JP6703686B2 - Light control element, light control member, and light control double glazing - Google Patents

Description

The present invention relates to a light control element, a light control member, and a light control multilayer glass.

Generally, in a building, a window is a place where light and heat come in and out much. For example, the percentage of light and heat that flows out of windows during heating in winter is about 50% of the total amount of heat that flows out of buildings, and the percentage of light and heat that flows in through windows during cooling in summer flows into the building. It is about 70% of the total heat. Therefore, it is possible to obtain an enormous energy saving effect by appropriately controlling the entrance and exit of light and heat in the window. The light control glass was developed for such a purpose and has a function of controlling inflow and outflow of light and heat.

There are several types of light control glass. Among them, the glass whose light transmittance changes reversibly by the application of current/voltage is called electrochromic light control glass, and the glass whose light transmittance changes reversibly with temperature is called thermochromic light control glass. The glass whose light transmittance reversibly changes depending on the atmospheric gas is called gas-chromic light control glass.

For example, an electrochromic light control glass using a tungsten oxide (WO ₃ ) thin film for a light control layer has almost reached the stage of practical use, and a commercially available product has been released. Further, the gas chromic light control glass is not so complicated in structure as the electrochromic light control glass, and is therefore expected as a light control glass that can be manufactured at low cost. Therefore, many studies have been made on the material of the gas chromic light control device and the structure of the light control glass.

Non-Patent Document 1 describes a gas chromic dimming device in which a layer of a mixture in which nanopalladium particles are attached to the surface of nickel oxyhydroxide particles is formed on a transparent substrate.

Patent Document 1 discloses a gas chromic light control device using a light control material containing tungsten oxide (WO ₃ ) and palladium particles dispersed in silicon dioxide.

Patent Document 2 discloses a reflective dimming thin film material including a multilayer thin film using a magnesium-zirconium alloy thin film as a dimming layer. Here, the reflection-type light control thin film material has a structure in which a catalyst layer is formed on the surface of the light control layer, or a structure in which a protective layer is further formed on the catalyst layer. Further, the reflective dimming thin film material has a chromic property that it becomes a colorless and transparent state by hydrogenation at around room temperature of 20° C. or a chromic property that it becomes a mirror state by dehydrogenation at around room temperature of 20° C.

Patent Document 3 discloses a method for manufacturing an electrochromic device using Prussian blue-type metal complex particles.

JP, 2005-161860, A JP, 2010-78890, A JP, 2011-180469, A

Chih-Wei Hu; Yasusei Yamada; Kazuki Yoshimura, “Fabrication of nickel oxyhydroxide/palladium (NiOOH/Pd) nanocomposite for gasochromic application”, Solar Energy Materials and Solar Cells, 2016, Issue 23, p.5390-5397.

However, in the light control element using oxyhydroxide described in Non-Patent Document 1, the color change due to the redox reaction is not remarkable under normal conditions, and the color changes between black and white. However, it was not in a transparent state, and its use as a light control element was limited.

Further, it is known that the light control element using the metal oxide described in Patent Document 1 has low durability, and the light control element using the metal alloy described in Patent Document 2 has weak weather resistance.

On the other hand, in the electrochromic light control glass as described in Patent Document 3, in order to obtain sufficient optical characteristics, the light control element needs to have a multilayer thin film structure of about 5 layers, and the cost of the transparent conductive film is low. There is a problem that becomes very high. In addition, the Prussian blue-type metal complex is an inorganic material, and it is considered that there is no major problem with respect to weather resistance. However, the electrolyte layer of the electrochromic element having the Prussian blue-type metal complex is used as an aqueous electrolyte or organic solvent-based A liquid is used, and weather resistance may be a problem in any case.

An object of one embodiment of the present invention is to provide a gas-chromic dimming element using a metal complex, which has excellent environment resistance.

[1] The following general formula (1) having gas chromic characteristics in which the light transmittance reversibly changes due to a redox reaction with an atmospheric gas.
A _x M ^A [M ^B (CN) ₆ ] _y ·zH ₂ O... (1)
A dimming device having a dimming layer containing a metal complex represented by, and a catalyst nanoparticle that promotes a redox reaction of the metal complex,
The light control element, wherein the atmosphere gas is a combination of a gas containing hydrogen and a gas containing oxygen or ozone.
[Represents wherein, A is a cation, ^{M A} is vanadium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, zinc, lanthanum, europium, gadolinium, lutetium, barium Represents one or more metal atoms selected from the group consisting of, strontium, and calcium, and M ^B is composed of vanadium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, nickel, platinum, and copper. Represents one or more metal atoms selected from the group, x is a number from 0 to 3, y is a number from 0.3 to 1.5, and z is a number from 0 to 30]

[2] The reduction potential of the metal complex is −0.22 [VvsAg/AgCl] or more, the oxidation potential is +0.62 [VvsAg/AgCl] or less, and the atmosphere gas is a gas containing hydrogen. , A gas containing oxygen, or a reduction potential of the metal complex of −0.22 [VvsAg/AgCl] or more and an oxidation potential of +0.62 [VvsAg/AgCl] or more, +2.3. The light control element according to [1], which is equal to or lower than [VvsAg/AgCl] and in which the atmosphere gas is a combination of a gas containing hydrogen and a gas containing ozone.

[3] The light control element according to [1] or [2], wherein the light control layer is formed by laminating a layer containing the metal complex and a layer containing the catalyst nanoparticles.

[4] The light control element according to [3], wherein the layer containing the catalyst nanoparticles has a film thickness of 2 nm or more and 100 nm or less.

[5] The light control element according to [1] or [2], wherein the light control layer is formed by dispersing the catalyst nanoparticles in the metal complex.

[6] The metal complex is a crystal of a metal complex formed by bridging a cyano group (CN) between the metal atom M ^A and the metal atom M ^B , and a positive electrode of the metal atom M ^{C is provided} around the crystal. ions and / or metal atom M ^D to the arrangement of those obtained by binding metal cyano complex anions, of which central metal is characterized by [1] to light control device according to any one of [5].
[The metal atom M ^C consists of vanadium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, zinc, lanthanum, europium, gadolinium, lutetium, barium, strontium, and calcium. It is one or more metal atoms selected from the group, and the metal atom M ^D is selected from the group consisting of vanadium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, nickel, platinum, and copper. One or more metal atoms]

[7] The catalyst nanoparticle layer contains one or more selected from the group consisting of palladium, palladium alloys, platinum, and platinum alloys, [1] to any one of [6]. Dimming element.

[8] The light control element according to any one of [1] 1 to [7], wherein the catalyst nanoparticles have a particle size of 1 nm or more and 100 nm or less.

[9] A light control member, wherein the film including the light control element according to any one of [1] 1 to [8] is formed on a transparent base material.

[10] The light control member according to [9], wherein the film thickness of the film is 10 nm or more and 2 μm or less.

[11] The light control member according to [9] or [10], wherein the transparent substrate is a glass substrate or a plastic substrate.

[12] having two or more glass substrates,
A light control double-glazing, wherein a film including the light control element according to any one of [1] to [8] is formed between two sheets of the glass base material.

[13] The light control double glazing according to [12], further comprising means for supplying and exhausting hydrogen, ozone, oxygen or air between the two glass substrates.

According to one aspect of the present invention, there is provided a gas-chromic light control device using a metal complex, which is excellent in environmental resistance.

