JP2008040422A - All-solid-state reflective dimming electrochromic element, method for manufacturing the same, and dimming member and car component using the element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reflective dimming electrochromic element having superior responsiveness, even in a wide area and with improved durability, and to provide a member that uses the element. <P>SOLUTION: The reflective dimming electrochromic element comprises a transparent conductive film layer, a proton accumulating layer, a proton conductive electrolyte layer, a catalyst layer and a magnesium-nickel alloy layer, deposited, in this order, wherein at least a part of the magnesium-nickel alloy layer has an electrode fabricated directly for energizing from the outside of the element. The method for manufacturing the element and the applications for the element for architecture and vehicles are also provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an all-solid-state reflective dimming electrochromic element used for dimming glass capable of controlling the amount of sunlight transmitted, a manufacturing method thereof, a dimming member using the element, and a vehicle component.

  Generally, a window glass (opening) in a building is a place where large heat enters and leaves. For example, the rate at which heat flows away from the window during heating in winter is about 48%, and the rate at which heat enters from the window during cooling in summer reaches about 71%. Therefore, energy consumption can be effectively reduced if light and heat in and out of the window glass can be controlled. A light control glass having a light control function capable of controlling light and heat has been developed for such a purpose.

  Also, in automobiles, compared to buildings, the window glass is larger than the interior space, there is less room for people in the car to avoid solar radiation, and the transmittance must be kept above a certain level due to the requirement of ensuring visibility when driving. Therefore, there is a strong demand for controlling the flow of light and heat, especially the inflow. As is well known, the interior of a vehicle placed under hot weather becomes very hot. In an example of measuring the summer environment in Japan, in the case of parking, the temperature of the air in the vehicle reaches close to 70 ° C. At the same time, the temperature of the interior material in the vehicle rises close to 100 ° C. on the top surface of the instrument panel and close to 70 ° C. on the ceiling. Needless to say, there is no uncomfortable feeling when riding in such a situation, but the temperature of the interior material does not drop easily even after the ventilation or cooling device is activated, and the passenger continues to receive radiant heat for a long time, improving comfort. It is greatly damaged. The main cause of this rise in temperature is the intrusion of solar radiation into the vehicle. In automobiles, as with buildings, the advent of light control glass is desired.

  As such a light control glass, an electrochromic element using a light control material whose transmittance is reversibly changed by application of current and voltage is known. The electrochromic element and the light control glass using the same are considered suitable for the following reason. Since the electrochromic element can electrically control the transmission state of light and heat, it can set a state according to a person's intention and does not require energy to maintain a mirror shape that is a constant state.

  Most electrochromic light control elements known so far, including tungsten oxide, are based on the principle that light control is performed by absorbing light with a light control material constituting the element. That is, when the light control material absorbs light, the entrance of heat in the form of light can be suppressed. However, a light-modulating material that has heat by absorbing light has a drawback that the energy saving effect is reduced because the heat is released into the room. In order to eliminate this, it is necessary to perform light control not by light absorption but by light reflection. That is, there is a demand for a light-modulating material that reversibly changes between a mirror state and a transparent state, and an all-solid electrochromic device using the same.

  For example, Patent Document 1 discloses a layer of a rare earth hydride such as yttrium and lanthanum and magnesium, a transparent and proton conductive material, an oxide such as niobium oxide, vanadium oxide, and tantalum oxide, magnesium fluoride, A reflective dimming material consisting of a fluoride layer such as lead fluoride is described. An element made by combining this material with an anhydrous proton conductive solid electrolyte, a proton storage layer, a transparent conductive film (all of which are solid), and a glass sandwiched between two laminated glass plates It is disclosed. Layers of rare earth hydrides and magnesium such as yttrium and lanthanum, transparent and proton conductive materials, oxides such as niobium oxide, vanadium oxide and tantalum oxide, and layers of fluoride such as magnesium fluoride and lead fluoride Is continuously formed by a PVD method (vacuum deposition method, sputtering method).

