as ITO in advance to prevent the EC film from being formed, and then remove the barrier layer after forming the EC film. Can be hired. Further, a method using a photosensitive resin, so-called photoresist, which is widely used in the IC and LSI industries, is effective for microfabrication. That is, for example, an EC film is formed on a substrate that will become a transparent conductive film, such as ITO (1), then a negative or positive photoresist is applied thereto, a mask for forming partitions for dividing into segments is overlapped, and then exposed. Dissolve the photoresist in the part that will become the partition, further treat with an acid, alkali, etc. that dissolves the EC film fTo in the part that will become the partition, and then remove the remaining photoresist and divide it into each segment. be.

〔Example〕

EXAMPLES In order to explain the present invention more specifically, examples will be described below, but the present invention is not limited to these examples.

(Preparation of ECn element) First, an IrO2 film and a WO5 film (hereinafter abbreviated as ① film and W film) as EC films were formed by the following method.

(2) The film was formed on a transparent conductive film by the high-frequency pulse method in a pure oxygen atmosphere. That is, a 99.99% iridium metal plate was used as the target, and a glass coated with a transparent conductive film (tin oxide film 20 ohms/hole) was used as the substrate.
After cutting into 5 pieces, thoroughly washing with an organic solvent and pure water, and drying, it is mounted in a vacuum chamber, and the inside of the vacuum chamber is first suctioned until the vacuum becomes less than ~4xlO-)-. Next, the substrate was heated in a high vacuum at about 100.degree. C. for several minutes, then cooled with water and kept at 40.degree. C. or lower, and pure oxygen was introduced to form a sludge film. Oxygen pressure is 10 millitorr.
The high frequency power was maintained at 0.5 W/cm''. At this time, the film formation rate was 10 Å/min, and the I film thickness was 700 Å/min.
It was angstrom.

The W film was formed on the same substrate as the Si I film by electron beam vacuum evaporation. A film of up to 3000 angstroms was formed at a rate of 4 to 5 angstroms/second using 99.99% WO5 TARDIT.

Segments to be described later were formed by the photoresist method on the composite film of the WO film and the transparent conductive film produced as described above.

Next, an ion conductive material was laminated on this composite film, and on top of that, a composite film of a transparent conductive film and iridium oxide prepared by the above-mentioned suffix 9 tutter method was laminated, and a GCN element was made using this as a counter electrode. Created. Using the ECn element manufactured in this way, evaluations were conducted as described in Examples described later.

Example 2 A sheet of I-polyethylene with a thickness of 30 microns was immersed in a mixture of chloromethyl ether, divinylbenzene, and penzoyl oxide to fully infiltrate these monomers into the film, and then boiled. Polymerization was carried out by immersing the sample in a saturated Glauber's salt solution [7]. The obtained film was immersed in a solution of acetone-water-trimethylamine to aminate the alkyl groups in the membrane to synthesize an anion exchange membrane having quaternary am7nium bases as ion exchange groups. This obtained membrane was mixed with methanol-acetone in a 1:1 solution.
It was thoroughly extracted and purified using a mixed solvent of

On the other hand, sodium styrene sulfonate was dissolved in water, polymerized using ammonium persulfate and sodium sulfite, and then dried using a rotary evaporator to take out the polymer. This polymer was passed through an H-type cation exchange resin (Amberlite IR-120B (trade name)) to obtain polystyrene sulfonic acid. After concentrating to a concentration of about 10%, this 101! A tube-shaped dialysis membrane made of cellulose with an average pore diameter of 481 was used to remove and purify low-molecular substances by placing pure water in the external liquid. This liquid was then freeze-dried to obtain solid purified polystyrene sulfonic acid (I) in a yield of 75 cm. Therefore, about 25 ts were removed as low molecular weight substances.

In addition, pure water was also collected from the above-mentioned external dialysis solution and concentrated to a temperature of 100 ml to extract an ionic low-molecular substance whose main component is solid styrene sulfonic acid oligomer.

In addition, the unpurified polystyrene sulfonic acid containing the low molecular weight substance obtained as described above is also concentrated as it is to form a solid (li).
It was taken out as t). The inorganic ion concentration in I above is 5
01) Ill, I [It was 2000 ppm 1200 P. Using these three types of polystyrene sulfonic acids ① to ②, electrochromic display devices were made in accordance with the preparation of the ECD device described above. That is, each polystyrene sulfonic acid was dissolved in ethylene glycol to a concentration of 50%, and applied as a thin film on the EC membrane and the counter electrode. Sandwiching a thin anion exchange membrane,
They were pressed together to make a three-type 0ECD element, being careful not to introduce air bubbles. At this time, the EC film was divided into 30 segments each on both the Y-axis and the Y-axis with a gap of 0.5 parts, and a driving voltage was applied to display the images. As a result, when a signal was sent to the 15th segment in the X-axis direction and the 15th segment in the Y-axis direction, the three 0ECD elements exhibited different behaviors. That is, when polystyrene sulfonic acid purified by dialysis was used, only the segment (15°15) was colored and discolored very clearly, but when polystyrene sulfonic acid from the external dialysis solution was used, the segment (15, 15) was clearly colored and discolored. The surrounding area was colored and discolored. In addition, when unrefined products were used, it was difficult to achieve clear coloring or decoloring between the two.