It is a figure which shows an example of the light control element of this embodiment. It is a figure which shows an example of the light control member of this embodiment. It is a figure which shows an example of the light control laminated glass of this embodiment. It is a figure which shows an example of the light control element of this embodiment. 3 is an FT-IR spectrum of the light control device of Example 1. 3 is a graph showing the integrated intensity of X-ray photoelectron spectroscopy spectra around Fe _2p and Pt _4f with respect to the depth of the thin film of the light control device of Example 1. 3 is a cyclic voltammogram of the metal complex of Example 1. 3 is a schematic diagram showing an optical device for measuring the light transmittance of the light control double glazing of Example 1. FIG. 3 is a light transmission spectrum of the light control double glazing of Example 1. FIG. 5 is a diagram showing a relationship (cycle: 4 times) between a change in the atmosphere of the gas-filled double-glazing glass-filled chamber and a change in the light transmittance in Example 1. FIG. 5 is a diagram showing a relationship (cycle: 380 times) between a change in the atmosphere of the gas-filled double-glazing glass-filled chamber and a change in the light transmittance in Example 1. 3 is a light transmission spectrum of the light control double glazing of Example 2. 5 is a light transmission spectrum of the light control double-glazing of Example 3. 4 is a light transmission spectrum of the light control double glazing of Example 4. 5 shows a cyclic voltammogram of the water-dispersible nickel-iron PB type complex of Example 5. 5 is a light transmission spectrum of the light control double-glazing of Example 5. It is a figure which shows the relationship (cycle: 33 times) of the change of the atmosphere of the gas filling chamber of the light control double glazing of Example 5, and the change of a light transmittance. 7 is a light transmission spectrum of the light control double-glazing of Example 6. It is a figure which shows the relationship (cycle: 14 times) with the change of the atmosphere of the gas filling chamber of the light control double glazing of Example 6, and the change of a light transmittance. 7 shows a cyclic voltammogram of the water-dispersible copper-iron PB type complex of Example 7. 9 is a light transmission spectrum of the light control double-glazing of Example 7. It is a figure which shows the relationship (cycle: 17 times) of the change of the atmosphere of the gas filling chamber of the light control laminated glass of Example 7, and the change of light transmittance.

Next, modes for carrying out the present invention will be described, but various modifications and substitutions can be added to the following embodiments without departing from the scope of the present invention. Further, in the present specification, when the numerical range is represented by "to", the numerical values at both ends of "to" are included unless otherwise specified.

[Light control element]
FIG. 1 shows an example of the light control element 10 according to the present embodiment. This embodiment is a so-called Prussian blue-type metal complex light control device (hereinafter, also referred to as PB-type complex light control device) using a Prussian blue-type metal complex. The light control element 10 reversibly changes the light transmittance by an oxidation-reduction reaction with an atmospheric gas, that is, reversibly changes between a colorless (transparent) state and a colored state. Therefore, the light control element according to the present embodiment can be suitably used for the light control glass that controls the inflow and outflow of light and heat.

In the example of FIG. 1, the light control element 10 includes a light control layer (laminated body) in which the catalyst nanoparticle layer 10b containing the catalyst nanoparticles 1b is attached to the surface of the metal complex layer 10a. The catalyst nanoparticle layer 10b functions as a catalyst for the redox reaction of the metal complex layer 10a.

The metal complex layer 10a may be colorless (transparent) in the oxidized state and colored in the reduced state. Further, it may be colorless in the reduced state and colored in the oxidized state. In the present embodiment, the transmittance of light having a wavelength of 400 to 870 nm changes, so that the transmittance may change between the colorless (transparent) state and the colored state. In this embodiment, the colorless (transparent) state and the colored state can be evaluated by measuring the transmittance of light having wavelengths of 700 nm, 420 nm, and 475 nm depending on the material.

The atmosphere gas that causes a color change in the Prussian blue-type metal complex (hereinafter, may be simply referred to as a metal complex) can be a gas containing hydrogen, oxygen, ozone, or the like. As the atmosphere gas, a combination of at least two gases, that is, a combination of a gas that promotes the reduction of the metal complex and a gas that promotes the oxidation of the metal complex can be used. For example, a gas containing hydrogen as the reducing gas and a gas containing oxygen as the oxidizing gas can be used in combination. Also, a combination of a gas containing hydrogen as a reducing gas and a gas containing ozone as an oxidizing gas can be used. As the oxidizing gas, a gas containing oxygen and ozone may be used, or air may be used.

In the present embodiment, it is preferable that the reduction potential of the metal complex layer 10a is −0.22 [VvsAg/AgCl] or higher and the oxidation potential is +2.3 [VvsAg/AgCl] or lower. Thereby, it is possible to have a gas chromic property for a specific atmosphere gas described later. Further, when the oxidation potential is +0.62 [VvsAg/AgCl] or less, a gas having a lower oxidizing power can be used as the oxidizing gas of the atmospheric gas, as described later. The potential [VvsAg/AgCl] is a standard potential measured with a silver-silver chloride electrode as a reference.

In addition, in order to measure the electrochemical properties of the metal complex, the reduction peak potential and the oxidation peak potential of a given metal complex can be measured by cyclic voltammetry (CV).

When the dimming element 10 including the metal complex having a reduction potential of −0.22 [VvsAg/AgCl] or more is exposed to an atmosphere containing hydrogen, the catalyst nanoparticle layer 10b attached to the surface of the metal complex layer 10a. The metal complex layer 10a is reduced by the catalytic action of, the light transmittance changes in the wavelength range of 400 to 870 nm, and the color of the metal complex layer 10a changes.

At this time, the following reaction occurs due to the atmosphere containing hydrogen and the metal complex light control device 10. That is, the metal complex layer 10a reacts with hydrogen as follows due to the catalytic action of the catalyst nanoparticle layer 10b attached to the surface thereof.

H ₂ →2H ⁺ +2e ⁻ (E=−0.22 [VvsAg/AgCl]) (2)

Here, E is a redox potential. It can be said that the atmosphere containing hydrogen has a reducing ability of −0.22 [VvsAg/AgCl]. Therefore, when the reduction potential of the metal complex is −0.22 [VvsAg/AgCl] or more, it can react well with hydrogen. Therefore, by using a gas containing hydrogen as the reducing gas, it is possible to cause a color change in the light control element 10.

On the other hand, when the light control element 10 is exposed to an atmosphere containing oxygen such as air, the following reaction occurs between oxygen and the light control element 10.

O ₂ +2H ₂ O+4e ⁻ →4OH ⁻ (E=+0.62 [V vs Ag/AgCl])... (3)

That is, it can be said that oxygen has an oxidizing ability of +0.62 [VvsAg/AgCl]. Therefore, if the oxidation potential of the metal complex is +0.62 [VvsAg/AgCl] or less, it can react well with oxygen. Therefore, by using a gas containing oxygen as the oxidizing gas, it is possible to cause a color change in the light control element 10.

Further, when the light control element 10 is exposed to an atmosphere containing ozone, the following reactions occur due to the ozone and the light control element 10.

O ₃ +2H ⁺ +2e ⁻ =O ₂ +H ₂ O (E=+2.3 [VvsAg/AgCl])...(4)

That is, it can be said that ozone has a stronger oxidizing ability of +2.3 [VvsAg/AgCl] than oxygen. Therefore, even if the oxidation potential of the metal complex is +0.62 [VvsAg/AgCl] or more, if it is +2.3 [VvsAg/AgCl] or less, it can react favorably with ozone. Therefore, by using a gas containing ozone as the oxidizing gas, it is possible to cause a color change in the light control element 10.

The light control element 10 can be produced by coating the metal complex layer 10a and the catalyst nanoparticle layer 10b with a spin coater. Further, in coating, other wet coating methods such as a spray method can be used.

During the coating, the metal complex and the catalyst nanoparticles are dispersed in a solvent to prepare a dispersion liquid, and the dispersion liquid is sequentially coated. The solvent used for preparing the dispersion liquid is not particularly limited, and examples thereof include water, methanol, ethanol and organic solvents. Of these, water is preferred.

[Prussian blue-type metal complex]
In the present embodiment, ultrafine particles of Prussian blue-type metal complex (hereinafter sometimes abbreviated as “PB-type complex”) are contained in the metal complex layer 10a. The PB-type complex is a crystal formed by bridging a cyano group (CN) between the metal atom M ^A and the metal atom M ^B. In the present specification, PB-type complexes include Prussian blue (hereinafter sometimes abbreviated as “PB”) and analogs having the same structure as PB.

The basic composition formula of the PB-type complex used is
A _x M ^A [M ^B (CN) ₆ ] _y ·zH ₂ O... (1)
As long as it is represented by In the formula (1), A is a cation, and M ^A and M ^B are each a metal atom. In the above formula, a part of the cyano group (CN) may be substituted with a hydroxyl group, an amino group, a nitro group, a nitroso group, water or the like.

