JPH03265822A - Fully solid state type electrochromic material and antidazzle mirror - Google Patents

Abstract

PURPOSE:To allow the control of the hue at the time of coloring by providing a light reflection-transmission characteristic adjusting part having the function to increase or decrease the spectral reflectivity and transmittance in visible light in the light transmission part of the material. CONSTITUTION:The fully solid state type electrochromic (EC) material 1 is obtd. by forming the light reflection-transmission characteristic adjusting part LC 1 on at least one side on a transparent substrate 2 and further successively laminating a transparent conductive film 3, a 1st film 4, a solid electrolyte 5, a 2nd film 6, and a conductive film 7 in the part where the above-mentioned part is formed or not formed, thereby forming the EC element part E 1. The light passing either or both of before and after the passage of the light through the EC element part E 1 passes the light reflection-transmission characteristic adjusting part LC 1 and, therefore, the light reflection and transmission characteristics are adjusted in this part. The hue to be obtained from the spectral reflection characteristic of the EC element E 1 as the whole of the EC material 1 is controlled in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an all-solid-state electrochromic material and its uses, and more specifically, to an all-solid-state electrochromic material that can control the hue when colored and It concerns an anti-glare mirror with a hue or black color.

[Prior art and its problems]

An electrochromic element is an element that utilizes a phenomenon (called electrochromism) in which an electrochemical reaction occurs when a voltage is applied, and the color of a substance changes reversibly.

Electrochromic elements come in various structures, such as solution type and all-solid type.Among them, as one of the elements with excellent electrochromic (hereinafter referred to as EC) characteristics and durability, EC material, electrolyte type, etc. There is also an all-solid-state EC device in which both are solid.

As shown in FIG. 2, the all-solid-state EC material 91 consists of five layers: a reduction coloring film 96, a dielectric film 95 as a solid electrolyte film, and an oxidation coloring film 94 sandwiched between two electrodes 9397. It is constructed by forming an EC element on a substrate 92''.

The reduction coloring film is tungsten oxide (WO3).
etc., but tantalum oxide (Ta205) is used as a dielectric film.
Iridium oxide (Ire) as an oxidized coloring film
It is known that it uses something like The lower electrode 93 is made of visible light transparent ITO (InO3-5w).
When the upper electrode 97 is used as a transmission type, ITO is used, and when it is used as a reflection type, Al1 is used. The coloring source of all-solid EC membranes is the water contained in the membrane, and the protons (Ha) produced by the decomposition of this water
, coloring and decoloring are repeated by implanting and extracting OH- ions. The reaction formula at this time is estimated as follows.

x H20: xH” +xOH---(1)xH”
+ xe-+ WO3 (transparent):==: H, W
O3 (dark blue) ... (2) xOH-+I
r(OH),.

= ■r(OH),, □(black)+xe(3) Here, whether WO3 and IrO are both colored, the hue at the time of coloring depends on the hue of H and WO3 from the ratio of coloring efficiency and film thickness, Appears blue (dark blue).

Incidentally, it has been desired to develop a material that has a hue close to black when colored to improve visibility as an optical function display element. As this black display EC element, M o O2 is added to WO3.
A material has been proposed in which a material added with is used for a reduction coloring film (US Pat. No. 4,009,935). However, although the coloring response of this W○, -M2O3 system is almost the same as that of WO3, the decoloring response is
, which is very bad because it becomes difficult to extract H+ from M2O3. Therefore, there was a problem in that it was not suitable for application to anti-glare mirrors, etc., which required quick response. In addition, in a high temperature atmosphere (approximately 85°C), the reflectance (transmittance) during decolorization decreases, and the durability under such atmosphere is poor, making it impossible to obtain sufficient reliability. There was a problem.

Therefore, the inventors of the present invention have made extensive research to solve the problems of the prior art as described above, and have completed various systematic experiments, resulting in the completion of the present invention.

[Purpose of the invention]

An object of the present invention is to provide an all-solid EC material whose hue during coloring can be controlled without impairing the EC characteristics of the EC element portion.

