JPS63221188A - Electrochromic element - Google Patents

Abstract

PURPOSE:To prepare the title element which eliminates the necessity of spacer and sealing, is high in the response speed and has excellent durability and large area and functions of display and dimming, by sandwiching a particular resin compsn. and an electrochromic substance between a pair of counter electrodes. CONSTITUTION:In 100pts. resin (A) having a polar group and high dielectric constant (e.g., polyvinyl butyral) is dispersed 5-500pts. org. substance (B) contg. a polyalkylene oxide chain of the formula II (wherein R is alkyl having a b.p. of pref. 100 deg.C or above), such as a dialkyl ester of the formula I (wherein R1-R2 are each alkyl; and n>2) (e.g., triethylene glycol 2-ethylbutyrate) and 0.1-200pts. electrolyte (C) pref. contg. Li (e.g., LiClO4), thereby preparing a resin compsn. 4. On a substrate comprising a transparent substrate 1 such as glass or plastic sheet, and, formed thereon, a transparent electrode 2 comprising a transparent conductor, such as tin oxide film or indium oxide-tin oxide, are laminated thereon an electrochromic layer 3 comprising WO3, IrO2, or polyisothianathene, a resin compsn. 4, and a counter electrode 5 comprising a conductive substance, such as gold, silver or carbon, optionally having a reversible redox substance.

Description

Detailed Description of the Invention (Industrial Application) The present invention relates to an electrochromic (hereinafter abbreviated as EC) element, and more specifically, an electrochromic (hereinafter abbreviated as EC) element.
Regarding the C element.

(Prior Art) Elements that utilize the EC phenomenon are used, for example, in display elements and anti-glare mirrors, and in the case of transmissive types, they are expected to be applied as light control elements to window materials for buildings and automobiles.

Conventionally, EC elements have a WOS between a pair of electrode plates.

Solid, liquid, and semi-solid electrolytes have been proposed as the electrolyte used here, sandwiching an EC substance such as IrOz or viologen and an electrolyte containing ions that color the EC substance. Looking at these from the perspective of large areas and the possibility of sufficient reflectance and transmittance modulation, solid electrolytes have slow response, small modulation width, and are low in productivity because they require multilayer coating. There is a problem in that it is difficult to ensure uniformity of characteristics. In the case of liquid electrolytes, panel technology,
The prevention of electrolyte threshold erosion is (!'1w1).Semi-solid electrolytes, especially organic electrolytes, are more effective than solid electrolytes and liquid electrolytes.
Although it is advantageous as a large-area EC element in terms of uniformity, processability, and productivity, it generally has no or small ionic conductivity, and many of them do not exhibit sufficient EC characteristics by themselves.

A conventionally proposed organic electrolyte with improved ionic conductivity is described in Japanese Patent Publication No. 54-43387. The sulfuric acid-containing polyvinyl alcohol, polyacrylamide, ethylene glycol, glycerin, etc. disclosed herein not only have no or low tackiness and are difficult to manufacture over a large area, but also require the use of highly concentrated sulfuric acid. Therefore, there are problems in terms of durability and handling. British Patent No. 2005856 discloses polystyrene, polystyrene sulfonic acid, perfluorosulfonic acid, etc., but these also have poor adhesive properties and are difficult to fabricate into large-area panels. Also, JP-A-57-79920 and JP-A-6
0-263922 contains polyvinyl butyral and Li
An electrolyte such as CI 04 dissolved in butanol or ethyl cellosolve has been disclosed, but it has high fluidity and not only requires a spacer to maintain the parallel state of the substrate when increasing the area. At high temperatures, the solvent evaporates, requiring a seal, which complicates device fabrication. Furthermore, in JP-A-58-207026, plasticizer and LiCIO
Although a resin containing an electrolyte such as No. 4 has been described, the response is slow due to low ionic conductivity and is of little practical use.

(Problems to be Solved by the Invention) The present invention has been made to solve the above-mentioned problems, and essentially eliminates the need for spacers and seals, has fast response, is durable, and does not leak. It is an object of the present invention to provide a large-area EC element that is easy to manufacture.

(Means for Solving the Problems) The electrochromic device according to the present invention includes a resin composition in which an organic substance containing a polyalkylene oxide chain and an electrolyte are dispersed in a resin, and an electrochromic substance.
It is characterized by being sandwiched between a pair of opposing electrodes.

The configuration of the present invention will be explained below using the drawings.

FIG. 1 shows an E having a display or dimming function of the present invention.
FIG. 2 is a cross-sectional view showing the configuration of a C element.

ECC5 is applied to a substrate on which a transparent electrode 2 is formed on a transparent substrate l.
0 resin composition 4 and facing type 8i15 are sequentially laminated.