In the formula (1), the metal atom M ^A is vanadium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, zinc, lanthanum, europium, gadolinium, lutetium, barium, strontium, And one or more metals selected from the group consisting of calcium and calcium. As the metal atom M ^A , iron, cobalt, nickel, vanadium, copper, manganese, or zinc is preferable, and iron, copper, or nickel is more preferable. When a combination of two kinds of metals is used for the metal atom M ^A , a combination of iron and nickel, a combination of iron and copper, or a combination of nickel and copper is preferable, and a combination of iron and nickel is more preferable. preferable.

In formula (1), the metal atom M ^B is one or more metal atoms selected from the group consisting of vanadium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, nickel, platinum, and copper. .. Among them, iron, chromium or cobalt is preferable as the metal atom M ^B , and iron is particularly preferable. Regarding the metal atom M ^B , a combination of iron and chromium, a combination of iron and cobalt, or a combination of chromium and cobalt is preferable, and a combination of iron and chromium is more preferable.

In the formula (1), the cation A does not necessarily have to be contained, and when it is contained, potassium, sodium, cesium, rubidium, hydrogen, ammonia and the like can be mentioned, but the cation A is not limited thereto. Moreover, you may contain other materials, such as an anion. Further, it is not always necessary to contain water (H ₂ O). Further, as long as at least half retains the structure represented by this composition formula, it may be mixed with another complex or the like. For example, metal ions, organic molecules, other metal complexes, etc. may be adsorbed in order to improve optical response, catalytic activity, dispersibility, adsorbability to a substrate, etc. It suffices if the main structure of the changing portion is the above composition formula.

In the formula (1), x is a number of 0 to 3, preferably 0 to 1. y is a number of 0.3 to 1.5, preferably 0.5 to 1. z is a number of 0 to 30, preferably 5 to 15.

As described above, the PB-type complex is a crystal formed by bridging a cyano group (CN) between the metal atom M ^A and the metal atom M ^B , and the cation of the metal atom M ^C is present around the crystal. And/or a metal cyano complex having a metal atom M ^D as a central metal and an anion bonded thereto may be arranged. The metal atom M ^C is selected from the group consisting of vanadium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, zinc, lanthanum, europium, gadolinium, lutetium, barium, strontium, and calcium. It may be one kind or two or more kinds of metal atoms selected. The metal atom M ^D is vanadium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, nickel, platinum, and it may be one or two or more metal atoms selected from the group consisting of copper.

The method for producing a light control layer (light control element) containing a Prussian blue-type metal complex is not particularly limited as long as a light control layer (light control element) capable of causing an oxidation-reduction reaction can be produced, but particles are included. Examples thereof include a method of preparing a dispersion liquid and coating the dispersion liquid on a substrate, and a method of forming a thin film by electrolytic deposition.

As a method for preparing a dispersion liquid containing particles and coating it on a substrate, in addition to the method described in Patent Document 3, a reverse micelle method, a method using ferritin or the like as a template, and an aqueous solution of excess hexacyano metal ion and metal ion. And the like. However, the coating method is not limited to the above-mentioned method, and the production method, the shape of the metal complex, the dispersed state, etc. are not limited as long as the PB-type complex particles can be dispersed in the solvent. The particle size of the PB-type complex is preferably 500 nm or less and more preferably 200 nm or less in order to disperse it uniformly in the solvent. There is no particular lower limit to the average particle size, but it is practical that the average particle size is 3 nm or more due to the manufacturing method. The particle size in this specification is the median size of the particle size distribution obtained by the dynamic light scattering method (photon correlation method).

Modification molecules for improving dispersibility may be adsorbed on the surface of the metal complex particles. From this point of view, it is preferable that a compound having an amino group is allowed to coexist with the above metal complex in the metal complex layer 10a. At this time, the compound having an amino group may be in an ionic state. For example, when an organic solvent or an alcohol such as butanol is used, it is desirable to use a compound having an amino group, particularly an amino group and an alkyl group (preferably having 3 to 100 carbon atoms, more preferably 3 to 30 carbon atoms). And more preferably a compound having both of 3 to 16 carbon atoms. Specifically, oleylamine, stearylamine, propylamine, hexylamine and the like are desirable, and oleylamine, hexylamine and propylamine are particularly desirable.

When obtaining a dispersion liquid of a PB type complex using water as a dispersion medium, it is desirable to contain ferrocyanide ions, ferricyanide ions and the like. Further, in the case of obtaining a dispersion liquid of a PB-type complex using an alcohol such as butanol as a dispersion medium, it is also desirable to adsorb both the above amine and the above ion, and particularly propylamine and ferrocyanide ion or ferricyanide. A combination with a compound ion is desirable. The concentration of ultrafine particles in the dispersion is not particularly limited, but in consideration of good coating and film-forming properties, it is necessary to adjust the concentration to an appropriate concentration by the coating method. For example, when the coating is performed by the spin coating method, the content is preferably 1% by mass or more and 50% by mass or less, and when the spraying method is used, the content is preferably 0.1% by mass or more and 15% by mass or less.

[Catalyst nanoparticles]
The material forming the catalyst nanoparticles 1b is not particularly limited as long as it functions as a catalyst for the redox reaction of the PB-type complex used, but examples thereof include palladium, palladium alloys, platinum, platinum alloys, and the like, in which two or more kinds are used in combination. You may.

By making the particle size of the catalyst nanoparticles 1b to be nano size, the surface area per unit volume increases, so that the catalytic ability can be improved as compared with, for example, particles of the micron order. The average particle size of the catalyst nanoparticles 1b is preferably 1 nm or more and 100 nm or less, and more preferably 2 nm or more and 30 nm or less.

The catalyst nanoparticles 1b preferably have a protective layer formed on the surface thereof. Examples of the compound constituting the protective layer include a water-soluble polymer, a compound having an amino group and a thiol group, and the like.

The water-soluble polymer mentioned above is not particularly limited, and examples thereof include polyvinylpyrrolidone and polyol. The amino group and the thiol group are not particularly limited, but for example, the following general formula (5)
R ¹ -NH ₂ (5)
[In the formula, R ¹ is a monovalent group having 2 to 20 carbon atoms and represents a saturated hydrocarbon group or an unsaturated hydrocarbon group. ]
Examples of the amine include compounds represented by the following formula (6).

The method for synthesizing the catalyst nanoparticles 1b is not particularly limited, and examples thereof include a chemical reduction method and a solution method (for example, Synthesis of monodisperse Au, Pt, Pd, Ru and Ir nanoparticles in ethylene glycol, Bonet, F; Delmas. , V; Grugeon, S; Herrera Urbina, R; Silvert, PY et al. (1999), Nanostructured Materials vol. 11 (8) p. 1277-1284, and Size Control and Growth Process of Alkylamine-Stabilized Platinum Nanocrystals: A Comparison between the Phase Transfer and Reverse Micelles Methods, Kjell Wikander, Christophe Petit, Krister Holmberg, and Marie-Paule Pileni, Langmuir, 2006, 22 (10), pp 4863-4868).

For example, nano platinum particles are produced by reacting an aqueous solution of a metal compound containing platinum as a main component with an ethylene glycol solution of a water-soluble polymer as a material forming the protective layer in a reaction tank at 150°C. Can be synthesized.

In a more specific example, 50 mg of platinum (IV) chloride (H ₂ PtCl ₆ ), 10 ml of water, 20 mg of polyvinylpyrrolidone (PVP), and 40 ml of 1.5 M sodium hydroxide (NaOH) ethylene glycol solution are stirred. After mixing while stirring, the mixture is reacted at 150° C. for 2 hours to obtain a dispersion liquid of nanoplatinum particles. At this time, the liquid before the reaction has a light yellow color, but when the nano platinum particles are generated, the liquid turns dark brown. The average particle size of the nanoplatinum particles can be measured using a particle size distribution analyzer Photol ELSZ-1000 (manufactured by Otsuka Electronics Co., Ltd.). By the synthesis described above, the average particle size of nano platinum particles can be 1.5 nm, the particle size distribution can be very narrow, and the particle size can be almost uniform.

The synthetic chemical reaction formula of nano platinum particles is shown below.