The present inventors have focused on the following regarding the problems of the prior art described above. That is, first, we focused on the responsiveness during erasing, which is the main cause of the drawbacks of the prior art. As in the prior art, a reduction coloring film (WO) is used to achieve blackening.
If an additive (MoO2) is added to 3), sufficient decoloring response cannot be obtained. Therefore, the present inventors believe that these problems of the prior art are fundamentally solved by WO3-M00.
We thought that this was due to a 3-system reduction coloring film, that is, the addition of additives, and conducted extensive research. As a result, as a means to overcome this problem, we focused on the spectral reflection characteristics of the reduction coloring film as a method to achieve black coloring without using additives.
We have discovered that when coloring a C element, the spectral reflection/transmission characteristics of the entire EC material can be improved to achieve blackening, and the present invention has been completed.

By configuring the EC material by providing a light reflection characteristic adjusting section that has the function of increasing or decreasing the reflection/transmittance within visible light in the light passing section of this EC material, the hue during coloring can be controlled. This led to the realization of EC materials.

[Description of the first invention] Structure of the first invention The all-solid EC material of the first invention is an all-solid EC material that increases or decreases the spectral reflection and transmittance of visible light in the light passing portion of the material. It is characterized by being provided with a light reflection/transmission characteristic adjustment section having a function.

Functions and Effects of the First Invention The all-solid EC material of the first invention has excellent EC properties and can control the hue during coloring.

The mechanism by which the all-solid EC material of the first invention exhibits the above-mentioned effects is not yet clear, or may be considered as follows.

That is, the all-solid EC material of the first invention is provided with a light reflection/transmission characteristic adjustment section having a function of increasing/decreasing spectral reflection/transmittance in visible light in the light passing section of the EC material. As a result, the light passing through the EC element section passes through the light reflection/transmission characteristics adjusting section either before or after passing the light, so that the spectral reflection/transmission characteristics are adjusted in this section.
The hue obtained from the EC material as a whole can be controlled by the spectral reflection characteristics of the EC element.

In addition, in order to achieve blackening as in the prior art, M
Rather than using a reduction coloring film containing additives such as oO2, we have achieved control of the hue, such as blackening, without making any changes to the EC element, so it does not impair the EC characteristics of the EC element. Never.

At this time, the spectral reflection/transmission characteristics during decolorization also change, but since the amount of change in reflectance or transmittance is smaller during decolorization than when coloring, the hue does not change much, so there is no problem.

[Description of the second invention] Below, other inventions of the first invention that make the first invention more specific will be described.

As shown in FIG. 1, the all-solid-state EC material l of the second invention has a transparent conductive film 3, a first film 4, a solid electrolyte film 5, a second film 6, and a conductive film 7 on a transparent substrate 2. It is an all-solid-state EC material having an EC element part E1 formed by sequentially laminating the first film 4 and the second film 6, in which one of the first film 4 and the second film 6 is colored by oxidation, and the other is colored by reduction. A light reflection/transmission characteristic adjusting section LCI having a function of increasing/decreasing spectral reflection/transmittance within visible light is provided in the light passing section.

The transparent substrate 2 of the all-solid-state EC material 1 of the present invention is a plate or film made of an inorganic material such as transparent glass and a resin, and its shape may be either a flat plate or a curved plate. The substrate 2 holds the EC element portion E1 that causes an EC reaction, and is designed such that the colored/decolored state of the all-solid-state EC element portion E1 can be directly observed from the transparent substrate 2 side.

The all-solid-state EC element portion E1 includes a transparent conductive film 3, a first film 4,
Solid electrolyte membrane 5, second membrane 6, and conductive membrane 7--7 The transparent conductive membrane 3 acts as an electrode, has low resistance, is transparent, and transmits light, and also serves as the first membrane 4, second membrane 6, and the like.
The state of coloring and decoloring can be observed from the substrate 2 side. Specifically, the material constituting the transparent conductive film 3 is iTO (Indium Tin Oxi).
de), ZnO-based substances, AT○ (Antimon
y Tin Oxide).

One of the first film 4 and the second film 6 is a film that is colored by oxidation (oxidation colored film), and the other is a film that is colored by reduction (reduction colored film). Specifically, examples of the oxidized colored film include iTO, NiO, and RhO2. In addition, as reduction colored films, WO3, MoO2, Ti
There are O2, etc.

The solid electrolyte membrane 5 is located between the first membrane 4 and the second membrane 6, and is a medium for moving protons and hydroxide ions, and has excellent electronic insulation and is a good conductor of protons and hydroxide ions. Use substances. Specifically, Ta2
0, SiO2, Cr203, etc.

