TWI627268B - Gas-induced variable-tone optical element and method of manufacturing the same, gas-induced color-changing optical component, and multi-layer glass - Google Patents

Abstract

One aspect of the present invention is a gas-induced color light element which is reversibly changeable in light transmittance by an oxidation-reduction reaction with an ambient gas, comprising: an electrochromic organic polymer; and as the electrochromic organic polymerization Nanoparticles that act as a catalyst for the redox reaction of the species. Wherein the reduction peak potential present at -0.6V vs Ag / AgNO ₃ or more, the oxidation peak potential of + 0.3V vs ₃ present in the Ag / AgNO.

Description

Gas-induced variable-tone optical element and method of manufacturing the same, gas-induced color-changing optical component, and multi-layer glass

The present invention relates to a gas chromic dimming element, a method of producing a gas-induced color light element, a gas-induced color light component, and a multilayer glass.

In general, in buildings, windows are places where the ratio of light and heat is large. For example, in a winter greenhouse, the ratio of light and heat flowing out of the window is about 50%, while in the summer cold room, the ratio of light and heat flowing through the window is about 70%. Therefore, by appropriately controlling the light and heat in and out of the window, a huge energy saving effect can be obtained. Dimming glass was developed to achieve such a purpose, and has a function of controlling the inflow and outflow of light and heat.

There are several types of dimming glass. Among them, a glass which can be reversibly changed in light transmittance by applying a current and a voltage is called an electrochromic light-adjusting glass; a glass which is reversibly changeable in light transmittance is thermochromic. (thermo chromic) dimming glass; and by ambient gas, glass with a reversible change in light transmittance is called a gas chromic dimming glass.

Among them, the research on the electrochromic light glass using the tungsten oxide (WO ₃ ) film in the dimming layer is the most advanced, and at present, it has basically reached the practical stage, and related products have appeared on the market.

However, in order to obtain sufficient optical characteristics, the electrochromic light glass needs to have a dimming element designed as a multilayer film structure of about five layers, and the cost of the transparent conductive film is extremely high.

On the other hand, the gas-induced tone light glass is not complicated in structure compared with the electrochromic light glass, and therefore is a material that is expected to be low-cost manufacturing, and has been used for the material of the light-adjusting element. Or the structure of the dimming glass has been studied variously.

Patent Document 1 discloses a reflective dimming film material composed of a multilayer film in which magnesium is used. The zirconium alloy film is used as a light control layer. Here, the reflective dimming film material has a structure in which a catalyst (catalyst) layer is formed on the surface of the light control layer or a structure in which a protective layer is formed on the catalyst layer. Further, the reflective dimming film material has a discoloration property which can be changed to a colorless transparent state by hydrogenation at room temperature of about 20 ° C, and has a mirror image by dehydrogenation at room temperature of about 20 ° C The color change characteristic of the state (reflected state).

Patent Document 2 discloses a thin film member in which a multilayer film is formed on a transparent substrate, which is changed from a mirror image state to a transparent state by a hydrogen-containing gas, and can be changed from a transparent state to a gas by an oxygen-containing gas. Mirrored state dimming material. Here, the multilayer film is composed of a light modulating layer, a buffer layer, and a catalyst layer. In addition, as a dimming layer, Y-Mg, La-Mg, Gd-Mg or Sm-Mg rare earths are also formed. Magnesium alloy or magnesium of Mg-Ni, Mg-Mn, M-Co or Mg-Fe. Transition metal alloy film.

Further, Non-Patent Document 1 discloses a light-adjusting material using tungsten oxide (WO ₃ ).

[Previous Technical Literature] [Patent Document]

[Patent Document 1] JP-A-2010-78890

[Patent Document 2] JP-A-2007-301778

[Non-patent literature]

[Non-Patent Document 1] Gasochromic windows, V. Wittwer, M. Datz, J. Ell, A. Georg, W. Graf et al., Solar Energy Materials and Solar Cells vol. 84 p. 305-314 (2004).

However, as for the material of the dimming element of the gas-induced color light glass, inorganic materials such as metal oxides such as W, Ni, V, and In, metal alloys, and the like are dominant, and therefore, the color change is mainly between colorless and blue. Between colorless and brown, and between transparent and mirrored states, there are fewer types.

It is an object of one aspect of the present invention to provide a gas-induced variable-tone optical element that can diversify color variations.

One aspect of the present invention is a gas-induced color light element which is reversibly changeable in light transmittance by an oxidation-reduction reaction with an ambient gas, comprising: an electrochromic organic polymer; and as the electrochromic organic polymerization Nanoparticles that act as a catalyst (catalyst) for the redox reaction of the species. Wherein the reduction peak potential present at -0.6V vs Ag / AgNO ₃ or more, the oxidation peak potential of + 0.3V vs ₃ present in the Ag / AgNO.

According to an aspect of the present invention, it is possible to provide a gas-induced color light element which can diversify color variations.

1‧‧‧ gas-induced color light components

1a‧‧‧Electrochromic organic polymer

1b‧‧‧Nanoparticles

2‧‧‧ gas-induced color light element film

3‧‧‧glass substrate

4‧‧‧ glass substrate

5‧‧‧Seal parts

10‧‧‧ gas-induced color light glass

60‧‧‧Vehicle exhaust

70‧‧‧Light source

80‧‧‧Spectrophotometer

S‧‧‧ gas filling room

Fig. 1 is a view showing an example of a gas-induced color light element of the present embodiment.

FIG. 2 is a view showing an example of a method of producing the gas-induced color light element of FIG. 1. FIG.

Fig. 3 is a view showing an example of a gas-induced color light member of the present embodiment.

FIG. 4 is a view showing an example of the multilayer glass of the present embodiment.

[Fig. 5] FT-IR spectrum of the gas-induced color light element of Example 1.

Fig. 6 is a cyclic voltammogram of the gas-induced color tone element film of Example 1.