  For example, Patent Document 2 proposes an optical switch element using magnesium nickel represented by MgNix (0.1 <x <0.3) as a reflective light control material. It is composed of a reflective light control material, a catalyst layer, a solid electrolyte layer, a proton accumulation layer, and a transparent conductive film layer. This element has a wiring connection portion for energizing the transparent conductive film layer, the magnesium and nickel layers from the outside. When the mirror shape is changed to transparent, protons are supplied from the proton accumulation layer, and electrons are supplied from the external wiring connected to the magnesium and nickel layers to the magnesium and nickel layers.

  In addition to the above two techniques, the following materials are known as materials that can be used for the reflective dimming element. Using these materials, it is possible to produce an all-solid reflective dimming element in which other materials are solid.

  For example, Non-Patent Document 1 describes rare earth hydrides such as yttrium and lanthanum, in which a transparent and mirror-like change occurs due to hydrogen storage and release. Since this material is also easily oxidized and deteriorated by oxygen and moisture, it is essential to cover a catalyst layer that can prevent the penetration of water and oxygen and permeate hydrogen.

  Furthermore, Patent Document 3 describes magnesium / nickel. This material also needs to be coated with a catalyst layer that can prevent the ingress of water and oxygen and can permeate hydrogen.

  The features of the above prior art are summarized as follows.

  Materials having reflection dimming characteristics include hydrides of rare earth metals such as yttrium and lanthanum (Patent Document 1), hydrides of rare earth metals and magnesium (Patent Document 1), and hydrides of magnesium and nickel (Patent Documents). 1 and 2) are known.

Since none of these materials has a high proton uptake rate, it is common to provide a catalyst layer that serves as a proton inlet / outlet. As described above, as the catalyst layer, a palladium layer (Non-patent Document 1, Patent Documents 2 and 3), an oxide such as niobium oxide, vanadium oxide, and tantalum oxide, or a fluoride such as magnesium fluoride and lead fluoride. A compound layer (Patent Document 1) may be mentioned.
JP 2000-204862 A JP-A-2005-274630 J. et al. N. Huberts, R.A. Griessen, J. et al. H. Rector, R.D. J. et al. Wijngaarden, J. et al. P. Dekker, D.M. G. de Groot, N.M. J. et al. Koeman, Nature, 380, 231 (1996) US 6647166 specification

  The present inventors consider that a magnesium / nickel alloy is suitable as a reflective dimming material, and palladium is suitable as a catalyst layer in view of the switching property between mirror and transparent, The glass using it was examined.

  All the materials were formed by a formation method in a vacuum atmosphere, a vacuum deposition method, a sputtering method, or an ion plating method. A tungsten oxide layer was formed as a proton storage layer in the presence of hydrogen on a glass substrate provided with a transparent conductive film layer, and then a tantalum oxide layer was formed as a solid electrolyte layer. Thereafter, a catalyst layer and a magnesium / nickel alloy layer were continuously formed to form an all-solid-state reflection dimming composition.

  The element needs to be energized for driving. External wiring necessary for energization was connected to the transparent conductive film layer and the magnesium / nickel alloy layer. This element has a problem that the time required to change from the mirror state in the vicinity of the electrode connected to the magnesium / nickel alloy layer to the transparent state is short, but the time required for the change increases as the distance from the electrode increases. It was difficult to apply to the area. Therefore, it has been desired to develop an element that can be applied over a wide area.

  The above phenomenon occurs because the movement speed of electrons supplied to the magnesium-nickel alloy layer is slower than the diffusion speed of protons. As a result of intensive studies, the present inventors have found that the cause is that the surface of the magnesium / nickel alloy layer that is not in contact with the catalyst layer is oxidized.

  Magnesium in the magnesium-nickel alloy layer easily reacts with oxygen in the air to form an oxide. The resulting oxide does not exhibit a reflective dimming function. Although this oxide layer is a very thin film, it is an insulator and hinders conduction between the magnesium / nickel alloy layer and the electrode. It also hinders the movement of electrons inside the magnesium / nickel alloy layer. This is one of the causes for reducing the responsiveness of the reflection light control element having a large area. Furthermore, the magnesium oxide layer absorbs moisture and carbon dioxide, and can cause oxidation and deterioration inside the magnesium / nickel alloy layer.

  This point will be described with reference to the drawings.