The conductive film 7 forms a pair with the transparent conductive film 3 and becomes the other electrode, and is made of the same material as the transparent conductive film 3 or A.
1. An electrode material made of an opaque substance such as Ag or Sn is used. At this time, if the conductive film 7 is made of the same material as the transparent conductive film 3, it will be a transmission type all-solid-state EC element, and if it is made of an opaque material, it will be a reflective all-solid-state EC element.
It becomes a C element.

The light reflection/transmission characteristic adjustment section LC+ is a hue control section of the EC material that has a function of increasing/decreasing the spectral reflection/transmittance within visible light of the EC element E1, and is formed in the light passage section of the EC material.

In addition, when the EC material is a reflective type, the light reflection/transmission characteristic adjusting section LCI is arranged on the light incident side from the EC element section.

Further, in the case of a transmission type, it may be disposed on the light incident side of the EC element part of the EC material, on the opposite side, or on both sides.

Specifically, the light reflection/transmission characteristic adjustment unit LCI adjusts the hue of an interference film filter having a visible light reflection increase/decrease property t't or a colored film filter that absorbs light of a specific wavelength of visible light. An example is an adjustment filter.

Further, the above characteristics may be imparted to any of the elements constituting the EC material.

When the EC material is a reflective type, the light reflection/transmission characteristic adjustment section LCI is a hue control section for adjusting the light reflection characteristic, and is disposed on the light incident side from the EC element section of the EC material. The adjustment part L
When an interference film filter having visible light reflection increase/decrease characteristics is used as C1, it is disposed at a position where mutual interference with other parts does not occur, such as on the light incident side surface of the substrate. Furthermore, when a colored film filter having spectral transmission characteristics that absorbs light of a specific wavelength of visible light and uniformizes spectral reflection characteristics is used, it is disposed on at least one of the substrates.

In the latter case, the colored film filter LCI1 is
As shown in FIG. 3, it is preferable to dispose the core between the substrate 12 and the EC element portion E1.1 because deterioration of the core due to the influence of the external environment can be prevented.

When the EC material is a transmissive type, the light reflection/transmission property adjustment unit LCI is a hue control unit that adjusts the light transmission property, and may be disposed on the light incident side of the EC element of the EC material or vice versa. It may be arranged on either side or on both sides. In any case, when an interference film filter having visible light reflection increase/decrease characteristics is used as the adjustment unit LCI, it is disposed on the outer surface of the substrate. Furthermore, when a colored film filter having spectral transmission characteristics that absorbs light of a specific wavelength of visible light is used, it is disposed on at least one of the substrates. In the latter case, as shown in FIG. 3, the colored film filter LCII is disposed between the substrate 12 and the EC element section Ell to prevent deterioration of the core section due to the influence of the external environment. It's nice to be able to do that.

When an interference film filter having visible light reflection increase/decrease properties is used as the light reflection/transmission property adjustment unit LCI, the hue at the time of coloring can be controlled by selecting the properties of this interference film filter as desired. I can do it. That is, the amplitude of reflectance change in visible light is 15% to 30%.
An interference film with a characteristic of 7% to 15% will produce a warm hue such as orange, and an interference film with a characteristic of 7% to 15% of the reflectance change amplitude in visible light will produce a green color. It is possible to control the hue to a cool color such as purple or black.

Further, by combining these and being able to control or select the reflectance change value as appropriate, it is also possible to arbitrarily set warm colors to cool colors.

Below, an interference film filter that has a blackish hue when colored will be described. The amplitude of reflectance change in visible light is 7%
Specific examples of interference film filters having a characteristic of 15% include those having a single layer structure, and those having a multilayer structure consisting of two or three layers. In the case of a single-layer film structure, a material with a refractive index of 90 to 2.30, for example,
203, Y2O3, Sn○2, ZrO2, CeO2, T
iO2 etc. at λ/2 (here, λ=450-500nm
) film thickness. In the case of a two-layer structure, MgO, ln2
C) +, Y2O3, 5nCL, ZrO2, Ce O2,
The refractive index of TiO2 etc. is 1.75-2.30 and the film thickness is λ
/2 substance and CaF2, NaF, LiF, SiO2,
The refractive index of MgF2 is 1.25 to 1.45 and the film thickness is λ.
/4 substance (in this case, λ-350~40
0nm). In the case of a three-layer structure, Al 203, Ce
The refractive index of F3 is 1.55 to 1.65 and the film thickness is λ
/4 substance and In2O5, Y2O3, Sn○2, Z
r O2, CeO2, T i 02, etc. refractive index or 1.
A substance with a film thickness of 90 to 2.30 or λ/2 and Ca F 2
, NaF, LiF, SiO2, MgF2, etc., with a refractive index of 1.25 to 1.45 and a film thickness of λ/4 (in this case, λ-350 to 400 nm). Other specific examples of the three-layer structure include CaF2, NaF, L
The refractive index of iF, SiO2, MgF2, etc. is 1.25 to 1.
．． ．． 45 and a material with a film thickness of λ/4, MgO, Sn○2,
The refractive index of In2O3, Zr0z, etc. is 1.75 to 2.1
0 and the film thickness is λ/2, SiO2, Al2O3, C
It is made of a material such as eF3, which has a refractive index of 1.45 to 1.65 and a film thickness of λ/4 (in this case, λ=300 to 3).
50 nm).