Fig. 7 is a schematic view showing an optical device for measuring the light transmittance of the multilayer glass of Example 1.

Fig. 8 is a transmission spectrum of the multilayer glass of Example 1.

Fig. 9 is a graph showing the relationship between the change in the ambient gas and the change in the light transmittance in the gas filling chamber of the multilayer glass of Example 1.

Fig. 10 is a graph showing the relationship between the change in the ambient gas and the change in the light transmittance in the gas filling chamber of the multilayer glass of Example 1.

[Fig. 11] FT-IR spectrum of the gas-induced color light element of Example 7.

Fig. 12 is a cyclic voltammogram of the gas-induced color tone element film of Example 7.

Fig. 13 is a graph showing the relationship between the change in the ambient gas and the change in the light transmittance in the gas filling chamber of the multilayer glass of Example 7.

[Fig. 14] A cyclic voltammogram of the light-adjusting element film of Comparative Example 3.

In the following, the embodiments for carrying out the invention will be described. However, various modifications and substitutions may be made to the embodiments described below without departing from the scope of the invention.

[gas-induced color light element]

Fig. 1 shows an example of a gas-induced color light element of the present embodiment.

In the gas-induced color tone element 1, the light transmittance can be reversibly changed by a redox reaction with an ambient gas, that is, it can be reversibly changed between a colorless (transparent) state and a colored state. Here, the gas-induced color light element 1 is coated with nanoparticles 1b on the surface of the electrochromic organic polymer 1a. Further, the nanoparticles 1b can function as a catalyst (catalyst) for the redox reaction of the electrochromic organic polymer 1a.

It is to be noted that the colorless (transparent) and colored states correspond to the oxidized state and the reduced state or the reduced state and the oxidized state of the electrochromic organic polymer 1a, respectively.

In the present embodiment, a colorless (transparent) state and a colored state can be generated by a change in transmittance of light having a wavelength of 370 to 2500 nm. In the present embodiment, the colorless (transparent) state and the colored state can be evaluated by measuring the transmittance of light having a wavelength of 700 nm.

In the gas-induced color tone element 1, the reduction peak potential is present at -0.6 V vs Ag/AgNO ₃ or more, and the oxidation peak potential is present at +0.3 V vs Ag/AgNO ₃ or less. Further, the reduction peak potential is not present at -0.6V vs Ag / AgNO ₃ or more oxidation peak potential or the case does not exist in the + 0.3V vs ₃ or less where the Ag / AgNO, does not have consistent color characteristics of air Electrochromic light element.

It should be noted that the reduction peak potential and the oxidation peak potential can be measured by cyclic voltammetry (CV).

After exposing the gas-induced color light element 1 to an ambient gas containing hydrogen, the electrochromic organic polymerization is carried out by the catalyst (catalytic) action of the nanoparticles 1b on the surface of the electrochromic organic polymer 1a. The substance 1a can be reduced, and the color can be changed. The transmittance of light can also be changed in the wavelength range of 400 to 2500 nm.

At this time, the following reaction can occur by the action of the catalyst of the nanoparticles 1b on the surface of the electrochromic organic polymer 1a and the ambient gas containing hydrogen.

H ₂ → 2H ⁺ +2e ^- (E=-0.6V vs Ag/AgNO ₃ )

Here, E is an oxidation-reduction potential, and an ambient gas including hydrogen has a reducing ability of -0.6 V vs Ag/AgNO ₃ .

On the other hand, in the air, the following reaction can occur by the action of the nanoparticles 1b on the surface of the electrochromic organic polymer 1a with oxygen.

O ₂ +2H ₂ O+4e ^- → 4OH ^- (E=+0.3V vs Ag/AgNO ₃ )

Here, the hydrogen in the air has an oxidation ability of +0.3 V vs Ag/AgNO ₃ .

[Manufacturing Method of Gas-Changed Color Light Element]

FIG. 2 shows an example of a method of manufacturing the gas-induced color light element 1.

The gas-induced color tone element 1 can be produced by mixing the electrochromic organic polymer 1a and the nanoparticles 1b in a solvent.

The solvent is not particularly limited, and examples thereof include water, methanol, ethanol, and an organic solvent. Among them, water is preferred.

[Electrochromic Organic Polymer]

The electrochromic organic polymer preferably has the general formula (wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 20 or less carbon atoms, and 1 or more carbon atoms; And an alkoxy group of 20 or less, an alkyl ester group having 1 or more and 20 or less carbon atoms, an aryl group, an amino group or a cyano group which may have a substituent. Unit. General unit represented by (wherein R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 20 or less carbon atoms, an alkoxy group having 1 or more and 20 or less carbon atoms, and the number of carbon atoms is An alkyl ester group of 1 or more and 20 or less, an aryl group, an amino group which may have a substituent group, or a cyano group, and a structural unit represented by the general formula (Chemical Formula 3) (wherein R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 20 or less carbon atoms, an alkoxy group having 1 or more and 20 or less carbon atoms, and the number of carbon atoms is An alkyl ester group of 1 or more and 20 or less, an aryl group, an amino group which may have a substituent group, or a cyano group. (wherein R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 20 or less carbon atoms, an alkoxy group having 1 or more and 20 or less carbon atoms, or carbon; An alkyl ester group having 1 to 20 or more atoms, an aryl group, an amino group or a cyano group which may have a substituent group, and a structural unit represented by the formula (wherein R ¹² and R ¹³ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 20 or less carbon atoms, an alkoxy group having 1 or more and 20 or less carbon atoms, and the number of carbon atoms is One or more selected from the group consisting of an alkyl group having 1 or more and 20 or less, an aryl group, an amino group which may have a substituent, or a cyano group.

The alkyl group represented by R ¹ to R ¹³ may be linear or branched, and may be cyclic.

The alkyl group represented by R ¹ to R ¹³ preferably has 1 or more and 6 or less carbon atoms.

