JPS6180126A - Variable transparency glass - Google Patents

Abstract

PURPOSE:To produce inexpensively large-sized variable glass which can change light transmittance by forming an electrode facing the electrodes of an electrochromic material formed on the conductive films of transparent substrates on a net-like conductive base. CONSTITUTION:Transparent electrodes 2 and the thin Prussian blue films consisting of the electrochromic material by an electrodeposition method are respectively formed on a pair of the transparent glass substrates 1 to face each other and the counter electrode 7 consisting of a titanium wire net is disposed therebetween. An electrolyte 5 is filled and sealed between the glass substrates. When -1V potential difference is applied between the electrodes 2 and the counter electrode 7, the film 3 is reduced and decolored and when +0.5V potential difference is applied thereto, said film is oxidized and colored. The quantity of coloration and decoloration can be thus controlled by the magnitude of the potential difference between the two electrodes. The middle coloring state is obtainable with the simple circuit. Since the thin film 3 is formed by the electrodeposition method, the large-sized variable transmittance glass is inexpensively produced.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) This invention relates to a variable transparency glass that can change light transmittance, particularly a large variable transparency glass.

(Prior Art) A conventional variable transparency glass that uses an electrochromic element that reversibly changes light absorption characteristics due to an electrochemical redox reaction is shown in FIG. 3. This variable transparency glass has a pair of transparent substrates 1
Electrochromic (ECi) which is colored when oxidized and discolored when reduced is on the transparent conductive electrode z provided on each substrate.
When oxidized with the X pole a of the substance (Prussian blue), the color disappears,
An electrode 12 of three substances (WO, E (3 substances are oxidized and the other EC substance is reduced, or the reverse reaction is carried out to effect coloring and decolorization.

(Problem to be solved by the invention) However, in such conventional variable transparency glasses, tungsten oxide (WO, ) is often used as one of the EC materials, but it is difficult to form a WO8 film. used thin film formation methods in vacuum such as vacuum evaporation and sputtering, but especially in the case of large devices, there is an advantage that if the entire device is transparent, it can be used for Sun/V-7 or architectural applications. Due to the increase in size, thin film formation methods using vacuum systems require larger equipment, making them extremely expensive, and even with large equipment, only a small amount can be deposited at one time, and it takes time to create a vacuum. However, there were problems in that the cost per sheet was high and mass production was not possible.

(Means for Solving the Problems) In the process of conducting various studies to solve the problems of the conventional variable transparency glass described above, the inventor printed a mesh of about 8 to 5 inches depending on the car model for a glass sunroof. Focusing on the fact that there are some types of glass provided by et al., the structure of the variable transparency glass when used for such applications is that the materials of the two opposing EC substance films are uniform films that can necessarily be transparent. There is no need, one E
It was discovered that the O* layer may be an opaque net-like layer that can be considered transparent as a whole.Based on this knowledge, further research revealed that a net-like metal layer could be used as the counter electrode of the EC film, which changes color. By depositing a substance that performs reversible redox on the membrane and causing it to react, it was confirmed that in this case, the substance on the mesh did not need to change color. This allows the EC material film to be made of only one type of material.
By selecting materials, for example, by selecting Prussian blue as an EC material, we discovered that it is possible to create glass with variable transparency without using vacuum-based film forming methods such as evaporation or sputtering, so that an EC material film can be formed with an electric layer. ,
Accordingly, in the variable transparency glass of the present invention, an electrolyte is sandwiched between a pair of transparent substrates, and an electrode of an electrochromic substance is formed on a conductive film provided on at least one of the substrates. 3. A variable transparency glass having a function of changing light transmittance, characterized in that an electrode facing the electrode of an electrochromic substance formed on the conductive film is formed on a reticular conductive support. The variable transparency glass of the present invention uses as a counter electrode an electrode opposite to the electrode of the EC material formed on a reticular conductive support. It is preferable to use a II electrode coated with a substance capable of electrochemical redox, such as an ECvIJ material such as Prussian blue, or a substance that rapidly performs redox such as polytriphenylamine. .

Further, in the present invention, a transparent electrode made of a conductive film such as 5nO8 is provided on a transparent substrate such as glass by a conventional method. The electrode is preferably an electrode of an EC substance, for example, Prussian blue, which is provided by a film forming method that does not use a vacuum system, such as vapor deposition or sputtering, such as electrodeposition. When the electrode of the above EC material is provided on one transparent conductive substrate, the counter electrode is located close to the other transparent substrate, and when it is provided in both transparent grooves on the substrate, the counter electrode is placed between them. Between the 0 and EC membrane electrodes placed in the
E A polymer membrane that can pass through a transparent supporting electrolyte to prevent scattering of the solution, that is, a transparent porous polymer membrane that is insoluble in the electrolyte solvent, and a transparent polymer that is soluble in the electrolyte solvent and covers the surface of the membrane. Preferably, a combination of membranes or a polymeric membrane is inserted which is partially soluble or swollen in the electrolyte solvent and is permeable to the supporting electrolyte.

Furthermore, if a mesh metal plate such as that used for forming a counter electrode is buried in the electrode of the EC material that changes color and fades, the conductivity of the EC film electrode increases, and even in the case of large-scale variable transparency glass, the overall conductivity increases. This makes it possible to respond quickly.

Hereinafter, the present invention will be described by way of examples based on the drawings.