In this case, it is preferable that the reflectance of the interference film filter corrected for luminous efficiency using the A standard light (hereinafter referred to as luminous reflectance) be equal to or 34 times lower than the luminous reflectance of the substrate. . By doing this,
It is possible to increase the contrast ratio, reduce double images, and achieve good EC characteristics. Incidentally, it is preferable that the interference film filter is composed of more layers because the luminous reflectance is reduced and the EC characteristics are improved.

In addition, anti-reflection films commonly used in the past (for example, in a three-layer structure, λ/4 - λ/2 - λ/4: λ = 550
nm) to the EC material, the luminous reflectance is reduced and double images are reduced, but the change in reflectance in the visible light range is less than 1%, so the hue when colored is the same as that of the conventional one. It is not possible to maintain a black hue.

Further, by using a colored film filter that absorbs light of a specific wavelength of visible light, the hue at the time of coloring can be controlled. For example, when the hue at the time of coloring is black, a color having characteristics complementary to the hues of H and WO3 is used. By disposing this colored filter in the light passing portion of the EC material, the spectral reflection characteristics during coloring are made uniform and a blackish hue is exhibited. Specifically, 5102 contains Ag, C
A composite film containing 0.30 to 10% of U and CdS may be mentioned. The film thickness varies depending on the amount of additive added, or is required to be about 200 nm when the amount added is 1%.

More specifically, reflective WOz/Ta205/IrO
This will be explained using an x-based EC element. The visible light spectral reflection characteristics of this element are shown in FIG. As shown in the figure, many waves are recognized, but this is the result of mutual interference between the multilayer films, and is observed by the human eye as spectral reflection characteristics as shown in Figure 5. The reflectance during decolorization or visible light is almost constant, making it an achromatic color (
It can be seen that the reflectance when colored decreases on the longer wavelength side of visible light, giving it a blue color.

In this case, the reflectance on the long wavelength side of visible light (>550 nm) may be increased from the reflectance of the substrate, or the reflectance on the short wavelength side of visible light (<
550 nm) is lower than the reflectance of the substrate, and has reflection increase/decrease characteristics such that the amplitude of the change in reflectance within visible light is 7 to 15% (note that the luminous reflectance is By forming the EC film on the opposite side of the EC film with the glass substrate sandwiched therebetween, the hue of the EC material can be blackened. Specifically, by setting the spectral reflection characteristics of the interference film filter as shown in FIG. 6, it becomes possible to blacken the EC material when coloring it.

In designing the interference film filter, theoretical calculations of optical properties were carried out, and as a result, interference films with characteristics matching relatively well with those shown in FIG. 6 were obtained in the form of a single layer, a double layer, and a triple layer.

Next, a specific example of blackening the hue during coloring using a colored film filter will be briefly described. The spectral transmission characteristics of this colored film filter for blackening are shown in FIG. As shown in the figure, the hue of the colored film filter is slightly orange or within an acceptable range. The colored film filter may be applied on the opposite side of the EC film with the substrate glass in between, but it is better to apply it inside the EC film where there is no risk of killing the surface.

In addition, when an interference film filter is used, the light reflection/transmission characteristic adjustment section must have a luminous reflectance of the A standard light, or a luminous reflectance that is equal to or lower than the luminous reflectance of the substrate. That's good. This is because as the luminous reflectance increases, the light that enters the EC material is increased and reversed, and the luminous reflectance and transmittance increase during decoloring and coloring, and the contrast ratio decreases and double images are more likely to occur. Therefore, it is preferable that the above conditions are satisfied. All of these problems become particularly noticeable when coloring.