Therefore, the injected charge for the voltage M of these ECD elements (
The results of measuring millicoulombs/sub 3) were as shown in Table 1. The results in Table 1 are also plotted in FIG. As shown in Figure 1, when using the three types I to ■ above, 0EC
The difference in the operation of the D element is clear.

Table 1 Example 2 50 parts of stearyl methacrylate and 50 parts of sodium styrene sulfonate were dissolved in 300 parts of dimethylformamide, 3 parts of benzoyl peroxide was added thereto to make a homogeneous solution, and the mixture was heated to 100°C for 5 hours. A polymer was obtained by heating. The viscous solution obtained here is poured into a large excess of 1.0N hydrochloric acid, stirred vigorously and left to stand.The precipitated polymer is dissolved again in dimethylformamide and poured into 1.0N hydrochloric acid. This process was repeated to convert the sodium sulfonate group into a sulfonic acid group. Then, after drying again, dissolving in dimethylformamide and pouring into pure water were repeated to remove excess acid, salt, and unreacted monomer of Olipmer, and a purified product was obtained with a yield of 70 cm. As a result of measuring the purified product by liquid chromatography, the above-mentioned low molecular weight substance could not be confirmed. Furthermore, the polymer obtained by drying under reduced pressure was dissolved in dimethylformamide, and this was coated on the EC membrane and the counter electrode, and left to scatter the solvent. A thin film having water-insoluble sulfonic acid groups was formed on the EC film.

On the other hand, polychloromethylstyrene having a molecular weight of about 500 was reacted with triethylamine to synthesize a water-soluble polymer having a quaternary ammonium base. This was placed as a water bath solution in a cellophane cylinder with an average pore diameter of about 48X, and purified water was placed on the outside to purify the synthesized polyamine. The yield of polyamine purified inside the cellophane cylinder was 65%, and as measured by liquid chromatography, the total amount of low-molecular substances was 150 parts, less than 1 ml.

Now, this polyamine was dissolved in ethylene glycol (ethylene glycol) to a concentration of 50% and sandwiched between the EC film on which the thin film was formed and the counter electrode to form a three-layered ECD element. . At this time, the EC membrane is 0.5 V
Both the Y-axis and the Y-axis were divided into 30 segments with a gap of m, and a driving voltage was applied to them to operate them.

As a result, when a signal was sent to the 15th segment in the X-axis direction and the 15th segment in the Y-axis direction, only the segment (15, 15) changed color and fading very clearly. For comparison, we assembled an ECD element using an unmanufactured polyamine sandwiched in the middle26) and carried out similar measurements.The result was a change in color similar to that of the purified polymer, but there was no effect on the surrounding segments. No bleeding of discoloration is seen.
,Ta.

Therefore, the polyamine was analyzed. ν1j When we analyzed the unpurified polyamine, the dialysis-purified polyamine, and the dialysis fluid by liquid chromatography, it was clear that low-molecular-weight substances were clearly removed from the dialysis-purified polyamine, and no traces of low-molecular-weight substances were observed in the dialysis fluid. Next. In addition, when all inorganic components were analyzed, unpurified polyamine was found in l'rl.
It contained KCL NaC1CaCt2 equivalent to 100 ppm, but in the purified polyamine, the total amount of low-molecular substances was 1:
It was below 150 ppm. When the molecular cap of the polymer was measured, it was about 14,000 when purified by dialysis.
Many of the external dialysis fluids contain less than Viiooo fn
was.

Example 3 Polystyrene sulfonic acid with a molecular weight of about 50 was placed inside a cylindrical cellophane membrane, pure water was placed in the outer solution, and the purified water was repeatedly replaced and purified by dialysis to obtain a purified product with a yield of 65 qb. Ta. When this was measured by liquid chromatography, it was found that the low molecular weight components were completely removed. This
Polyvinyl alcohol with an rrr degree of 1500 was dissolved in completely hot water, and the same was obtained by dialysis and purification with cellophane to remove impurities, and this was concentrated to form a solid. The purified polystyrene sulfonic acid obtained above and polyvinyl alcohol were mixed in a total weight ratio of 1=1, and this was cast onto a board made entirely of polytetrafluoroethylene, and then heated at 80°C for 50 minutes.
After heating for a period of time, the mixture was immersed in a formalization bath consisting of formalin, sulfuric acid, and sulfuric acid at 60° C. for 30 minutes to carry out a formalization reaction. The obtained film was repeatedly conditioned with 0.5N hydrochloric acid and 1.0N saline water.
g) After that, the membrane was immersed in 0.5N hydrochloric acid to make it into an acid form. Next, the membrane was immersed in pure water repeatedly while changing the pure water to completely remove the acid adsorbed in the membrane. The film obtained here with a thickness of 50 microns was immersed in ethylene glycol to replace the water in the film with ethylene glycol.