(Examples) Example 1 Figure (A) shows a variable transparency glass according to an example of the present invention. In Fig. 1 (A), 1 is a transparent substrate, 2 is a transparent electrode, 3 is an electrode using Prussian blue as an electrochromic substance, 4 is a spacer made of 50 μm glass fiber, and 5 is an electrolyte (IMLiOJO4+ double ht water + propylene carbonate)), 13 is 0.7
My polyvinyl butyral (Pv・B) sheet was coated with polyacrylonitrile (PAN) 111: about 50 μm thick, and about 25 to 77 holes with a diameter of about I All/cIIL2 (opening ratio of about 20 to ao
%) transparent porous polymer membrane formed by opening), 7 is a titanium mesh (expanded wire mesh) that is a conductive support and Prussian blue is electrodeposited on it, 8 is a sealing material, and 9 is a lead wire. This variable transparency glass was produced according to the following steps.

(a) A Prussian blue film 8 is formed in accordance with a conventional method using an electrodeposition method on a pair of transparent conductive glasses on which transparent electrodes 2 are provided respectively on a pair of transparent glass substrates 1 (15 mC/CIr
L2) Si facing each other (B) Titanium wire mesh 7 electrodeposited with Prussian blue of 100 me/CrIL2 or more between the above two glasses.
was placed.

→ In order to prevent short circuits and to prevent the electrolyte yt+ from being lost in the event of damage, the Prussian blue $8 on the conductive glass and the wire mesh are made of PVB coated with PAN through space 4. The film was sandwiched and sealed with sealant 8.

) There is an electrolyte inlet (not shown) between the glasses.
It was filled with MLiCVO and propylene carbonate containing 2 parts by weight of water, and sealed with epoxy resin.

Figure 1 CB) is a cross-sectional view taken along the line x-X of Figure 1 (A), in which 5US-304 is coated with colloidal graphite instead of the titanium mesh electrodeposited with Prussian blue as shown in the figure. You can also use

In order to drive the variable transparency glass produced in this way, a potential difference -
When a voltage of 1V is applied, the Prussian blue film 8 is reduced and decolored, and when a potential difference of +0.5V is applied, the Prussian blue film is oxidized and colored.

Next, in the variable transparency glass shown in FIG. 1(A),
Although the EC material film is formed on the transparent electrodes of the pair of transparent glass substrates, it is also possible to simply form the EC material film on the transparent electrode on either one of the transparent glass substrates. In this case, it is advantageous because only one piece of Nesa glass is required, which accounts for the large cost of transparent variable glass. However, in this case, the amount of change in transmittance will be small (the change in absorbance will be halved).Example 2 1x (Example 2) A variable transparency glass was produced in the same manner as in Example 1 using a counter electrode containing liphenylamine.
Thickness tl ) o, 1 mm as shown in figure (A)
The following titanium plate 10 (t work = Oll when shown)
mx) with polytriphenylamine:acetylene black:polytetrafluoroethylene at a stop ratio of 6:3:0.
The material 11 kneaded in Step 5 was crimped to a thickness of t, = 9.51111 or less, and then, as shown in Fig. 2 (B), cuts were made and pulled on both sides as shown by the arrows to form a net, and then pressed again. In this case, water in the electrolytic solution is unnecessary.

(Effects of the Invention) As explained above, according to the present invention, an electrode that is not used for coloring and decoloring uses an electrode that can be further oxidized than the initial state (in this case, the second wave of Prussian blue). Assistance for electricity supply on the way 1! There is no need for initial decolorization of the electrodes, and the pair of electrodes that perform acid f, atomization and reduction have a significantly higher concentration than the other, so the potential is stable and creates a potential difference between the two electrodes. Since the absolute potential can be determined by the driving method, the coloring/decoloring style can be controlled by the magnitude of the potential difference between the two electrodes, and intermediate colored states can be obtained with a simple circuit. in a large setting (i
: Since it can be formed without using I, 300ixxa
Benefits include the ability to manufacture large-scale variable transparency glass of ooaIIE or higher at low cost.

[Brief explanation of drawings]

FIG. 1(A) is a cross-sectional view of a variable transparency glass as an example of the present invention, FIG. 1(B) is a cross-sectional view taken along the X7 line of FIG. 1(A), and FIG. 2(A) is an embodiment. Cross-sectional view of the titanium plate shown in Figure 2, in which the kneaded mixture of polytriphenylamine, acetylene black, and polytetrasulfo 1r ethylene was crimped. Figure 2 (B) is an extract from the titanium plate shown in Figure 2 (A) with cuts made. FIG. 3 is a cross-sectional view of a conventional example of variable transparency glass. l...Transparent substrate 2...Transparent electrode 3...Electrochromic material IT electrode 4...Spacer 5...Electrolyte 6...PVB sheet coated with PAN 7...
Counter electrode 8 in which Prussian blue was electrodeposited on a titanium mesh... Sealing material 9... Lead wire 10... Titanium plate 11... Kneaded material of polytriphenylamine, acetylene black and polytetrafluoroethylene 12. ...Electrochromic material electrode Figure 1 (A) (B)

Claims (1)

[Claims] 1. An electrolyte is sandwiched between a pair of transparent substrates, and an electrode of an electrochromic substance is formed on a conductive film provided on at least one of the substrates to change the transmittance of light. A variable transparency glass having a function, characterized in that an electrode facing the electrode of an electrochromic substance formed on the conductive film is formed on a reticular conductive support.