2(CH ₂ OH) ₂ →2CH ₃ CHO+2H ₂ O (7)
^{_{2CH 3 CHO + Pt 4+ + 5OH}} - + H 2 O → CH 3 COO - + 6H 2 O + Pt ··· (8)

Other methods for synthesizing platinum nanoparticles include, for example, in a reaction tank at room temperature, a toluene organic solution of a metal compound containing platinum as a main component, a toluene solution of dodecylamine as a material forming the protective layer, and hydrogenation. Nano platinum particles can be synthesized by reacting with a sodium boron reducing agent (NaBH ₄ ).

In a more specific example, platinum (IV) chloride (H ₂ PtCl ₆ ) 104 mg, water 10 ml, toluene 30 ml and the phase transfer catalyst tetra(decyl)ammonium bromide (tetra(decyl) ammonium) are placed in a reaction vessel at room temperature. 330 mg of bromide) can be mixed and stirred for 30 minutes. As a result, the platinum ions originally present in the water layer can be changed to the toluene organic layer by the effect of the phase transfer catalyst. Then, by adding 690 mg of dodecylamine as a material for forming the nanoparticle protective layer and stirring for 1 hour, the original orange color of the toluene layer can be changed to a uniform milky white. Finally, by adding 125 mg of a sodium borohydride reducing agent (NaBH ₄ ) and reacting, nano platinum particles dispersed in the organic solvent toluene can be synthesized. By such synthesis, the average particle size of the nano platinum particles can be 2.6 nm, the particle size distribution can be very narrow, and the particle size can be almost uniform.

The method of applying the catalyst nanoplatinum particles 1b on the metal complex layer 10a is not particularly limited, for example, 1 wt% of the catalyst nanoplatinum particles 1b of water or a toluene solvent is dropped on the surface of the dried metal complex layer 10a, By the spin coating method, the uniformly dispersed catalytic nano platinum particles 1b can be formed on the surface of the metal complex layer 10a. As another method of applying the catalyst nano platinum particles 1b, for example, a spray coating method of spraying on the surface of the dried metal complex layer 10a can be mentioned.

When the dimming element 10 having the catalytic nano platinum particle layer 10b containing the catalytic nano platinum particles 1b attached to the surface of the metal complex layer 10a to form the dimming layer is exposed to an atmosphere containing hydrogen, the dimming layer is formed. Changes to colorless. Specifically, when Prussian blue is used as the metal complex, it changes from blue to colorless. When a nickel-iron PB type complex is used as the metal complex, the color changes from yellow to colorless, and when a copper-iron PB type complex is used, the color changes from brown to colorless.

[Light control member]
FIG. 2 shows the light control member 30 as an example of the present embodiment. The light control member 30 includes the glass base material 20 and the light control element 10 formed on the glass base material 20.

The thickness of the light control element 10 (the total thickness of the metal complex layer 10a and the catalyst nanoparticle layer 10b in the illustrated example) is preferably 10 nm or more and 2 μm or less, and 50 nm or more and 1 μm or less. More preferably. When the film thickness of the light control element 10 is 10 nm or more and 2 μm or less, it is easy to visually recognize a change in color of the light control element 10. When the light control device 10 includes the metal complex layer 10a and the catalyst nanoparticle layer 10b as shown in FIG. 1, the thickness of the catalyst nanoparticle layer 10b is preferably 2 nm or more and 100 nm or less, It is more preferably 5 nm or more and 70 nm or less.

The film of the light control element 10 can be formed by a wet coating method. Thereby, the film of the light control element 10 having a large surface area can be formed at high speed. Further, since an expensive vacuum device or the like is not used, it is possible to manufacture the light control member 30 at an extremely low cost as compared with the case of using a conventional inorganic material or metal.

The wet coating method is not particularly limited, and examples thereof include a spin coating method, a spray coating method, a dip coating method and a drop coating method.

The material forming the substrate 20 is not particularly limited as long as it transmits visible light, but examples thereof include glass substrates, for example, oxides such as quartz, sapphire, and lithium niobate. A transparent substrate such as a plastic substrate may be used instead of the glass substrate.

The material forming the plastic substrate is not particularly limited as long as it transmits visible light, and examples thereof include polyethylene terephthalate (PET) and acrylic resin. Cellophane tape or the like may be used as the plastic substrate. The shape of the base material is not particularly limited, and examples thereof include a plate shape and a sheet shape.

The above-mentioned form has a structure in which the layer (metal complex layer) 10a containing the PB-type complex and the layer 10b containing the catalyst particles are laminated on the substrate, but the form of the light control element is as follows. It is not limited to the laminated structure. For example, as shown in FIG. 4, it is possible to adopt a structure in which a PB type complex and a catalyst are mixed. That is, the light control element 110 can be provided with a light control layer in which the catalyst nanoparticles 11b are dispersed in the metal complex 11a. In this case, as shown in FIG. 4, a part of the catalyst nanoparticles 11b may be exposed on the surface of the light control layer. Such a light control layer can be prepared on the substrate 120 by preparing a dispersion liquid containing the metal complex 11a and the catalyst nanoparticles 11b and by the wet coating method as described above, to manufacture the light control member 130. it can. In that case, the thickness of the light control element 110 is preferably 10 nm or more and 2 μm or less, and more preferably 50 nm or more and 1 μm or less.

Thus, unlike the electrochromic device, the light control device according to the present embodiment does not need to introduce a current from the outside. Therefore, compared to the electrochromic device, a large degree of freedom in structure is created. The present embodiment is not limited to the illustrated one as long as the gas that induces redox reaches the catalyst appropriately and the catalyst and the PB-type complex are installed close to each other to some extent. For example, a structure in which a PB-type complex is supported on a non-woven fabric or the like and further catalyst particles are supported thereon may be used.

Further, in the illustrated example, the base materials (substrates) 20 and 120 have a flat plate shape, but the base material may have another shape. For example, if a PB-type complex and a catalyst are appropriately provided on a spherical structure, a certain space is provided above the spherical structure and sealed, and if a gas that controls color change can be introduced into that space, the color A change occurs and it can function as a gaschromic dimmer.

[Light control double glazing]
FIG. 3 shows an example of the light control laminated glass 70 of the present embodiment. In the light control multi-layer glass, the light control element 10 is formed between two glass substrates 20 and 60, and the opening is sealed by a seal member 40.

Argon gas is previously filled in the gas filling chamber S, and hydrogen, oxygen, or air can be supplied or exhausted by the atmosphere controller 50. For example, the atmosphere controller 50 can electrolyze water to supply hydrogen or oxygen to the gas filling chamber S, and use a vacuum pump to exhaust hydrogen or oxygen from the gas filling chamber S.

When hydrogen or a gas containing hydrogen is supplied to the gas filling chamber S, the light control element 10 is reduced and the color changes. Further, when oxygen or a gas containing oxygen such as air is supplied to the gas filling chamber S, the light control element 10 is oxidized and returns to the original state.

Therefore, by controlling the atmosphere of the gas filling chamber S by the atmosphere controller 50, the light control element 10 can be reversibly controlled between the reduced state and the oxidized state. Further, when the air supply/exhaust by the atmosphere controller 50 is interrupted, the reduction state or the oxidation state can be maintained. As a result, a dimmable double-layer glass capable of dimming by the gas chromic method is obtained.

At present, light-modulating double glazing is widely used in homes, and the use of double glazing is becoming the mainstream in new homes. By providing the light control element using the PB-type complex inside the double glazing, the internal space can be used as the gas filling chamber S for switching.

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.

<Preparation Example 1: Synthesis of water-dispersible PB nanoparticles>
PB nanoparticles and a dispersion liquid thereof were prepared by a method similar to the method described in Patent Document 3. Specifically, it is as follows.

An aqueous solution prepared by dissolving 14.5 g of sodium ferrocyanide decahydrate in 60 mL of water was mixed with 30 mL of an aqueous solution prepared by dissolving 16.2 g of iron nitrate nonahydrate in water and stirred for 5 minutes. The blue precipitate thus deposited was centrifuged, washed with water three times and then with methanol once, and dried under reduced pressure. The yield was 11.0 g, and the yield was 97.4% as Fe ₄ [Fe(CN) ₆ ] ₃ ·15H ₂ O.