Examples of the alkyl group represented by R ¹ to R ¹³ include a methyl group, an ethyl group, an n-propyl (propyl) group, an isopropyl group, and an n-butyl group. Base, tert-butyl, pentyl group, hexyl group, octyl group, dodecyl group, cyclohexyl group, bicyclooctyl group, adamantane (adamantyl) base and so on. Among them, a methyl group, an ethyl group, an n-butyl group or a hexyl group is preferred, and a methyl group or an ethyl group is preferred.

It is to be noted that at least a part of the hydrogen atoms contained in the alkyl group may be replaced by a fluorine atom.

Examples of the alkyl group substituted by the fluorine atom include a trifluoromethyl group.

The alkoxy group represented by R ¹ to R ¹³ may be linear or branched, and may be cyclic.

The alkoxy group represented by R ¹ to R ¹³ preferably has 1 or more and 8 or less carbon atoms.

Examples of the alkoxy group represented by R ¹ to R ¹³ include a methoxy group, an ethoxy group, an isopropoxy group, an n-butoxy group, and a tert. a butoxy group, an ethylhexyloxy group, an octyloxy group, a benzyloxy group or the like. Among them, a methoxy group, an ethoxy group or an isopropyl group is preferred, and a methoxy group or an isopropyl group is preferred.

Examples of the aryl group represented by R ¹ to R ¹³ include a phenyl (phenyl) group, a biphenyl group, a fluorenyl group, a naphthyl group, a fluoranthenyl group, and an anthracene. (anthryl) group, phenanthryl group, pyrenyl group, perylenyl group and the like. Among them, a phenyl group is preferred.

In addition, the aryl group is an alkyl group having 1 or more and 8 or less carbon atoms (the number of carbon atoms is preferably 1 or more and 4 or less), and the number of carbon atoms is 1 or more and 8 or less (the number of carbon atoms is preferably One or more and four or less of the alkoxy group, the aralkyl group, the amino group which may have a substituent group, or the substituted group such as a silyl group which may have a substituent group may be substituted.

Specific examples of the substituent are phenyl, biphenyl, naphthyl, benzyl, dimethylamino, triisopropylsilyl, and the like. .

Examples of the heterocyclic group represented by R ¹ to R ¹³ include a pyridyl group and an indolyl group. Among them, a pyridyl group is preferred.

The electrochromic organic polymer preferably has an origin derived from anions, 3,4-ethylenedioxythiophene, propylenedioxythiophene, pyrrole and thiophene. a constituent unit of one or more monomers selected from the group consisting of.

The electrochromic organic polymer is preferably water soluble.

The method for synthesizing the electrochromic organic polymer is not particularly limited, and examples thereof include chemical oxidative polymerization, polycondensation, polyaddition, addition condensation, and ion polymerization. , cation polymerization, anion polymerization, and the like.

For example, it can be used in a reaction tank at room temperature by using an aniline as a main component (A NI), an aqueous solution of poly(poly)(styrene sulfonic acid) (PSS), 1 M hydrochloric acid, or ammonium peroxodisulfate as a by-component, to synthesize PANI/PSS ( For example, refer to Fabrication of Water-Dispersible Polyaniline-Poly (4-styrenesulfonate) Nanoparticles For Inkjet-Printed Chemical-Sensor Applications Jang, J.; Ha, J.; Cho, J. (2007), Advanced Materials vol. 19 (13 ) p.1772-1775.).

The mass of the nanoparticles relative to the electrochromic organic polymer is preferably 0.01% or more and 25% or less, preferably 0.1% or more and 5% or less. If the mass ratio of the nanoparticles to the electrochromic organic polymer is 0.01% or more and 25% or less, it is easy to visually recognize the color change of the gas-induced color light element.

[Nanoparticles]

The material constituting the nanoparticles is not particularly limited as long as it functions as a catalyst for the redox reaction of the electrochromic organic polymer, and examples thereof include palladium, palladium alloy, and platinum (platinum). For the platinum alloy or the like, two or more of them may be used at the same time.

In the case of nanoparticles, the catalytic ability can be greatly improved as compared with general particles by an increase in the surface area of the nano-sized particles accompanying the particle diameter.

The average particle diameter of the nanoparticles is preferably 1 nm or more and 100 nm or less.

Preferably, the nanoparticles form a protective layer on the surface.

The protective layer preferably contains a water-soluble polymer.

The water-soluble polymer is not particularly limited, and examples thereof include polyvinylpyrrolidone (PVP) and polyhydric alcohol.

The method for synthesizing the nanoparticles is not particularly limited, and examples thereof include a chemical reduction method. Solution method or the like (for example, refer to Synthesis of monodisperse Au, Pt, Pd, Ru and Ir nanoparticles in ethylene glycol, Bonet, F; Delmas, V; Grugeon, S; Herrera Urbina, R; Silver, PY et al. (1999) , Nanostructured Materials vol. 11 (8) p. 1277-1284.).

For example, in a reaction vessel at 150 ° C, an aqueous solution of a platinum-containing metal compound as a main component and an ethylene glycol solution of a water-soluble polymer as a material constituting the protective layer can be reacted. Synthesis of nano platinum particles.

Gas-induced color-changing optical element (PANI/PSS-) coated with nano-platinum particles on the surface of polyaniline/poly(styrene sulfonic acid) (PANI/PSS) In the case of Pt), it can be changed from green to colorless after being exposed to a hydrogen-containing atmosphere.

In addition, nanometers are deposited on the surface of poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonic acid) (PEDOT/PSS). In the case of a gas-induced color-changing optical element (PEDOT/PSS-Pt) of platinum particles, it can be changed from colorless to blue after being exposed to a hydrogen-containing ambient gas.

[gas-induced color light component]

FIG. 3 shows a gas-induced color light glass 10 as an example of the gas-induced color light member of the present embodiment.

In the gas-induced color light glass 10, the gas-induced color light element film 2 including the gas-induced color light element 1 is formed on the glass substrate 3.