  FIG. 1 is a schematic diagram showing an example of a reflective dimming electrochromic element used by the present inventors for examination. In FIG. 1A, a reflective dimming electrochromic element 10 is formed in the order of a magnesium / nickel alloy layer 6, a catalyst layer 5, a proton conductive electrolyte layer 4, a proton storage layer 3, a transparent conductive film layer 2, and a substrate 1. . One end of the power supply 15 is connected to the magnesium / nickel alloy layer 6 via the electrode 7a, and the other end is connected to the transparent conductive film layer 2 via the electrode 7b. Here, the surface 6A of the magnesium / nickel alloy layer 6 not contacting the catalyst layer 5 is oxidized. In particular, the electrode 7a is connected to the magnesium / nickel alloy layer 6 through the magnesium oxide layer (FIG. 1B).

  Therefore, in order to improve the electrical conductivity between the electrode and the magnesium / nickel alloy layer, it is necessary to directly connect the electrode to the magnesium / nickel alloy layer. Furthermore, by forming the surface of the magnesium / nickel alloy layer with an antioxidant layer, it is possible to prevent the surface layer of the layer and the internal oxidation including the surface layer. The magnesium / nickel alloy layer is extremely thin, for example, up to about 100 nm. By preventing the magnesium in the magnesium / nickel alloy from being oxidized, the electrical conductivity in the layer is not impaired and good. It is possible to ensure high electrical conductivity.

  Therefore, an object of the present invention is to provide a reflective dimming electrochromic element having excellent responsiveness even in a large area and having improved durability, a manufacturing method thereof, and a member using the same.

  In the present invention, a transparent conductive film layer, a proton accumulation layer, a proton conductive electrolyte layer, a catalyst layer, and a magnesium / nickel alloy layer are laminated in this order, and at least a part of the magnesium / nickel alloy layer In addition, the present invention relates to a reflective dimming electrochromic device characterized by comprising an electrode for energizing from outside the directly formed device.

  Furthermore, the present invention provides the magnesium-nickel alloy layer when the transparent conductive film layer, the proton accumulation layer, the proton conductive electrolyte layer, the catalyst layer, the magnesium-nickel alloy layer, and the electrode layers are laminated in this order. And a method of manufacturing a reflective dimming electrochromic device, characterized in that the electrode is formed under a reduced pressure atmosphere.

  The present invention also includes a transparent conductive film layer, a proton accumulation layer, a proton conductive electrolyte layer, a catalyst layer, and a magnesium / nickel alloy layer in this order, and is not in contact with the catalyst layer. When directly forming an electrode and an antioxidant layer for energizing from outside the element on the surface of the alloy layer, the magnesium-nickel alloy layer, the electrode and the antioxidant layer are placed under a reduced pressure atmosphere. The present invention relates to a method of manufacturing a reflective dimming electrochromic element, characterized in that it is formed.

  According to the reflective dimming electrochromic device of the present invention, since the oxidation of magnesium in the magnesium-nickel alloy layer is prevented, the electrical conductivity between the electrodes is excellent, and the electron mobility inside the layer is also provided. Excellent light control with high response speed from mirror to transparent. Further, since no magnesium oxide is present, deterioration of the layer due to oxidation is suppressed.

  According to the manufacturing method of the reflective dimming electrochromic device of the present invention, oxidation of magnesium in the magnesium-nickel alloy layer can be prevented during the manufacturing process.

(Reflective dimming electrochromic element: Embodiment 1)
The reflective dimming electrochromic device of the present invention comprises a transparent conductive film layer, a proton accumulation layer, a proton conductive electrolyte layer, a catalyst layer, and a magnesium / nickel alloy layer laminated in this order. An electrode for energizing from the outside of the element is directly formed on the surface of the nickel-based alloy layer that is not in contact with the catalyst layer.

  In this specification, “directly forming” means forming or stacking without an oxide layer of a metal such as magnesium. This is because the presence of such an oxide layer hinders energization between the two layers. The presence of the oxide can be confirmed by an analysis method such as an EDX (energy dispersive X-ray fluorescence analyzer) method.

  The reflective dimming electrochromic device of the present invention will be described with reference to the drawings.