0.40 g of the obtained PB (aggregate) was suspended in 8 mL of water. To this suspension, 180 mg of sodium ferrocyanide decahydrate was added, and when it was stirred, it changed into a blue transparent solution or dispersion. A dispersion liquid (A1) of PB nanoparticles was obtained.

<Preparation Example 2: Synthesis of water-dispersible nickel-iron PB type complex nanoparticles>
In Preparation Example 1, by changing the iron salt to a nickel salt, water-dispersible nickel-iron PB type complex nanoparticles and a dispersion liquid thereof were prepared. Specifically, it is as follows.

A solution prepared by dissolving 25.3 g of potassium ferricyanide in 80 mL of water and a solution prepared by dissolving 33.6 g of nickel nitrate hexahydrate in 20 mL of water were mixed at once and stirred for 5 minutes. The precipitated yellowish brown nickel-iron complex complex nanoparticles were taken out by centrifugation, washed with water three times, then with methanol once, and dried under reduced pressure. The yield was 30.0 g, and the yield was almost 100% as Ni ₃ [Fe(CN) ₆ ]2·10H ₂ O.

0.30 g of the obtained aggregate was suspended in 10 mL of water, and 150 mg of sodium ferrocyanide decahydrate was added to the suspension to disperse the nickel-iron PB type complex nanoparticles in water. The dispersion (A2) thus obtained was obtained.

<Preparation Example 3: Synthesis of water-dispersible copper-iron PB type complex nanoparticles>
In Preparation Example 1, by changing the iron salt to a copper salt, water-dispersible copper-iron PB type complex nanoparticles and a dispersion liquid thereof were prepared. Specifically, it is as follows.

A solution prepared by dissolving 1.98 g (6 mmol) of potassium ferricyanide in water and a solution prepared by dissolving 1.53 g (9 mmol) of a hydrate in copper chloride in water were mixed at once and stirred for 5 minutes. The deposited brown copper-iron PB-type complex nanoparticles were taken out by centrifugation, washed with water three times and then with methanol once, and dried under reduced pressure. The yield was 2.5 g, and the yield was almost 100% as Cu ₃ [Fe(CN) ₆ ] 2·10H ₂ O.

2.0 g of the obtained aggregate was suspended in 10 mL of water, and water in which 0.634 g (1.5 mmol) of sodium ferrocyanide was dissolved was added to disperse the copper-iron PB type complex nanoparticles in water. A dispersion (A3) was obtained.

<Preparation Example 4: Synthesis of toluene dispersible catalyst nano platinum particles>
Platinum (IV) chloride (H ₂ PtCl ₆ ) 104 mg, water 10 ml, tetra(decyl)ammonium bromide (C ₄₀ H ₈₄ BrN) 330 mg, and toluene 30 ml were mixed with stirring and then reacted at room temperature for 2 hours. As a result, the platinum component was transferred from the aqueous phase to the organic phase. Furthermore, when 690 mg of dodecylamine (C ₁₂ H ₂₇ N) was added and stirred, the solution became white. 125 mg of a reducing agent sodium borohydride (NaBH ₄ ) was added and stirred to obtain a dispersion liquid (B1) of nano platinum particles having toluene dispersibility. At this time, the solution before the reaction had a pale yellow color, but when nano platinum particles were formed, the solution turned dark brown.

The obtained solution was mixed with 200 ml of water with a separating funnel, and the upper layer toluene was collected. The upper layer toluene and 400 ml ethanol were mixed and stored in a freezer at −18° C. for 24 hours, whereby nano platinum particles having organic solvent dispersibility were precipitated. The nano platinum particles were dispersed in toluene to obtain a 0.2 wt% solution. The average particle size of the nanoplatinum particles was 2.6 nm when measured using a particle size distribution analyzer (Photoal ELSZ-1000, manufactured by Otsuka Electronics Co., Ltd.).

<Preparation Example 5: Synthesis of ethylene glycol dispersible catalyst nano platinum particles>
50 mg of platinum (IV) chloride (H ₂ PtCl ₆ ), 10 ml of water, 20 mg of polyvinylpyrrolidone (PVP) and 40 ml of an ethylene glycol solution were mixed with stirring and then reacted at 150° C. for 2 hours to disperse ethylene glycol. A dispersion liquid (B2) of nano platinum particles having properties was obtained. At this time, the liquid before the reaction had a pale yellow color, but when nano platinum particles were generated, the liquid turned dark brown. The average particle size of the nano platinum particles was measured and found to be 1.5 nm.

The synthetic chemical reaction formula of nano platinum particles is shown below.

2(CH ₂ OH) ₂ →2CH ₃ CHO+2H ₂ O...(7)

_{^{2CH 3 CHO + Pt 4+ + 5OH}} - + H 2 O → CH 3 COO - + 6H 2 O + Pt ... (8)

<Preparation Example 6: Preparation of mixed solution of PB type complex and ethylene glycol dispersible catalyst nano platinum particles>
5.0 ml of the PB nanoparticle dispersion liquid (A1) (concentration 9 wt%) prepared in Preparation Example 1 and 1 ml of the nanoplatinum particle dispersion liquid (B2) in Preparation Example 5 were stirred for 2 hours to obtain a mixed liquid (C1). Got

<Preparation Example 7: Preparation of mixed liquid of PB type complex and ethylene glycol dispersible catalyst nano platinum particles>
5.0 ml of the PB nanoparticle dispersion (A1) prepared in Preparation Example 1 and 1 ml of the dispersion of nanoplatinum particles (B2) in Preparation Example 5 and potassium bis(trifluoromethanesulfonyl)imide (K- 0.15 g of TFSI) was stirred for 2 hours to obtain a mixed solution (C2).

<Preparation Example 1: PB nanoparticle metal complex layer spin-coated film formation>
The PB nanoparticle dispersion liquid (A1) (concentration 9 wt%) prepared in Preparation Example 1 was spin-coated on a glass substrate (length 3.0 cm, width 3.0 cm, thickness 1.1 mm) to obtain a metal. The complex layer (L1) was produced. Specifically, a glass substrate was placed on a spin coater, 0.1 ml of the dispersion liquid (A1) was dropped, and spin coating was performed at 1500 rpm for 10 seconds and then at 2000 rpm for 10 seconds. This was left to stand in the air at about 25° C. for 30 minutes to prepare a light control layer containing PB nanoparticles. The film thickness was measured using a stylus profilometer (manufactured by KLA-Tencor Corp., stylus profilometer: α-STEP (trade name)), and it was about 200 nm.

<Production Example 2: Drop coat film formation of nickel-iron PB type complex layer>
The nickel-iron PB type complex nanoparticle dispersion liquid (A2) (concentration 8 wt%) prepared in Preparation Example 2 was used. Specifically, a glass substrate (length 3.0 cm, width 3.0 cm, thickness 1.1 mm) is set, 30 μl of the dispersion liquid 2 is dropped, and the dispersion liquid 2 is gradually dried on the substrate surface. This was left to stand in the air at about 25° C. for 120 minutes to prepare a metal complex layer (L2) containing nickel-iron PB type complex nanoparticles. When the film thickness was measured in the same manner as in Preparation Example 1, it was about 350 nm.

<Preparation Example 3: Spin coating film formation of copper-iron PB type complex layer>
Film formation was performed using the copper-iron PB type complex nanoparticle dispersion liquid (A3) (concentration 5 wt%) prepared in Preparation Example 3. Specifically, a glass substrate was placed on a spin coater, 0.2 ml of the dispersion liquid (A3) was dropped, and spin coating was performed at 500 rpm for 10 seconds and at 1000 rpm for 10 seconds. This was left to stand for 30 minutes in the air at about 25° C. to prepare a metal complex layer (L3) containing copper-iron PB type complex nanoparticles. When the film thickness was measured in the same manner as in Production Example 1, it was about 400 nm.