The film thickness of the gas-induced color tone photosensor film 2 is preferably 10 nm or more and 1000 μm or less. When the film thickness of the gas-induced color light element film 2 is 10 nm or more and 1000 μm or less, the color change of the gas-induced color light element film 2 can be easily visually recognized.

The gas-induced color tone photosensor film 2 can be formed by a wet coating method. According to this, even the gas-induced color tone photosensor film 2 having a large surface area can be formed at a high speed. Further, since it is not necessary to use an expensive vacuum device or the like, the gas-induced color tone light glass 10 can be manufactured at a very low cost as compared with the case of using an inorganic material or a 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 dropping method.

In addition, the solvent in the coating film can be removed to form the gas-induced color light element film 2, or the gas-induced color light element film 2 can be formed without removing the solvent in the coating film.

The material constituting the glass substrate 3 is not particularly limited as long as it can transmit visible light, and examples thereof include oxides such as quartz, sapphire, and lithium niobate.

Instead of the glass substrate 3, a transparent substrate such as a plastic substrate can also be used.

The material constituting the plastic substrate is not particularly limited as long as it can transmit visible light, and examples thereof include polyethylene terephthalate (PET) and acrylic resin.

As the plastic substrate, a cellophane tape can also be used.

The shape of the transparent substrate is not particularly limited, and examples thereof include a plate shape and a sheet shape.

[multilayer glass]

Fig. 4 shows an example of the multilayer glass of the present embodiment.

In the case of the multilayer glass, the gas-induced color light element film 2 can be formed between the two glass substrates 3 and 4, and the opening portion can be sealed by the sealing member 5.

In the gas filling chamber S, argon gas is preliminarily sealed, and hydrogen gas, oxygen gas or air is supplied and vented by the ambient gas controller 60. For example, the ambient gas controller 60 can power the water Hydrogen or oxygen is supplied to the gas filling chamber S, and hydrogen or oxygen can be discharged from the gas filling chamber S using a vacuum pump.

After the hydrogen gas is supplied into the gas filling chamber S, the gas-induced color tone photosensor film 2 can be reduced and the color can be changed. For example, the gas-induced color tone photosensor film 2 including the electrochromic organic polymer colored by oxidation can be made colorless after supplying hydrogen gas. On the other hand, the gas-induced color tone photosensor film 2 including the electrochromic organic polymer colored by reduction can be colored after hydrogen gas is supplied.

Further, after supplying oxygen or air into the gas filling chamber S, the gas-induced color tone photosensor film 2 can be oxidized and can be changed to the original state.

Therefore, by controlling the ambient gas in the gas filling chamber S by the ambient gas controller 60, the gas-induced color tone photosensor film 2 can be reversibly controlled between the reduced state and the oxidized state. Further, after the supply and exhaust of the ambient gas controller 60 is interrupted (stopped), the reduced state or the oxidized state can be maintained. According to this, a multilayer glass which can be dimmed by a gas-chromic method can be obtained.

At present, the multi-layer glass of residential houses is becoming more and more popular, and in the newly built houses, the use of multi-layer glass is becoming the mainstream. By arranging the gas-induced color light element inside the multilayer glass, the internal space can be used as the gas filling chamber S for switching.

Further, the gas-induced color tone photosensor film 2 in the reduced state can be returned to the oxidized state at a high speed after supplying ozone (O ₃ ) instead of oxygen or air.

[Examples]

(Example 1)

<Synthesis of PANI/PSS>

1.0 ml of 97.0% pure aniline (C ₆ H ₅ NH ₂ ), 2.0 g of poly(poly)(styrene sulfonic acid) (PSS), 30 ml of 1.0 M hydrochloric acid (HCl) was mixed for 3 hours while stirring, thereby obtaining a mixed solution.

5.0 ml of 0.5 M ammonium peroxodisulfate ((NH ₄ ) ₂ S ₂ O ₈ ) (APS) aqueous solution and mixed solution were mixed while stirring, and about 1 at room temperature After an hour of reaction, a green PANI/PSS precipitate formed. Next, after performing telecentric separation at a speed of 15,000 rpm, water washing was performed three times, thereby recovering PANI/PSS.

PANI/PSS can be changed to green after oxidation, and can be changed to a colorless electrochromic organic polymer after reduction.

The synthetic chemical reaction formula of PANI/PSS is shown below.

[6]

<Synthesis of nano-platinum particles>

For 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 (ethylene) The glycol solution was mixed while stirring, and then reacted at a temperature of 150 ° C for 2 hours to obtain a dispersion of nano platinum particles. At this time, the liquid before the reaction was pale yellow, however, after the formation of the nano-platinum particles, the liquid changed to a rich brown color. The average particle diameter of the nano platinum particles was measured using a particle size distribution analyzer Photal ELSZ-1000 (manufactured by Otsuka Electronics Co., Ltd.), and it was 1.5 nm.

The synthetic chemical reaction formula of the nanoplatinum particles is shown below.

2(CH ₂ OH) ₂ → 2CH ₃ CHO+2H ₂ O. . . (1)

2CH ₃ CHO+Pt ⁴⁺ +5OH ^- +H ₂ O → CH ₃ COO ^- +6H ₂ O+Pt‧‧‧(2)

<Production of gas-induced color light element>

The dispersion of 1.0 g of PANI/PSS, 50 ml of water, and 3 ml of nanoplatinum particles was mixed while stirring for 3 hours. Next, after performing telecentric separation at a speed of 15,000 rpm, water washing was performed three times, thereby recovering a gas-induced color light element (PANI/PSS-Pt) to which nano-platinum particles were applied on the surface of PANI/PSS. According to the calculation of the raw materials, the mass ratio of the nano platinum particles to the PANI/PSS was 0.5%.