A transparent material such as glass or a plastic plate is used for the transparent substrate 1, and a transparent conductor such as a tin oxide (SnOz) film or indium oxide-tin oxide (ITO) is used for the transparent electrode 2. ECC50WOs, I r02
Alternatively, it can be formed using an EC material such as polyinthianaphthene. Resin composition 4 is a composition in which an organic substance containing a polyethylene oxide chain and an electrolyte are dispersed in a resin.

This resin is not particularly limited, but examples include epoxy resin, silicone resin, acrylic resin, xylene resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl acetal resin, polyvinyl carbazole resin, polyvinyl chloride resin, Acrylonitrile resin, polyvinylidene fluoride resin, methacrylic resin, polyvinyl alcohol, polyvinyl butyral, etc. can be used, and in particular, resins with polar groups and high dielectric constant such as polyvinyl chloride resin, polyacrylonitrile resin, and polyvinylidene fluoride resin are used. It is preferable.

Furthermore, the electrolytes described here are not particularly limited, but include, for example, LiCIO4, LiI, LiBF4゜NIC104, KClO4, LiCl, CBrxCO.
OLi, CFsCOOLi, (C4Hv)4NI
, LiOH, CBrgCOOH, etc. can be used. LI ions have a small ionic radius, have high ionic conductivity, and unlike protons, do not attack the EC layer or electrode, so LI ions are especially suitable for L.
Electrolytes containing i are preferred. The amount of electrolyte added is 10% of the resin.
The amount is 0.1 to 200 parts to 0 parts. Below this range, there are few ions and the ionic conductivity is low, and above this range, the electrolyte will precipitate. Considering this, it is 2 to 50 copies.

The organic substance containing a polyalkylene oxide chain mentioned here is not particularly limited, but for example, dialkyl esters such as triethylene glycol di-2-ethyl butyrate, hexaethylene glycol di-2-ethyl butyrate, and hexaethylene glycol dibutyrate are used. In particular, it is desirable that the alkylene oxide chain is a methylene oxide or ethylene oxide chain, and that the boiling point is 100° C. or higher in view of sealing properties. The amount of organic matter added is 5 to 500 parts per 100 parts of ILS fat; below this range, the interaction between ions and polyethylene oxide chains is small, and the flexibility of the resin itself is low, so the ionic conductivity hardly changes. Above this, the resin becomes too flexible and requires a seal or spacer. A preferable addition amount is 20 parts to 100 parts from the viewpoint of ionic conductivity and flexibility of the resin.

For the counter electrode 5, a conductive substance such as gold, silver, copper, carbon, or stainless steel can be used, and if the transparent substrate described above is used, it is also possible to make a transmission type light control element.
It is preferable to provide a reversible redox substance such as WO5, IrO2, Prussian blue, etc. on the conductive substance.

Next, the manufacturing method will be explained.

The following is an EC having display or dimming function of the present invention.
An example of manufacturing the device will be shown. An organic material containing polyalkylene oxide chains and an electrolyte are dispersed in a resin and formed into a film in an extruder. This film and ECtl! !
I′j1 is deposited on a transparent substrate such as a glass or plastic plate, and a transparent electrode is laminated by any method such as spraying or coating, and a counter electrode made of a bait metal plate, a conductive polymer material, or the transparent substrate. The EC element of the present invention can be obtained by press-bonding the resin composition with scissors.The manufacturing process is extremely simple, as the EC element can be produced simply by pressure-bonding the resin composition.

Further, it is also possible to disperse a resin, an organic substance containing a polyalkylene oxide chain, and an electrolyte in a solvent, cast it on a transparent electrode or a counter electrode, and then press it. Also by this method, the EC element of the present invention can be easily manufactured.

(Effects of the Invention) As described above, according to the electromic device of the present invention,
Since it uses a resin, it has low fluidity and does not require a spacer, so there is no need to worry about it breaking.Since it uses a high boiling point organic substance, it has almost no volatile components even at high temperatures, so there is no need for a seal, and it does not contain polyalkylene oxide chains. Since the resin is also flexible, it has high ionic conductivity and quick response, and it is also possible to easily obtain a large-area electrochromic device.

(Example) Example 1 An EC element having the structure of the present invention shown in FIG. 1 was manufactured by the method shown below. In2O5 was provided as a transparent electrode 2 on a transparent glass substrate 1 by vacuum evaporation. On this electrode 2, 400% WOs was applied as an electrochromic layer 3.
A resin composition 4 was prepared based on the following formulation.

Polyvinyl butyral 10
0 parts triethylene glycol di-2-ethyl butyrate
A mixture of over 10 parts of 50 parts LIC104 in 400 parts of ethanol was cast onto the EC layer 3. Further, as a counter electrode 5, IrO2 was provided on a stainless steel plate by high frequency reactive sputtering and bonded under pressure.