(Example 1)
<Production of light control member>
The dispersion liquid (B1) of Preparation Example 4 was applied onto the metal complex layer (L1) (10a in FIG. 1) prepared in Preparation Example 1 by spin coating to form a catalyst nanoparticle layer (10b in FIG. 1). ) Is formed to form a laminated body of the light control layer, whereby a light control element (10 in FIG. 1) is prepared. Specifically, the metal complex layer (L1) was placed on a spin coater so that the PB nanoparticles were on the top, 0.2 ml of the dispersion liquid (B1) of Preparation Example 4 was dropped, and rotation was performed at 1000 rpm. Spin coating was performed for 10 seconds, and further for 5 seconds by rotation at 1500 rpm. Then, the medium was left standing for 30 minutes in the atmosphere of about 25° C. to remove the medium by drying. Thus, a light control member including the light control element and the substrate was manufactured. The thickness of the entire light control device formed on the substrate was about 210 nm.

FIG. 5 shows an FT-IR spectrum of the light control element in the light control member of Example 1 obtained as described above. It can be seen that an absorption peak (2078 cm ⁻¹ ) due to Prussian blue is observed. The light control member of Example 1 was a blue uniform film. The FT-IR spectrum of the light control element was measured using an FT-IR Fourier transform near infrared/middle infrared/far infrared spectroscopic analyzer (Perkin Elmer Japan, Frontier (trademark)).

FIG. 6 shows the integrated intensity of the X-ray photoelectron spectroscopy spectrum around Fe _2p and Pt _4f of the light control element of Example 1 versus the depth of the thin film. The X-ray photoelectron spectroscopy spectrum of the light control element was measured using an X-ray photoelectron spectroscopy device (Theta Probe Angle-Resolved Spectrometer system, manufactured by Thermo Fisher Scientific). From FIG. 5, it can be seen that it was confirmed that platinum nanoparticles were present on the surface of the light control device in Example 1.

<Electrochemical characteristics of PB type complex>
The electrochemical characteristics of the PB type complex (Prussian blue) used in this example were measured. Using the PB-type complex nanoparticle dispersion liquid (A1) (concentration 9 wt%) prepared in Preparation Example 1, 100 μl was spin-coated on an ITO film of a glass substrate with an ITO film having a size of 3 cm×3 cm to form a metal film having a thickness of 200 nm. A complex layer (PB nanoparticle light control layer) was formed.

The metal complex layer (PB nanoparticle light control layer) thus formed was used as a working electrode, the Ag/AgCl electrode was used as a reference electrode, and a platinum electrode was used as a counter electrode. )Imide (K ⁺ TFSI ⁻ ) was used as an electrolyte, and cyclic voltammetry (CV) was carried out in a propylene carbonate solution. The water dispersible PB nanoparticle light control layer is insoluble in propylene carbonate.

FIG. 7 shows a cyclic voltammogram of the above metal complex layer (PB nanoparticle light control layer) (sweep rate: 1 mV/s). In FIG. 7, the waveform is a surface adsorption wave, which suggests that the metal complex layer is stably present in the propylene carbonate solution. Further, it can be seen that the oxidation peak potential exists at least at +0.1 [VvsAg/AgCl] and +0.3 [VvsAg/AgCl]. On the other hand, the reduction peak potential exists at least at −0.05 [VvsAg/AgCl] and +0.28 [VvsAg/AgCl]. Therefore, the above metal complex has at least two redox couples.

Thus, in the PB-type complex (Prussian blue) obtained in Preparation Example 1, the reduction potential was −0.22 [VvsAg/AgCl] or higher, and the oxidation potential was +0.62 [VvsAg/AgCl] or lower. Found to exist.

<Preparation of light control double-glazing and measurement of light transmission characteristics>
The above-mentioned light control member and a glass substrate were combined to produce the light control multi-layer glass as described above with reference to FIG. 3, and the light transmittance of the light control multi-layer glass was measured. An optical device (FIG. 8) equipped with a light source 80 and a spectrophotometer 90 was used for the measurement.

Specifically, as shown in FIG. 8, the light control member 30 of the light control multilayer glass 70 is disposed between the light source 80 and the spectrophotometer 90 such that each surface thereof faces the glass base material 60. After that, the opening was sealed with the sealing member 40, and the light transmittance of the light control double-glazing was measured.

As shown in FIG. 7, in order to supply/exhaust gas to/from the gas filling chamber S, an atmosphere controller 50 was installed. A silica glass substrate was used as the glass substrate 20. A USB4000 (manufactured by Ocean optics) was used as the spectrophotometer 90.

FIG. 9 shows the light transmission spectrum of the light control double glazing of Example 1. In FIG. 9, the light transmission spectra in the oxidized state and the reduced state show that the atmosphere in which the content of air and hydrogen is 100% (hereinafter referred to as hydrogen atmosphere) is supplied to the gas filling chamber S at room temperature for 1 minute, It is measured at room temperature.

As shown in FIG. 9, the dimming control double glass of Example 1 has a large change in the transmittance of light having a wavelength of 700 nm in the oxidized state and the reduced state (transmissivity change amount 76.6%), and has high performance. It can be seen that it has gaschromic properties.

Next, after supplying the gas filling chamber S with the hydrogen atmosphere for 30 seconds, the supply of the hydrogen atmosphere was stopped for 30 seconds. Here, when the supply of the hydrogen atmosphere is stopped, the air flows into the gas filling chamber S through the opening. The air supply control of the hydrogen atmosphere, which is one cycle, was repeated 4 times, and the transmittance of light having a wavelength of 700 nm was measured every 1 second during that time.

FIG. 10A shows the relationship between changes in the atmosphere of the gas filling chamber S and changes in the light transmittance. From FIG. 10A, it can be seen that in the first hydrogen supply control of the hydrogen atmosphere, the transmittance of the light having the wavelength of 700 nm changes from 12.0% to 88.6% by the supply of hydrogen. In addition, in the second to fourth hydrogen supply control of the hydrogen atmosphere, the transmittance of the light having the wavelength of 700 nm is changed from 86.1% to 15.9% by stopping the hydrogen supply and allowing the air to flow in. I know what to do.

FIG. 10B shows the result of the long-term evaluation experiment. After the hydrogen atmosphere was supplied to the gas filling chamber S for 60 seconds, the cycle of stopping the supply of the hydrogen atmosphere for 120 seconds was repeated. In the 380th cycle, the change in the transmittance changed from 76.6% to 41.2% due to the supply of the hydrogen atmosphere being stopped.

(Example 2)
<Production of light control member>
The metal complex layer (L1) prepared in Preparation Example 1 was baked on a hot plate at 150° C. for 30 minutes to remove water. A layer of the dispersion liquid (B2) of the nanoplatinum particles obtained in Preparation Example 5 was prepared on the metal complex layer (L1) by a spin coating method to obtain a light control device. Specifically, a metal complex layer (L1) was placed on a spin coater with PB nanoparticles on the top, 0.2 ml of the dispersion liquid (B2) of Preparation Example 5 was dropped, and spin coating was performed at 500 rpm. Spinning was done for 10 seconds, followed by spinning at 1500 rpm for 5 seconds. This was left to stand in the atmosphere at about 25° C. for 5 hours to dry and remove the medium. Thus, a light control member including the light control element and the substrate was manufactured. The thickness of the light control element formed on the substrate was about 200 nm.

<Preparation of light control double-glazing and measurement of its light transmission characteristics>
A light control laminated glass was produced in the same manner as in Example 1, and the light transmission characteristics were measured by the same method using the same optical device as in Example 1.

FIG. 11 shows the light transmission spectrum of the light control double glazing of Example 2. After supplying a hydrogen atmosphere to the gas filling chamber S at room temperature for 1 minute, the light transmittance was measured. As a result, the transmittance was significantly changed (the transmittance change amount at the wavelength of 700 nm was 72.0%), and it can be seen that the light control multilayer glass of Example 2 has high-performance gas chromic characteristics.

(Example 3)
<Production of light control member>
The mixed liquid (C1) obtained in Preparation Example 6 was applied onto a substrate by spin coating to prepare a light control member including a light control element using a PB type complex. The coating method and the film thickness were measured in the same manner as the metal complex layer (L1) of Preparation Example 2. The thickness of the light control element formed on the substrate was about 180 nm.

FIG. 4 schematically shows an example of the light control member of the third embodiment. The catalyst nanoparticles 11b of this example are dispersed in the metal complex 11a to form the light control element (light control layer) 110. The light control member 130 includes a base material 120 and a light control element 110.