The FT-IR spectrum of PANI/PSS-Pt was measured using a FT-IR apparatus Frontier transform near-infrared/mid-infrared/far-infrared spectroscopic analyzer (manufactured by Perkinelmer Japan Co., Ltd.).

Figure 5 shows the FT-IR spectrum of PANI/PSS-Pt.

Seen from FIG. 5, the absorption peak was observed due to the PANI / PSS-Pt a ^{(668cm -1, 1031cm -1, 1004cm} -1, 1154cm -1, 1121cm -1, 1303cm -1, 2857cm -1, 2930cm -1, 3343cm ^-1 ).

Table 1 shows the assignment of absorption peaks due to PANI/PSS-Pt.

<Production of gas-induced color light glass>

In the case of <Preparation of gas-induced color light element>, PANI/PSS-Pt was not recovered, but it was diluted with water, thereby obtaining an aqueous dispersion of PANI/PSS-Pt of 10% by mass.

200 μl of PANI/PSS-Pt water-dispersed droplets were coated on a 3 cm × 3 cm quartz glass substrate to form a gas-induced color light element (PA) with a film thickness of 5 μm. NI/PSS-Pt) film, thereby obtaining a gas-induced color light glass. The PANI/PSS-Pt film is a green uniform film.

<Electrochemical characteristics of gas-induced color light elements>

200 μl of PANI/PSS-Pt water-dispersed droplets were applied onto an ITO film of a 3 cm × 3 cm glass substrate with an ITO film, thereby forming a gas-induced color light element (PANI/PSS) having a film thickness of 5 μm. -Pt) film. In a three-electrode cell in which a PANI/PSS-Pt film is used as a working electrode, a silver-nitric acid silver electrode is used as a reference electrode, and a platinum wire is used as a counter electrode, 0.1 M tetra-n-butyl perchloric acid is used. Ammonium (tetrabutylammonium perchlorate) (TBA ⁺ ClO ₄ ^- ) and 10 mM hydrochloric acid were used as electrolytes, and CV was carried out in a propylene carbonate solution. The PANI/PSS-Pt film is insoluble in propylene carbonate.

Figure 6 shows a cyclic voltammogram of a PANI/PSS-Pt film.

As can be seen from Fig. 6, the waveform is a surface sorption wave, suggesting that the PANI/PSS-Pt film can be stably present in a propylene carbonate solution. In addition, the oxidation peak potential was present at -0.2 V vs Ag/AgNO ₃ , +0.2 V vs Ag/AgNO ₃ , +0.8 V vs Ag/AgNO ₃ . On the other hand, the reduction peak potential was present at -0.3 V vs Ag/AgNO ₃ , 0.0 V vs Ag/AgNO ₃ , +0.5 V vs Ag/AgNO ₃ . These are all attributed to the redox pair of PANI/PSS.

From the above, the reduction peak potential of the PANI/PSS-Pt film was present at -0.6 V vs Ag/AgNO ₃ or higher, and the oxidation peak potential was present at +0.3 V v s Ag/AgNO ₃ or less.

<Light transmission characteristics of multilayer glass>

The optical state of the multilayer glass having the gas-induced color light glass and the glass substrate and the light transmittance in the reduced state were measured using the optical device shown in FIG. 7 .

The optical device is composed of a light source 70 and a spectrophotometer 80, and the gas-induced color light element film 2 of the gas-induced color light glass 10 is opposed to the glass substrate 4 between the light source 70 and the spectrophotometer 80. After the arrangement was performed, the opening was sealed by the sealing member 5, whereby the light transmittance of the multilayer glass was measured. At this time, in order to supply and exhaust the gas to the gas filling chamber S, the feeder 60 is also provided.

Fig. 8 shows the transmission spectrum of the multilayer glass.

Here, the transmission spectra in the oxidized state and the reduced state were each measured by using an ambient gas having a content of air and hydrogen of 4% (hereinafter referred to as "hydrogen atmosphere gas") to the gas at room temperature. After the filling chamber S was supplied with air for 5 minutes, it was measured at room temperature.

At this time, a quartz glass substrate was used as the glass base material 4. Further, U-4100 (manufactured by Hitachi, Ltd.) was used as the spectrophotometer 80, and USB 4000 (manufactured by Ocean Optics Co., Ltd.) was used as a detector.

As is apparent from Fig. 8, the transmittance of light having a wavelength of 700 nm in the oxidized state and the reduced state of the multilayer glass greatly changed, so that it has high-performance gas-chromic properties.

Next, after supplying gas to the gas filling chamber S for 60 seconds, the supply of the hydrogen ambient gas was stopped for 70 minutes. Here, after the supply of the hydrogen ambient gas is stopped, the air can flow into the gas filling chamber S from the opening. Repeat 6 times as a cycle (cycle) The supply of hydrogen gas is controlled by the transmittance of light having a wavelength of 700 nm per second. In addition, in the supply control of the second to sixth hydrogen atmosphere gases, the time for stopping the supply of the hydrogen ambient gas was 10 minutes.

Fig. 9 shows the relationship between the change in the ambient gas of the gas filling chamber S and the change in the light transmittance. As can be seen from Fig. 9, in the gas supply control of the first hydrogen atmosphere gas, the transmittance of light having a wavelength of 700 nm was changed from 58% to 5.9%. Further, it is also known that in the second to sixth hydrogen supply gas supply control, the transmittance of light having a wavelength of 700 nm is changed from 43.2% to 16.8%.

On the other hand, in the case of the multi-layer glass which was reduced by the hydrogen atmosphere gas and became colorless, the ozone generator SoecV350 (manufactured by Maluko Co., Ltd.) was used, and the output of ozone was 35 mg/h and the air volume was 5 L/min. After the gas is supplied to the gas filling chamber S for 5 minutes, it can be oxidized and returned to green. For this reason, the light transmittance of the multilayer glass can be switched at high speed.