When +2V was applied to the opposite electrode using the transparent electrode having the above configuration as a negative electrode, the color was colored in several hundred m5ec to several seconds, and the color disappeared immediately when a reverse voltage was applied.

Example 2 In Example 1, 10 parts of titanium dioxide was added to increase the contrast during coloring. When +2V was applied to the opposite electrode using the transparent electrode of this EC element as a negative electrode, the color was colored in several hundred m5ec to several seconds, and when a reverse voltage of -2V was applied, the color disappeared in several hundred m5ec to several seconds. Further, no particular change was observed in the EC element even after coloring and decoloring was repeated 10,000 times.

Example 3 In Example 1, as the counter electrode 5, an In2O5 transparent electrode was deposited on a transparent glass substrate and Ir0z was provided thereon. When +2V was applied to the opposite electrode using the transparent electrode of this EC element as a negative electrode, the total light transmittance decreased from 85 cm to 20% in several hundred m5IIe to several times. Furthermore, when a reverse voltage was applied, the color quickly disappeared and the total light transmittance returned to 85%.

*Example 4 Polyvinyl chloride 10 was used as resin composition 4 in Example 1.
0 parts triethylene glycol di-2-ethyl butyrate
A mixture of 50 parts LiCIO and 45 parts in 400 parts of tetrahydrofuran was cast onto the EC layer 3. Further, as a counter electrode 5, IrO2 was provided on a stainless steel plate by high-frequency reactive sputtering and bonded under pressure.

When +1.8V was applied to the opposite electrode using the transparent electrode with the above configuration as a negative electrode, it took several hundred ms! It was colored using the lc~ formula and quickly disappeared when a reverse voltage was applied.

Example 5 In Example 4, 10 parts of titanium dioxide was added to increase the contrast during coloring. When +1.8V was applied to the opposite electrode using the transparent electrode of this EC element as a negative electrode,
It was colored with several hundred mMg (8), and when a reverse voltage of -1.8V was applied, the color disappeared by several hundred mMg. Further, even after performing this coloring/decoloring process 100,000 times, no particular change was observed in the EC element.

Example 6 In Example 4, as the counter electrode 5, a 20g In transparent electrode was deposited on a transparent glass substrate and IrO2 was provided thereon. When +1.8V was applied to the opposite electrode using the transparent electrode of this EC element as a negative electrode, several hundred m511e
In equation (6), the total light transmittance decreased from 80 cm to 15%, and when a reverse voltage was applied, the color quickly disappeared and the total light transmittance returned to 80 cm.

Example 7 In Example 1, hexaethylene glycol dibutyrate was used instead of triethylene glycol di-2-ethylbutyrate, CF3CO0Li was used instead of LiClO4, and the transparent electrode of this EC element was used as a negative electrode, and the opposite electrode was +
When 2V is applied, it is colored according to a mathematical formula, and when a reverse voltage of 2V is applied, it is several hundred msI! c~ Discolored in a few chapters. Furthermore, although this element was exposed to a high temperature of 100° C. for 100 hours, no particular change was observed in the EC element.

Comparative Example 1 In Example 1, dioctyl phthalate was used instead of triethylene glycol di-2-ethyl butyrate. The transparent electrode of this EC element was used as a negative electrode, and +2V was applied to the opposite electrode, but no change in color was observed even after 1 minute.

Comparative Example 2 In Example 7, ethyl carpitol was used instead of hexaethylene glycol dibutyrate. When this element was exposed to a high temperature of 100° C. for 100 hours, electrolyte leakage and foaming occurred.

[Brief explanation of the drawing]

FIG. 1 is a conceptual diagram showing the structure of the EC element of the present invention. 19. Transparent substrate, 2. Transparent electrode, 3. electrochromic layer, 4. resin composition, 5. Counter electrode,

Claims (1)

[Claims] 1. A resin composition in which an organic substance containing a polyalkylene oxide chain represented by the following formula and an electrolyte are dispersed in a resin, and an electrochromic substance are sandwiched between a pair of opposing electrodes. Electrochromic element. -(R-O)-_n where n>2 R is an alkyl group 2, and the organic substance containing the polyalkylene oxide chain is a dialkyl ester represented by the following formula, Claim 1
The electrochromic device described in Section 1. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, R_1, R_2 alkyl group 3, the organic substance containing the polyalkylene oxide chain is composed of a polyalkylene oxide monoalkyl ether represented by the following formula and a monovalent or polyvalent carboxylic acid organic compound. The electrochromic device according to claim 1, which is the obtained ester compound. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Where m≧1 R_1 and R_2 are alkyl groups