<Preparation of light control double-glazing and measurement of its light transmission characteristics>
A light control laminated glass was produced in the same manner as in Example 1, and the light transmission characteristics were measured by the same method using the same optical device as in Example 1.

FIG. 12 shows the light transmission spectrum of the light control double glazing of Example 3. After hydrogen atmosphere was supplied to the gas filling chamber S at room temperature for 30 minutes, the light transmittance was measured. As a result, since the transmittance is largely changed (transmission change amount at wavelength of 700 nm is 53.9%), it can be seen that the light control multilayer glass of Example 3 has high-performance gas chromic characteristics.

(Example 4)
<Production of light control member>
The liquid mixture (C2) obtained in Preparation Example 7 was applied onto a substrate by a spin coating method to prepare a light control member including a light control element. The coating method and the measurement of the film thickness are the same as those in the production of the metal complex layer (L1) in Production Example 2. The thickness of the light control element formed on the substrate was about 250 nm.

<Production of multi-layer glass and measurement of its light transmission characteristics>
A light control laminated glass was produced in the same manner as in Example 1, and the light transmission characteristics were measured by the same method using the same optical device as in Example 1.

FIG. 13 shows the light transmission spectrum of the light control double glazing of Example 4. After supplying a hydrogen atmosphere to the gas filling chamber S at room temperature for 3 minutes, the light transmittance was measured. As a result, the transmittance is greatly changed (the transmittance change amount at a wavelength of 700 nm is 82.1%), and it can be seen that the light control multilayer glass of Example 4 has a high-performance gas chromic property.

(Example 5)
<Production of light control member>
The catalyst nanoparticle layer was formed by applying the dispersion liquid (B1) of Preparation Example 4 onto the nickel-iron PB type complex layer (L2) prepared in Preparation Example 2 by spin coating to form a PB type. A PB type complex light control member including a complex light control device was produced. The coating method and the film thickness were measured in the same manner as in Example 1. The thickness of the light control element formed on the substrate was about 400 nm.

<Electrochemical characteristics of PB type complex>
The electrochemical characteristics of the PB type complex (nickel-iron PB type complex) used in this example were measured. The measurement was performed in the same manner as the measurement of the electrochemical characteristics of the PB-type complex (Prussian blue) in Example 1 except that the PB-type complex nanoparticle dispersion liquid (A2) prepared in Preparation Example 2 was used.

FIG. 14 shows a cyclic voltammogram of the obtained metal complex layer (nickel-iron PB type complex layer) (sweep rate: 1 mV/s). In FIG. 14, the waveform is a surface adsorption wave, which suggests that the metal complex layer is stably present in the propylene carbonate solution. Further, it can be seen that the oxidation peak potential exists at +0.62 [VvsAg/AgCl] and +0.78 [VvsAg/AgCl]. On the other hand, the reduction peak potential exists at +0.59 [VvsAg/AgCl] and +0.72 [VvsAg/AgCl]. Therefore, the metal complex obtained in Preparation Example 2 has at least two redox couples.

Therefore, in Example 5, when a combination of a gas containing hydrogen and a gas containing oxygen or air was used as the atmospheric gas, the first redox couple (+0.62V, +0.59 [VvsAg/AgCl]) was used. By utilizing, the light control member exhibits gas chromic characteristics. When a combination of a gas containing hydrogen and a gas containing ozone is used as the atmospheric gas, the first redox couple (+0.62 V, +0.59 [VvsAg/AgCl]), and/or the second Redox couple (+0.78V, +0.72[VvsAg/AgCl]) can be used. Since ozone has a higher redox potential than oxygen and has a stronger oxidizing ability than air, a larger color change is obtained when ozone is used.

<Preparation of light control double-glazing and measurement of its light transmission characteristics>
A light control laminated glass was produced in the same manner as in Example 1, and the light transmission characteristics were measured by the same method using the same optical device as in Example 1.

FIG. 15 shows the light transmission spectrum of the light control double glazing of Example 5. After the hydrogen atmosphere was supplied from the air state to the gas filling chamber S at room temperature for 3 minutes, the light transmittance was measured. As a result, the transmittance is greatly changed (the transmittance change amount at the wavelength of 400 nm is 28.7%), and it can be seen that the light control multilayer glass of Example 5 has excellent gas chromic properties.

Next, after the hydrogen atmosphere was supplied to the gas filling chamber S for 60 seconds, the supply of the hydrogen atmosphere was stopped for 120 seconds. Here, when the supply of the hydrogen atmosphere is stopped, the air flows into the gas filling chamber S through the opening. The supply control of the hydrogen atmosphere, which is one cycle, was repeated 33 times, and the transmittance of the light having the wavelength of 400 nm was measured every 1 second during that time.

FIG. 16 shows the relationship between changes in the atmosphere of the gas filling chamber S and changes in the light transmittance. It can be seen from FIG. 16 that in the first hydrogen supply control of the hydrogen atmosphere, the transmittance of the light having the wavelength of 400 nm changed from 22.0% to 57.3% by the hydrogen supply. Further, in the air supply control of the hydrogen atmosphere of the 2nd to 33rd times, the hydrogen supply was stopped and the air was made to flow in, whereby the transmittance of light having a wavelength of 400 nm was changed from 53.1% to 27.8%. I know what I did.

(Example 6)
<Production of light control member>
In the same manner as in Example 5, a light control member including a light control element using the PB type complex was produced.

<Preparation of light control double-glazing and measurement of light transmission characteristics>
FIG. 17 shows the light transmission spectrum of the light control double glazing of Example 6. A state in which the gas filling chamber S was filled with ozone was constructed, and then a hydrogen atmosphere was supplied at room temperature for 1 minute, and then the light transmittance was measured. An ozone generator (SoecV350, manufactured by Marco) was used to generate ozone. Further, the supply of ozone was performed under the conditions of an ozone output of 35 mg/h and an air flow rate of 5 L/min.

As a result of the above measurement, it was found that the transmittance changed more greatly as compared with Example 5 (the transmittance change amount at the wavelength of 400 nm was 38.1%). That is, it was found that the light control double glazing of Example 6 in which hydrogen and ozone were used as the atmosphere gas had better gas chromic characteristics.

Next, after supplying hydrogen atmosphere to the gas filling chamber S for 2 minutes, ozone was supplied for 1 minute. The hydrogen atmosphere and ozone air supply control in which this is one cycle were repeated 15 times, and the transmittance of light having a wavelength of 400 nm was measured every 1 second during that time.

FIG. 18 shows the relationship between changes in the atmosphere of the gas filling chamber S (ozone and hydrogen) and changes in the light transmittance. From FIG. 18, it is understood that in the air supply control of the hydrogen atmosphere and the ozone atmosphere, the transmittance of the light having the wavelength of 400 nm changed from 68.0% to 25.1% by the air supply of ozone. When ozone is used instead of air (oxygen), the time required for switching the light transmittance of the light control double glazing is significantly reduced, and the change amount of the light transmittance of the light control double glazing is increased.

(Example 7)
<Production of light control member>
The dispersion (B1) obtained in Preparation Example 4 was applied onto the metal complex layer (L3) prepared in Preparation Example 3 by a spin coating method to form a layer of catalyst nanoplatinum particles, and dimming was performed. A light control member including an element was manufactured. The coating method and the film thickness were measured in the same manner as in Example 1. The thickness of the light control device formed on the substrate was about 400 nm.

<Electrochemical characteristics of PB type complex>
The electrochemical characteristics of the PB type complex (copper-iron PB type complex) used in this example were measured. The measurement was performed in the same manner as the measurement of the electrochemical characteristics of the PB-type complex (Prussian blue) in Example 1 except that the metal complex nanoparticle dispersion liquid (A2) prepared in Preparation Example 2 was used.

FIG. 19 shows a cyclic voltammogram of the copper-iron PB type complex (sweep rate: 1 mV/s). From FIG. 19, it is found that the waveform is a surface adsorption wave, and it is suggested that the water-dispersible copper-iron PB type complex nanoparticle light control layer is stably present in the propylene carbonate solution. Further, it was found that the oxidation peak potential was present at +0.86 [VvsAg/AgCl]. On the other hand, the reduction peak potential was at +0.81 [VvsAg/AgCl]. Therefore, the copper-iron PB type complex layer has a redox couple.