Next, after supplying air to the gas filling chamber S for 2 minutes, the gas was supplied to the ozone for 5 minutes. The supply control of the hydrogen atmosphere gas and ozone, which is one cycle (cycle), was repeatedly performed, and the transmittance of light having a wavelength of 700 nm per second was measured therebetween.

Fig. 10 shows the relationship between the change in the ambient gas of the gas filling chamber S and the change in the light transmittance. As can be seen from Fig. 10, in the gas supply control of the hydrogen atmosphere gas and ozone, the transmittance of light having a wavelength of 700 nm was changed from 64.2% to 0.8%. For this reason, the time required for switching the light transmittance of the multilayer glass is greatly reduced, and the amount of change in the light transmittance of the multilayer glass is also increased.

(Examples 2 to 6)

<Production of gas-induced color light element>

The gaschromic color was produced in the same manner as in Example 1 except that the mass ratio of the nanoplatinum particles to the PANI/PSS was changed to 0.1%, 1.0%, 2.0%, 10%, and 25%, respectively. Dimming element.

<Production of gas-induced color light glass>

The gaschromic color was produced in the same manner as in Example 1 except that the mass ratio of the nanoplatinum particles to the PANI/PSS was changed to 0.1%, 1.0%, 2.0%, 10%, and 25%, respectively. Dimming glass.

<Light transmission characteristics of multilayer glass>

After supplying hydrogen gas to the gas filling chamber S for 2 minutes, ozone was supplied for 5 minutes. The supply of hydrogen ambient gas and ozone, which is one cycle (cycle), was repeated 10 times, and the transmittance of light having a wavelength of 700 nm per second was measured therebetween. As a result, in the multilayer glass of Examples 2 to 6, the average values of the changes in the transmittance of light having a wavelength of 700 nm were 62.5%, 62.2%, 61.5%, and 40.3, respectively. %, which shows that it has high-performance gas-chromic properties.

(Example 7)

<Synthesis of PEDOT/PSS>

2.0 ml of 3,4-ethylene dioxythiophene (EDOT; C ₆ H ₆ O ₂ S) having a purity of 97.0%, 1.0 g of PSS, and 30 ml of water were stirred while stirring. The mixture was mixed for 3 hours, thereby obtaining a mixed solution.

10.0 ml of an aqueous solution and a mixed solution of 0.5 M ammonium peroxodisulfate ((N H ₄ ) ₂ S ₂ O ₈ ) were mixed while stirring, and about 3 at room temperature. After an hour of reaction, a pale blue PEDOT/PSS precipitate formed. Next, the telecentric separation was carried out at a speed of 5000 rpm, and water washing was performed three times, thereby recovering PEDOT/PSS (for example, refer to PEDOT/PSS: synthesis, characterization, properties and applications, Louwet, F.; Groenendaal, L.; Dhaen, J.; Manca, J.; Van Luppen, J. et al. (2003), Synthetic Metals vol. 135 p. 115-117.).

PEDOT/PSS is an electrochromic organic polymer which can be changed to colorless after oxidation and which can be changed to blue after reduction.

The chemical structure of PEDOT/PSS is shown below.

<Production of gas-induced color light element>

The dispersion of 1.0 g of PEDOT/PSS, 50 ml of water, and 3 ml of nanoplatinum particles was mixed while stirring for 3 hours. Next, the telecentric separation was performed at a rate of 15,000 rpm, and water washing was performed three times, thereby recovering a gas-induced color light element (PEDOT/PSS-Pt) to which nano-platinum particles were applied on the surface of PEDOT/PSS. Based on the calculation of the raw materials, the mass ratio of the nano platinum particles to the PEDOT/PSS was 0.5%.

Figure 11 shows the FT-IR spectrum of PEDOT/PSS-Pt.

Seen from FIG. 11, an absorption peak was observed due to the PEDOT / PSS-Pt a ^{(686cm -1, 840cm -1, 924cm} -1, 971cm -1, 996cm -1, 1094cm -1, 1134cm -1, 1075cm -1, ^{1240cm -1, 1413cm -1, 1533cm -1} ).

Table 2 shows the assignment of absorption peaks due to PEDOT/PSS-Pt.

〔Table 2〕

<Production of gas-induced color light glass>

In the case of <Preparation of a gas-induced color light element>, PEDOT/PSS-Pt was not recovered, but diluted with water, thereby obtaining an aqueous dispersion of PEDOT/PSS-Pt of 10% by mass.

150 μl of PEDOT/PSS-Pt water-dispersed droplets were coated on a 3 cm × 3 cm quartz glass substrate to form a gas-induced color light element (PEDOT/PSS-Pt) film having a film thickness of 3 μm, thereby obtaining gas. Tonal color light glass. The PEDOT/PSS-Pt film is a light blue uniform film.

<Electrochemical characteristics of gas-induced color light elements>

150 μl of a water-dispersed PEDOT/PSS-Pt droplet was applied onto an ITO film of a 3 cm × 3 cm glass with an ITO film to form a gas-induced color light element (PEDOT/PSS-Pt) having a film thickness of 5 μm. membrane. CV was carried out in the same manner as in Example 1 except that the PEDOT/PSS-Pt film was used as the working electrode. PED The OT/PSS-Pt film is insoluble in propylene carbonate.

Figure 12 shows a cyclic voltammogram of a PEDOT/PSS-Pt film.

Figure 12 suggests that the waveform is a surface sorption wave and the PEDOT/PSS-Pt film can be stably present in a propylene carbonate solution. In addition, the oxidation peak potential was present at 0.0 V vs Ag/AgNO ₃ , +0.3 V vs Ag/AgNO ₃ , +1.0 V vs Ag/AgNO ₃ . On the other hand, the reduction peak potential exists at -0.6 V vs Ag/AgNO ₃ . These are all attributed to the redox couple of PEDOT/PSS-Pt.

From the above, it is understood that in the PEDOT/PSS-Pt film, the reduction peak potential exists at -0.6 V vs Ag/AgNO ₃ or more, and the oxidation peak potential exists at +0.3 V vs Ag/AgNO ₃ or less.