The all-solid-state EC material 1 of the present invention has a light reflection/transmission characteristic adjustment section formed on at least one side of the transparent substrate 2, and a transparent conductive film 3 and a first film 4 on the formed section or non-formed section.
, the solid electrolyte membrane 5, the second membrane 6, and the conductive film 7 are sequentially laminated to form an EC element section. Furthermore, a substrate or the like may be laminated on the EC element portion.

The specific method for manufacturing this all-solid-state EC material is briefly explained below.

First, a transparent substrate 2 is prepared, and the surface of the substrate is coated with light reflecting material.
A transmission characteristic adjustment section is formed.

7 8 In the case of an interference film filter, the core portion is made of a single, double, or triple layer of materials with different refractive indexes. This film formation is performed using PVD (Physical Vapor
CVD (Chemical Vapor Deposition) and CVD (Chemical Vapor Deposition) using plasma.
position). In the case of a colored film filter, a composite film is produced by multi-source sputtering, or a simultaneous film formation method of sputtering and ion blasting or vacuum evaporation.

Next, a transparent conductive film, a first film, a solid electrolyte film, a transparent conductive film, a first film, a solid electrolyte film, A second film and a conductive film are sequentially laminated. This lamination is
This is carried out by methods such as vacuum evaporation, sputtering, and ion blating, and from this, the all-solid-state type E according to the present invention is produced.
C material is obtained.

[Description of the Third Invention] The third invention relates to an application invention in which the all-solid EC material of the first invention is applied to an anti-glare mirror.

OBJECTS OF THE INVENTION The object of the present invention is to provide an anti-glare mirror of the third aspect of the present invention, which has a black hue during anti-glare without impairing the EC characteristics of the EC element portion, and has an excellent anti-glare effect.

Structure of the Invention The anti-glare mirror of the third invention has an EC element portion formed by sequentially laminating a transparent conductive film, a first film, a solid electrolyte film, a second film, and a conductive film on a transparent substrate. EC in which either the first film or the second film is colored by oxidation, and the other is colored by reduction.
An anti-glare mirror having an element part, wherein a light reflection characteristic adjustment layer made of a spectral reflection increasing/decreasing metal compound is formed in a light passing part of the anti-glare mirror, and an anti-glare part is formed together with at least the EC element part. It is characterized by this.

Functions and Effects of the Invention The anti-glare mirror of the third invention can blacken the hue during anti-glare without impairing the EC characteristics of the EC element portion, and has an excellent anti-glare effect.

The mechanism by which this anti-glare mirror exerts the above-mentioned effect is not yet fully clear, but it is thought to be as follows.

That is, in the anti-glare mirror of the third invention, a light reflection property adjusting layer made of a metal compound for increasing and decreasing spectral reflection is provided in the light passing portion of the anti-glare mirror, and the anti-glare portion is formed together with at least the EC element portion. Become. As a result, the light passing through the EC element section either before or after passing through, or both, passes through the light reflection characteristic adjustment section, so that the spectral reflection characteristics are adjusted at the core section. By forming an anti-glare part with the core part and the EC element part, the hue obtained from the spectral reflection characteristics of the EC element for the entire anti-glare mirror is adjusted by the light reflection characteristics adjustment part to create a blackish hue. can be controlled.

In addition, in order to achieve blackening as in the prior art, M
Rather than using a reduction coloring film containing additives such as oO2, blackening was achieved without modifying the EC element, so the EC characteristics of the EC element are not impaired. Therefore, this anti-glare mirror can have a black hue during anti-glare without impairing the EC characteristics of the EC element portion, and has an excellent anti-glare effect.

[Description of the fourth invention] Below, other inventions of the third invention, which are more specific versions of the third invention, will be described.

Note that the transparent substrate, the transparent conductive film, the first film, the solid electrolyte film, the second film, the conductive film, and the EC element section may be the same as those described in the second invention. hand,
Detailed explanation will be omitted.

The light reflection property adjustment layer is a hue control part that has the property of increasing or decreasing the spectral reflectance in visible light of the EC element part, and is made of a metal compound. It uniformizes the spectral reflection characteristics in the light range, and is formed in the light passage part of the anti-glare mirror, and has at least an EC
An anti-glare portion is formed together with the element portion.