Therefore, in Example 7, when a combination of a gas containing hydrogen and a gas containing ozone is used as the atmospheric gas, a redox couple (+0.86 V, +0.81 [V vs Ag/AgCl]) should be used. From this, it can be seen that the light control element exhibits gas chromic characteristics.

<Preparation of light control double-glazing and measurement of light transmission characteristics>
FIG. 20 shows the light transmission spectrum of the light control double glazing of Example 7. After the hydrogen atmosphere was supplied to the gas filling chamber S from the ozone state at room temperature for 2 minutes, the light transmittance was measured. As a result, the transmittance was changed (the transmittance change amount at the wavelength of 475 nm was 14.3%), and it was found that the light control double glazing of Example 7 had gas chromic characteristics.

Next, after supplying hydrogen atmosphere to the gas filling chamber S for 2 minutes, ozone was supplied for 1 minute. The hydrogen atmosphere and ozone air supply control with this as one cycle were repeated 17 times, and the transmittance of light having a wavelength of 400 nm was measured every 1 second during that time. The ozone was supplied in the same manner as in Example 6.

FIG. 21 shows the relationship between changes in the atmosphere of the gas filling chamber S (ozone and hydrogen) and changes in the light transmittance. From FIG. 21, it was found that in the hydrogen atmosphere and ozone air supply control, the maximum change in transmittance of light having a wavelength of 475 nm due to hydrogen air supply was 60.0% to 38.2%.

(Comparative Examples 1 to 3)
<Production of light control member>
Preparation was performed in the same manner as in Example 1 except that the metal complex layers (L1) to (L3) obtained in Preparation Examples 1 to 3 were used and the catalyst nanoplatinum particles (dispersion liquid (B1)) were not used. An optical device was produced.

<Preparation of light control double-glazing and measurement of light transmission characteristics>
A light control double-layered glass including each of the metal complex layers (L1) to (L3) was produced in the same manner as in Example 1 except that the catalyst nanoplatinum particles were not used.

In the dimming control glass of Comparative Examples 1 to 3, even when air or a hydrogen atmosphere was supplied to the gas filling chamber S, the redox reaction did not sufficiently occur, and the color change could not be visually recognized. Therefore, it was found that the light control double glazings of Comparative Examples 1 to 3 do not have gas chromic properties. This is because the catalytic nanoplatinum particles do not exist in the light control element, so that the spillover phenomenon does not occur, the hydrogen molecule does not change favorably to the hydrogen atom, and further, the hydrogen atom changes into a proton (H ⁺ ) and an electron (e). ^This is because the change to ⁻ ) does not occur well.

(Comparative example 4)
<Production of light control member>
In the same manner as in Example 7, a light control member including a light control element using the PB type complex was produced.

<Production of light-modulating double-glazing and measurement of light transmission characteristics>
In the same manner as in Example 7, a light control double glass was prepared.

In the same manner as in Example 7 except that air was used instead of ozone, the light transmittance of the dimming control glass in the oxidized state and the reduced state was measured.

In the light control double glazing of Comparative Example 4, even if air or a hydrogen atmosphere was supplied to the gas filling chamber S, the redox reaction did not sufficiently occur and the color change could not be visually recognized. It was found that the double glazing of Comparative Example 4 did not have gas chromic properties. It is considered that this is because the oxidation peak potential of the light control element in Comparative Example 4 did not exist below +0.62 [VvsAg/AgCl], and there was no redox pair corresponding to the combination of hydrogen and oxygen gas.

As described above in detail, in the present embodiment, a gas chromic light control device having catalyst nanoparticles on the surface or in the PB type complex layer having gas chromic properties, and a film including the gas chromic light control device are formed on a substrate. The present invention relates to the gas-chromic light control member and the PB-type complex light control double-glazing. According to this embodiment, a gas-chromic light control device can be manufactured using a PB type complex material.

Further, the light control element of the present embodiment is inexpensive, and it is possible to manufacture it at low cost because expensive nanoparticles can be used in a very small amount. Furthermore, the light control element of this embodiment has high environmental resistance. Moreover, it can be manufactured by a simple process, and the structure is simple. Therefore, according to the present invention, it is possible to realize a metal complex light control element, a metal complex light control member, and a metal complex light control double-layer glass which are excellent in performance and inexpensive.

The present embodiment is useful as a window material technology for controlling the sunlight transmittance in buildings and vehicles.

This application claims priority based on Japanese Patent Application No. 2017-038803 filed with the Japan Patent Office on Mar. 1, 2017, the entire contents of which are incorporated herein by reference.

1b Catalyst nanoparticles 10a, 110a Metal complex layer 10b Catalyst nanoparticle layer 10, 110 Light control element (light control layer)
11a Metal Complex 20 Transparent Base Material 30, 130 Light Control Member 40 Seal Member 50 Atmosphere Controller 60 Transparent Base Material 70 Light Control Double-Layer Glass 80 Light Source 90 Spectrophotometer S Gas Filling Chamber

Claims (13)

The following general formula (1) has a gas chromic property that reversibly changes the light transmittance due to a redox reaction with an atmospheric gas.
A _x M ^A [M ^B (CN) ₆ ] _y ·zH ₂ O... (1)
A dimming device comprising a dimming layer containing a metal complex represented by, and a catalyst nanoparticle that promotes a redox reaction of the metal complex,
The light control element, wherein the atmosphere gas is a combination of a gas containing hydrogen and a gas containing oxygen or ozone.
[Represents wherein, A is a cation, ^{M A} is vanadium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, zinc, lanthanum, europium, gadolinium, lutetium, barium Represents one or more metal atoms selected from the group consisting of, strontium, and calcium, and M ^B is composed of vanadium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, nickel, platinum, and copper. Represents one or more metal atoms selected from the group, x is a number from 0 to 3, y is a number from 0.3 to 1.5, and z is a number from 0 to 30] The reduction potential of the metal complex is −0.22 [VvsAg/AgCl] or more, the oxidation potential is +0.62 [VvsAg/AgCl] or less, and the atmosphere gas contains a hydrogen-containing gas and oxygen. Or a reduction potential of the metal complex is −0.22 [VvsAg/AgCl] or more, and an oxidation potential is +0.62 [VvsAg/AgCl] or more, +2.3 [VvsAg/ AgCl] or less, and the atmosphere gas is a combination of a gas containing hydrogen and a gas containing ozone. The light control element according to claim 1, wherein the light control layer is formed by laminating a layer containing the metal complex and a layer containing the catalyst nanoparticles. The light control device according to claim 3, wherein the layer containing the catalyst nanoparticles has a film thickness of 2 nm or more and 100 nm or less. The light control element according to claim 1, wherein the light control layer is formed by dispersing the catalyst nanoparticles in the metal complex. The metal complex is a crystal of a metal complex in which a cyano group (CN) is bridged between the metal atom M ^A and the metal atom M ^B , and a cation of the metal atom M ^C and / or light control device according to claim 1, characterized in that a one obtained by combining the metal cyanide complex anion, of which central metal is a metal atom M ^D.
[The metal atom M ^C consists of vanadium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, zinc, lanthanum, europium, gadolinium, lutetium, barium, strontium, and calcium. It is one or more metal atoms selected from the group, and the metal atom M ^D is selected from the group consisting of vanadium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, nickel, platinum, and copper. One or more metal atoms] The light control device according to claim 1, wherein the catalyst nanoparticles include one or more selected from the group consisting of palladium, palladium alloys, platinum, and platinum alloys. The light control device according to claim 1, wherein the catalyst nanoparticles have a particle size of 1 nm or more and 100 nm or less. A light control member, wherein the film including the light control element according to claim 1 is formed on a transparent base material. The light control member according to claim 9, wherein the film thickness of the film is 10 nm or more and 2 μm or less. The light control member according to claim 9, wherein the transparent base material is a glass base material or a plastic base material. Has two or more glass substrates,
A light control double glazing, wherein a film including the light control element according to claim 1 is formed between two glass base materials. The light control double glazing according to claim 12, further comprising means for supplying and exhausting hydrogen, ozone, oxygen or air between the two glass substrates.