<Light transmission characteristics of multilayer glass>

The light transmittance in the oxidized state and the reduced state of the multilayered glass was measured in the same manner as in Example 1 except that the obtained gas-induced color light glass was used.

Figure 13 shows the transmission spectrum of the multilayer glass.

As is apparent from Fig. 13, the multilayer glass has a gas-transmissive property in the oxidized state and the reduced state, and thus has a gasotropic property.

(Comparative Example 1)

<Production of dimming element>

A light control element was produced in the same manner as in Example 1 except that the mass ratio of the nano platinum particles to PANI/PSS was changed to 0%.

<Production of dimming glass>

A light control glass was produced in the same manner as in Example 1 except that the mass ratio of the nano platinum particles to PANI/PSS was changed to 0%.

<Light transmission characteristics of multilayer glass>

The light transmittance in the oxidized state and the reduced state of the multilayered glass was measured in the same manner as in Example 1 except that the light-adjusting glass was used instead of the gas-induced color light glass.

In the case of the multilayer glass, the mass ratio of the nano-platinum particles to the PANI/PSS is 0%. Therefore, even if air or hydrogen ambient gas is supplied to the gas filling chamber S, the redox reaction occurring is not sufficient, and it is not recognized. The change in color. From this, it is understood that the multilayer glass does not have gasotropic properties.

(Comparative Example 2)

<Production of dimming element>

A light control element was produced in the same manner as in Example 7 except that the mass ratio of the nano platinum particles to PEDOT/PSS was changed to 0%.

<Production of dimming glass>

The preparation of the light-adjusting glass was carried out in the same manner as in Example 7 except that the mass ratio of the nano-platinum particles to the nano-platinum particles of PEDOT/PSS was changed to 0%.

<Light transmission characteristics of multilayer glass>

The light transmittance in the oxidized state and the reduced state of the multilayered glass was measured in the same manner as in Example 1 except that the light-adjusting glass was used instead of the gas-induced color light glass.

In the case of the multilayer glass, the mass ratio of the nano-platinum particles to the PEDOT/PSS is 0%. Therefore, although the air or hydrogen ambient gas is supplied to the gas filling chamber S, the redox reaction occurring is not sufficient, and it is not recognized. The change in color. It can be seen that the multi-layer glass does not have Gasotropic properties.

(Comparative Example 3)

Synthesis of <Fe(II)-2(bis)(tripyridine) hybrid polymer >

For an equimolar (mol) amount of ligand, 2 (bis) (tripyridine), and iron acetate Fe(OAc) 2, by bubbling for a long time by argon gas The CH ₃ COOH (1 mg of the ligand, about 1 mL of CH ₃ COOH) from which oxygen or the like was removed was refluxed for 24 hours. The reaction solution was cooled to room temperature, and a small amount of insoluble residue was removed by filtration. After the filtrate was transferred to a petri dish, CH ₃ COOH was slowly evaporated to dry. The crisp film remaining on the culture dish was collected and dried overnight in a vacuum, thereby obtaining a Fe(II)-2(bis) (tripyridine) mixed polymer (for example, referring to Electrochromic Organic- Metallic Hybrid Polymers: Fundamentals and Device Applications, Higuchi, Masayoshi (2009), The Society of Polymer Science, Japan vol. 41 (7) p. 511-520.).

The Fe(II)-2(bis) (terpyridine) mixed polymer is an electrochromic mixed polymer which becomes colorless after oxidation and which becomes purple after reduction.

The synthetic chemical reaction formula of Fe(II)-2(bis) (terpyridine) mixed polymer is shown below.

〔化8〕

<Production of dimming element>

A dispersion of 100 mg of Fe(II)-2(bis) (terpyridine) mixed polymer, 20 ml of methanol, and 2 ml of nanoplatinum particles was mixed while stirring for 3 hours. Next, the telecentricity is performed at a speed of 15000 rpm. Immersed and washed with methanol for 3 times, thereby modulating the nano-platinum particles on the surface of the Fe(II)-2(bis) (terpyridine) mixed polymer (Fe(II) -2 (bis) (tripyridine) mixed polymer - Pt) was recovered. Based on the calculation of the raw materials, the mass ratio of the nano platinum particles to the Fe(II)-2(bis) (tripyridine) mixed polymer was 0.5%.

<Production of dimming glass>

In the <production of the dimming element>, the Fe(II)-2(bis) (terpyridine) mixed polymer Pt was not recovered, but diluted with methanol, thereby obtaining Fe(II)- 2 (bis) (terpyridine) mixed polymer - Pt was 1.0 mass% of a methanol dispersion.

100 μl of Fe(II)-2(bis) (terpyridine) mixed polymer-Pt methanol dispersion was sprayed onto a 3 cm × 3 cm quartz glass substrate to form a dimming element having a film thickness of 250 nm ( Fe(II)-2(bis) (tripyridine) mixed polymer) film, thereby obtaining a dimming glass. The Fe(II)-2(bis) (tripyridine) mixed polymer film is a purple uniform film.

<Electrochemical Characteristics of Dimming Element>

100 μl of Fe(II)-2(bis) (terpyridine) mixed polymer-Pt methanol dispersion was sprayed onto an ITO film of a 3 cm × 3 cm glass substrate with an ITO film to form a film. A 5 μm thick dimming element (Fe(II)-2(bis) (tripyridine) mixed polymer-Pt) film. In addition to the Fe(II)-2(bis) (terpyridine) mixed polymer-Pt membrane as the working electrode, 0.1 M tetrabutylammonium perchlorate (TBA ⁺ ClO _{4 )} ^- CV was carried out in the same manner as in Example 1 except that CV was carried out as an electrolyte in an acetonitrile solution. Fe(II)-2(bis) (terpyridine) mixed polymer-Pt film is insoluble in acetonitrile.