Specifically, the light reflection property adjustment layer may be a hue adjustment filter such as an interference film filter that has visible light reflection increase/decrease properties or a colored film filter that absorbs light of a specific wavelength of visible light. It will be done. Further, the above characteristics may be imparted to any of the elements constituting the anti-glare mirror.

When an interference film filter having visible light reflection increase/decrease characteristics is used as the light reflection characteristic adjustment layer, it is disposed at a position where mutual interference with other parts does not occur, such as on the light incident side surface of the substrate. Furthermore, when a colored film filter having spectral transmission characteristics that absorbs light of a specific wavelength of visible light and uniformizes spectral reflection characteristics is used, it is disposed on at least one of the substrates. Note that the latter case is preferable because it is possible to prevent deterioration of the core portion due to the influence of the external environment by disposing it between the substrate and the EC element portion.

When using an interference film filter having visible light reflection increase/decrease characteristics as the light reflection property adjustment layer, the interference film should have a characteristic of 7% to 15% of the reflectance change amplitude within visible light, and the A standard It has a luminous reflectance of light, or a luminous reflectance that is equal to or lower than the luminous reflectance of the substrate. By doing so, it is possible to increase the contrast ratio, reduce double images, and achieve good anti-glare properties. Note that the larger the luminous reflectance is, the more light entering the EC material is reflected, which is undesirable because the luminous reflectance increases during decoloring and coloring, and the contrast ratio decreases and double images are more likely to occur. . Further, the more layers the interference film filter has, the lower the luminous reflectance and the better the anti-glare properties, which is preferable.

As a specific example, a multilayer film structure consisting of two or three layers is used. In the case of a two-layer film, Mg0
, 1n203, Y2O3, S n O2, ZrO2, C
e The refractive index of O2, TiO2, etc. is 1.70 to 2.30
and a substance with a film thickness of λ/2, Ca F 2, NaF, Li
The refractive index of F, SiO2, MgF2 is 1.25 to 1.
45 and a material with a film thickness of λ/4 (in this case, λ
=350-400nm). In the case of a three-layer structure, A I
Refractive index of 2203, CeF3, etc. is 1.55 to 1.65
3-4 In203, Y2O3, SnO2, ZrO2, CeO2
, a substance with a refractive index of 1.90 to 2.30 and a film thickness of λ/2 such as TiO2, and CaF2, NaF, LiF, SiO2
, a material with a refractive index of 1.25 to 1.45 such as M g F 2 and a film thickness of λ/4 (in this case, λ=35
0-400 nm). Other specific examples of the three-layer structure include:
CaF2, NaF, LiF, SiO2, MgF2
A material with a refractive index of 1.25 to 1.45 and a film thickness of λ/4, and a material with a refractive index of 1.75 to 2.10 and a film thickness of MgO, 5nCL, In2O3, and ZrO2. λ/2 material, SiO2, AI! 203, CeF3, or the like, with a refractive index of 1.45 to 1.65 and a film thickness of λ/4 (in this case, λ-300 to 350 nm).

The spectral reflection characteristics of these interference film filters, when transparent glass is used as a substrate, have a reflectance change amplitude of 7% to 15% in visible light, and a characteristic in which the amplitude of reflectance change in visible light is 7% to 15%, and the amplitude is small on the short wavelength side of visible light (<550 nm). The reflectance is lower than the reflectance of the substrate, and the reflectance is higher than the reflectance of the substrate on the long wavelength side of visible light (>550 nm), and the color of the reflection is slightly orange. This color is complementary to the hue of HA W03, and when the reflected light is observed through the light reflection property adjustment layer,
The spectral reflection characteristics of visible light become flat, and the hue becomes black when anti-glare (when colored).

This interference film filter has spectral reflection characteristics or a reflectance of 4.
The reflectance rises from around 50 nm, then increases monotonically until around 600 nm, and exhibits a substantially constant reflectance from 600 nm onwards. At this time, if the amplitude of the change in reflectance is at most 15%, the color becomes closest to black. Furthermore, in order to prevent the interference film filter from deteriorating the EC characteristics, it is desirable that the luminous reflectance of the interference film filter be equal to or lower than the luminous reflectance of the glass substrate. To achieve this, the reflectance on the short wavelength side of visible light (<550 nm) must be lowered than the reflectance of the substrate, and the reflectance on the long wavelength side of visible light (>550 nm) must be lowered than that of the substrate.
It is necessary to increase the reflectance of the substrate (50 nm) from that of the substrate. An interference membrane filter having such characteristics can be obtained by using the two-layered or three-layered membrane, or
The latter 356 layer structure has better properties. In addition, since this spectral reflection characteristic depends on the spectral reflection characteristic of the EC element portion, it is advisable to appropriately design the spectral reflection characteristic (profile) of the interference film filter according to the spectral reflection characteristic.