On the other hand, 4-vinylpyridine was suspended in pure water and polymerized by heating at 80°C in a nitrogen atmosphere using 7penzoylno-9-oxide as a catalyst. Rubber-like polymer obtained? Separate from water;
After drying, it was dissolved in toluene and poured into a large lid of pyridine to completely precipitate it. This process was repeated five times to remove unreacted 4-vinylpyridine and 4-vinylpyridine oligomers, and the product was purified in a yield of 68 cm. Next, this was dissolved in nitromethane, 7 equivalents of methyl iodide, about twice the amount of pyridine groups in the polymer, was added, and the mixture was heated to reflux at 70°C. The precipitated polymer was separated, dried, dissolved in water, and passed through an anion exchange resin IRA-4000 column in the form of chloride ions to obtain poly(N-methyl-4-vinylpyridium chloride) in the form of iodine ions. Converted to .

The solution was collected and concentrated, and purified by dialysis using a -1=077 membrane in the same manner as in the case of polystyrene sulfonic acid to obtain a purified polymer with a yield of 80 qb. The polymer was dried to form a poly-(N-methyl-4-vinylpyridinium chloride) solid, which was dissolved in ethylene glycol to approximately 50%. Next, it was coated on the EC membrane and the counter electrode to a thickness of about 50 microns, and the previously obtained cation exchange membrane was sandwiched between the two electrodes to form an ECD layer 8. As in Example 1, the EC membrane was divided into segments on the X and Y axes at intervals of 0 and 5 ms, and when a signal was sent to the (15, 15) segment as in Example 1, (15 , 15) only the segment was clearly colored.

On the other hand, for comparison, a cation exchange membrane was prepared without dialysis and purification of nipolystyrene sulfonic acid during the total synthesis of the above cation exchange membrane, and the same procedure was used when making poly(N-methyl-4-vinylpyridinium chloride). When used without toluene-pyridine purification or dialysis purification, (n, m
) The periphery of the segment was also clearly colored and the display was extremely unclear.The content of the inorganic salt in the purified poly(N-methyl-4-vinylpyridinium chloride) was 30 ppm. The molecular MU of purified poly(N-methyl-4-vinylpyridinium chloride) was approximately 40,000. Not yet
Vcr in polymer made of Pi, r molecule loo.

It contained approximately 20 pieces of the following:

Example 4 Non-full 4 mouths (3,6-noki”)-4-#fk-7
A film of 0171 with a copolymer of octene sulfonyl flumeride) and detrafluoroethylene (exchange volume when converted to sulfonic acid) of 0.91 mm (rl normal hydrochloric acid and methanol) It was immersed in a 1:1 mixed solution to convert it into the sulfonic acid form.7'1 It was immersed in a 4=1 mixed bath solution of total isozorobyl alcohol and water and heated under pressure. I7 dissolved most of the film.

Here, Jun et al. repeated the solution uniformly over the entire EC membrane and the counter electrode.

Is it a thin film of a nose fluorocarbon with sulfonic acid content?
Formed. Next, using the polyamine synthesized in Example 1, a three-layer electrolytic IR layer was formed to form an ECr) 8 layer according to the invention. In the same manner as in Example 1, the matrix-driven all-segment segment 15.15 t was very clearly colored and faded, but when unpurified amine and polyamine from the external dialysis fluid were used, as in Example 1, the coloring and fading V1 was unclear. there were.

[Brief explanation of drawings]

Figure 1 of the attached drawing is a graph of the results of measuring tl vs. large charge MV against the voltage of the ECD element carried out in Example 1 [7
There are a lot of things.

Claims (9)

[Claims] (1) An ionic polymer with a molecular weight of 3,000 or more that has an ion exchange group or a functional group that converts into an ion exchange group under the conditions of use, and the molecular weight that dissociates into ions under the conditions of use is 1.
Maximum 1000ppm of ionic low molecular weight substances below 000
An ion conductive material for electrochromic display elements consisting of an ionic polymer. (2) The ion conductive material according to claim (1), wherein the ionic polymer has a molecular weight of 5,000 or more. (3) The ion conductive material according to claim (1), wherein the ionic polymer is a liquid substance. (4) Does the ionic polymer have a cation exchange group, or does it have a cation exchange group and an anion exchange group that become a cation exchange group under the conditions of use? Claims formed by laminating at least two or more layers of anionic polymers (
1) The ionic conductive material described. (5) The ion conductive material according to claim (4), wherein either the cationic polymer or the anionic polymer is a liquid, and the other is a solid. (6) The ion conductive material according to claim (5), wherein the pores of the solid material are of a size that does not allow passage through the cationic polymer or anionic polymer of the liquid material. (7) The ion conductive material according to claim (1), wherein the ionic low molecular substance is a low molecular weight polymer having an ion exchange group or a functional group that converts into an ion exchange group under usage conditions. (8) The ion conductive material according to claim (1), wherein the ionic low-molecular substance is a monomeric substance having an ion exchange group or a functional group that converts into an ion exchange group under usage conditions. (9) The ionic conductive material according to claim (1), wherein the ionic low-molecular substance is an inorganic salt, an inorganic acid, or an inorganic base compound that dissociates into ions under use conditions.