Figure 14 shows a cyclic voltammogram of a Fe(II)-2(bis) (tripyridine) mixed polymer-Pt film.

Figure 14 suggests that the waveform is a surface sorption wave, and the Fe(II)-2(bis) (tripyridine) mixed polymer-Pt film can be stably present in an acetonitrile solution. In addition, the oxidation peak potential was present at +0.8 V vs Ag/AgNO ₃ and the reduction peak potential was present at +0.75 V vs Ag/AgNO ₃ . These are all attributed to the redox couple of the Fe(II)-2(bis) (terpyridine) mixed polymer.

From the above, in the Fe(II)-2(bis) (terpyridine) mixed polymer-Pt film, the reduction peak potential exists above -0.6 V vs Ag/AgNO ₃ , and the oxidation peak potential Does not exist below +0.3V vs Ag/AgNO ₃ .

<Light transmission characteristics of multilayer glass>

The light transmittance in the oxidized state and the reduced state of the multilayered glass was measured in the same manner as in Example 1 except that the light-adjusting glass was used instead of the gas-induced color light glass.

In the case of a multilayer glass, there is a dimming glass in which a Fe(II)-2(bis) (terpyridine) mixed polymer-Pt film is formed, so that even if an air or hydrogen environment is supplied to the gas filling chamber S The gas, the redox reaction that occurs is not sufficient, and the change in color cannot be recognized. From this, it is understood that the multilayer glass does not have gasotropic properties.

[Industrial use possibilities]

As described above, the present embodiment relates to a gas-induced color light element in which nanoparticles are coated on the surface of an electrochromic organic polymer having gasotropic properties, and a gas in which a film including a gas-induced color light element is formed. The tone-changing optical member and the multilayer glass can be produced by using the electrochromic organic polymer in the present embodiment.

Further, in the dimming element of the present embodiment, the electrochromic organic polymer is inexpensive, and only a very small amount of expensive nanoparticles are used, so that it can be produced at low cost.

In addition, the dimming element of the present embodiment has chromaticity compared with an inorganic material, can be produced by a simple process, and has a simple structure, so that a gas-chromic property with superior performance and low price can be realized. Dimming elements, gas-induced color light components, and multiple layers of glass.

This embodiment is useful as a window material technique for controlling the solar transmittance of a building or a vehicle.

The present application claims the priority of Japanese Patent Application No. 2016-091233, filed on Apr. 28, 2016, the entire content of

Claims (11)

A gas-induced color-changing optical element capable of reversibly changing light transmittance by an oxidation-reduction reaction with an ambient gas, characterized in that it comprises: an electrochromic organic polymer; and nanoparticles, Acting as a catalyst for the redox reaction of the electrochromic organic polymer, wherein the reduction peak potential exists at -0.6 V vs Ag/AgNO ₃ or more, and the oxidation peak potential exists at +0.3 V vs Ag/AgNO ₃ the following. The gas-induced color light element according to claim 1 of the patent application, characterized in that the electrochromic organic polymer has a general formula (wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 20 or less carbon atoms, and an alkoxy group having 1 or more and 20 or less carbon atoms. a constituent unit represented by a group having an alkyl group having 1 or more and 20 or less carbon atoms, an aryl group, an amino group which may have a substituent group or a cyano group, and a general formula (wherein R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 20 or less carbon atoms, an alkoxy group having 1 or more and 20 or less carbon atoms, and the number of carbon atoms is A constituent unit or a general formula represented by an alkyl ester group, an aryl group, an amino group which may have a substituent group or a cyano group of 1 or more and 20 or less (wherein R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 20 or less carbon atoms, an alkoxy group having 1 or more and 20 or less carbon atoms, and the number of carbon atoms is a constituent unit represented by an alkyl ester group, an aryl group, an amino group which may have a substituent group or a cyano group of 1 or more and 20 or less, and a general formula [Chemical Formula 4] (wherein R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 20 or less carbon atoms, an alkoxy group having 1 or more and 20 or less carbon atoms, or carbon; a constituent unit represented by an alkyl ester group having 1 to 20 atoms and 20 or less alkyl group, an aryl group, an amino group which may have a substituent group, or a cyano group, and a general formula (wherein R ¹² and R ¹³ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 20 or less carbon atoms, an alkoxy group having 1 or more and 20 or less carbon atoms, and the number of carbon atoms is One or more selected from the group consisting of constituent units represented by an alkyl ester group of 1 or more and 20 or less, an aryl group, or an amino group which may have a substituent group or a cyano group. The gas-induced color light element according to claim 1, wherein the electrochromic organic polymer is derived from aniline, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene, A constituent unit of one or more selected monomers selected from the group consisting of pyrrole and thiophene. The gas-induced color light element according to the first aspect of the invention, characterized in that the nanoparticle comprises a group selected from the group consisting of palladium, palladium alloy, platinum, and platinum alloy. More than one. The gas-induced color light element according to the first aspect of the invention is characterized in that the mass ratio of the nanoparticles to the electrochromic organic polymer is 0.01% or more and 25% or less. A gas-induced color tone optical member characterized in that a film comprising the gas-induced color tone element of claim 1 is formed on a transparent substrate. The gas-induced color tone member according to claim 6 of the invention is characterized in that the film has a film thickness of 10 nm or more and 1000 μm or less. A gas-induced color tone member according to item 6 of the patent application, characterized in that the transparent substrate is a glass substrate or a plastic substrate. A multilayer glass comprising two or more glass substrates, and a film including the gas-induced color light element of the first aspect of the patent application is formed between two glass substrates. A multiple glazing according to the ninth aspect of the invention, characterized in that the glass substrate further has means for supplying and venting hydrogen, ozone, oxygen or air between the two glass substrates. A method of producing a gas-induced color tone optical element according to the first aspect of the invention, characterized in that the electrochromic organic polymer and the nanoparticles are mixed in a solvent.