In addition, when using a colored film filter that absorbs light of a specific wavelength of visible light, a filter having a characteristic of being a complementary color to the hues of H and WO2 is used. As a result, the spectral reflection characteristics during anti-glare are made uniform and a blackish hue is exhibited. in particular,
Examples include composite films in which 0.1-10% of Ag, Cu and CdS are added to S]02. The film thickness varies depending on the amount of additive added, but when the amount added is 1%, it is required to be about 200 nm.

It should be noted that by adding a colored film filter, the reflectance in the non-anti-glare state (decolored state) and the anti-glare state (colored state) is slightly lowered, but there is no problem in using it as an anti-glare mirror. Also, due to the colored filter, the hue when not anti-glare may be slightly orange.
This is within the allowable range and poses no practical problem.

〔Example〕

The present invention will be explained in detail below.

Example 1 Tn20a (n=2°0) was formed on one surface of a glass substrate by 125 nm ion blasting or sputtering, and a single-layer interference film filter was applied to the glass substrate. After that, ITO was applied to the other side of the glass substrate.
+50n each in the order of lI rOx, Ta205, WO2
A film of 15 m, 30 nm, 800 nm, and 500 nm was formed and coated using the ion blating method, and then Aff of 15 nm was applied on top of it.
A reflective single-layer interference film-equipped EC material was prepared by forming and coating a film using a 0 nm vacuum evaporation method (Sample No. 1).

Example 2 A first material having a refractive index shown in Table 1 was coated on one surface of a glass substrate to a thickness of λ/2, and a second material was further coated on top of it to a thickness of λ/4. A two-layer interference film having reflection increase/decrease characteristics was formed using a vacuum evaporation method so as to have the following properties. Note that here, λ was set to 400 nm. After that, ITOlIrOiT a 205 was applied to the other side of the glass substrate.
, WO2 were formed and coated in the order of 7 8 150 nm, 30 nm, 800 nm, and 500 nm using the ion blating method, and then AI
! A reflective two-layer interference film-equipped EC material was prepared by forming and covering the sample with a thickness of 150 nm using a vacuum evaporation method (sample numbers 2 to 4).

Table 1 Example 3 A first material having a refractive index shown in Table 2 was coated on one surface of a glass substrate to a thickness of λ/4, and a second material was placed on top of it to a thickness of λ/4.
The material is coated to a thickness of λ/2, and then a third layer is added on top of it.
A three-layer interference film having reflection increase/decrease characteristics was formed using a vacuum evaporation method using a material to a film thickness of λ/4. In addition, here,
λ was set at 400 nm or 320 nm. after that,
IT○, IrOTa on the other side of the glass substrate
205, WO2 in order of 150 nm, 30 nm, 8
00nm, 500nm ion blating method
A reflective three-layer interference film-equipped EC material was produced by coating and further coating A and A with a thickness of 150 nm using a vacuum evaporation method. (Sample numbers 5-8).

9 0 Table 2 Example 4 SiO2Ag(Cu.

CdS etc.) at 1% (0.1-10% may be used)
A composite film doped with 1 each in order
Films of 50 nm, 30 nm, 800 nm, and 500 nm were formed and coated using the ion blating method, and then a 150 nm film of Al was formed and coated using the vacuum evaporation method to prepare a reflective colored EC material (sample number 9). ).

Comparative Example 1 ITO, IrO, Ta20 on one side of the glass substrate
5. 150nm, 30nm, 800n respectively in the order of WO3
A reflective EC material for comparison was prepared by forming and covering A and ff with a thickness of 150 nm using a vacuum evaporation method (sample number C1).

Comparative Example 2 A A 203 (n = l
, 60), ITO (n=1.90), MgF2 (n
= 1.38), the film thickness is λ/4, λ/2,
A three-layer antireflection film was formed using a vacuum evaporation method or an ion blating method so that the thickness was λ/4 (λ=550 nm).

After that, ITOllro on the other side of the glass substrate,
, Ta205, and WO2 in order of 150 nm and 30 nm, respectively.
, 800 nm, and 500 nm were formed and coated using the ion blasting method, and then a 150 nm film of AA was formed and coated using the vacuum evaporation method to prepare a reflective type EC material with an antireflection film for comparison (sample number C2). ).

Performance Evaluation Test The EC materials obtained in Examples 1 to 3 and Comparative Examples 1 and 2 and the comparative EC materials were examined for changes in hue and reflectance during decoloring and coloring during 1.35 square drive. The results are shown in Table 3.

As is clear from Table 3, the chromaticity coordinates of the EC materials provided with the interference film or the colored film of this example when colored are:
It can be seen that compared to the comparative EC material, the chromaticity is closer to that of A light (white), and the color is black. In particular, sample numbers 1.7 and 9 are closer to black. This is because the interference and colored films used in these EC materials are better designed. On the other hand, the hue of the comparative EC material (sample number C2) provided with an antireflection film was as follows:
Like the conventional product, it has a blue color and cannot be turned black.

Hayashi 3 34- On the other hand, the chromaticity coordinates of the EC material with an interference film or a colored film when decolored are slightly orange compared to the conventional product, which is within the allowable range, and there are no problems when using it as an anti-glare mirror. do not have.

Further, the change in reflectance when decoloring and when coloring varies greatly depending on the type of interference film used, and in the case of an EC material using a single-layer interference film, the reflectance when decoloring and coloring increases considerably. In particular, since the reflectance increases when colored, the anti-glare effect decreases, making it unsuitable for application as an anti-glare mirror. On the other hand, with the EC material using a two-layer interference film or a three-layer interference film, the change in reflectance during decoloring and coloring is the same as that of the conventional EC material (sample number C1) that does not use any material. It can be seen that is obtained. In particular, sample number 5, which has a three-layer interference film, has a contrast ratio that is lower than that of the conventional product (sample number C).
It is slightly larger than 1), indicating that the anti-glare effect is excellent. In addition, with EC materials using colored films, the reflectance when decolored decreases slightly, but the reflectance when colored also decreases.
It can be seen that the contrast ratio is considerably larger than that of the conventional product (sample number CI), indicating that the anti-glare effect is excellent. Note that the decrease in reflectance during decolorization is slight and poses no problem in practice.

In this way, the anti-glare mirror using the interference film or colored film can blacken the hue during anti-glare without impairing the EC characteristics of the EC element part, and the contrast ratio can be the same as or higher than that of conventional products. As described above, an excellent effect can be achieved in that double reflection during anti-glare can be reduced to the same level or lower than that of conventional products.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view of an embodiment of an all-solid-state EC material embodying the present invention, FIG. 2 is a cross-sectional view of a conventional EC material, and FIG.
The figure is a cross-sectional view of one embodiment of an all-solid-state EC material embodying the present invention, FIG. 4 is a diagram showing the spectral reflection characteristics in the visible light range of a specific example of the EC element part, and FIG. 5 is the same as that of FIG. FIG. 6 is a diagram showing an example of the spectral reflection characteristics of the interference film filter of the present invention, and FIG. 7 is a diagram showing the observed spectral reflection characteristics of a specific example.
56- is a diagram showing an example of the spectral transmission characteristics of the colored film filter of the present invention. 1.11...All-solid electrochromic material 2,
2... Transparent substrate 3, 3... Transparent conductive film 4, 4... First film 5, 5... Solid electrolyte film 6, 6... Second film 7, 7... Conductive film

Claims (2)

[Claims] (1) In all-solid-state electrochromic materials,
An all-solid-state electrochromic material characterized in that a light-transmitting part of the material is provided with a light reflection/transmission characteristic adjusting part having a function of increasing/decreasing spectral reflection/transmittance in visible light. (2) It has an EC element portion formed by sequentially laminating a transparent conductive film, a first film, a solid electrolyte film, a second film, and a conductive film on a transparent substrate, and either the first film or the second film An anti-glare mirror having an EC element part colored by oxidation and the other colored by reduction, a light reflection property adjusting layer made of a spectral reflection increasing/decreasing metal compound is formed in the light passing part of the anti-glare mirror, and at least the above-mentioned An anti-glare mirror characterized by forming an anti-glare part together with an EC element part.