  FIG. 2 is a schematic view showing an example of the reflective dimming electrochromic element of the present invention. In FIG. 2, the reflective dimming electrochromic element 10 includes an electrode 7 a, a magnesium / nickel alloy layer 6, a catalyst layer 5, a proton conductive electrolyte layer 4, a proton accumulation layer 3, a transparent conductive film layer 2, and a substrate 1. Are stacked. In this case, the electrode 7a is made of a transparent conductive material, is directly formed on the magnesium / nickel-based alloy layer 6, and covers the whole.

  At that time, if necessary, a part of the surface of the transparent conductive film layer 2 on which the proton accumulation layer 3 is formed is left for installation of the sealing layer 8b and the electrode 7b. Furthermore, the side surface of the element 10 is preferably covered with a sealing layer 8 for preventing water and oxygen from entering from the end.

  One end of the external wiring from the power supply 15 is connected to the electrode 7a, and the other end is connected to the electrode 7b.

  The electrode used in Embodiment 1 of the present invention is not particularly limited as long as it also has the function of an antioxidant layer. When the electrode also serves as an antioxidant layer, the electrode is made of a transparent conductive material, and specifically, zinc oxide, indium tin oxide, tin oxide, or fluorine-doped tin oxide is preferably used.

  The thickness of this layer is not particularly limited as long as it is an electrode and can prevent oxidation of the magnesium-nickel alloy layer, but is usually in the range of 20 nm to 200 nm. The visible light transmittance of the electrode is usually 40% or more. In the first embodiment, the electrode can take the form of a transparent conductive film layer.

  The magnesium-nickel alloy layer used in Embodiment 1 is a material having a reflective dimming function that changes transparently by occluding hydrogen and conversely changes by releasing hydrogen. In this layer, the ratio (mass) of magnesium to nickel is preferably in the range of 0.1 to 0.3 nickel with respect to magnesium 1. This is the range in which the transmittance increases when the magnesium-nickel alloy layer becomes transparent due to occlusion of hydrogen. When it is out of the above range, the transmittance during occlusion of hydrogen decreases, which is not preferable.

  The thickness of the magnesium-nickel alloy layer is usually in the range of 20 to 200 nm. If it is less than 20 nm, the reflectivity when it is mirror-like is low, while if it exceeds 200 nm, the transmittance when transparent is low, which is undesirable for glass applications.

  For the magnesium / nickel alloy layer, for example, a sputtering method, a vacuum deposition method, an electron beam deposition method, a chemical vapor deposition method (CVD), or a plating method can be employed. Specifically, a vacuum deposition method, an ion plating method, or a sputtering method is preferable.

  The catalyst layer used in the first embodiment has a function of supplying protons to the magnesium / nickel alloy layer 6 and releasing them from the magnesium / nickel alloy layer. As a component of the catalyst layer, palladium or palladium-gold alloy is usually preferable because of its high hydrogen permeability. The thickness of the catalyst layer is usually in the range of 0.5 to 10 nm. If the thickness is less than 0.5 nm, the function as the catalyst cannot be sufficiently exhibited. Conversely, if the thickness exceeds 10 nm, the improvement of the function is not observed.

  The catalyst layer can employ, for example, a sputtering method, a vacuum deposition method, an electron beam deposition method, a chemical vapor deposition method (CVD), or a plating method. Specifically, a vacuum deposition method, an ion plating method, or a sputtering method is preferable.

  The proton conductive electrolyte layer 4 used in the first embodiment includes various materials such as liquid and solid, but it is desirable that the proton conductive electrolyte layer 4 be a solid material in consideration of being able to be used stably over a long period of time. As the solid material, an organic material, an inorganic material, or a mixture of both can be adopted. The proton electrolyte needs to be anhydrous. This is because the presence of moisture can cause oxidation and deterioration of the magnesium / nickel alloy layer. Specific examples include tantalum oxide and zirconium oxide. In addition, a polymer comprising a sulfonated polyether ketone can also be used.

  The proton accumulation layer 3 used in the first embodiment stores protons necessary for switching between the transparent state and the mirror shape of the magnesium / nickel alloy layer. Specific examples include tungsten oxide, molybdenum oxide, niobium oxide, vanadium oxide, and the like. Of these, tungsten oxide is particularly suitable. The thickness of the proton accumulation layer is usually in the range of 500 to 1,000 nm.

  The transparent conductive film layer 2 used in Embodiment 1 is made of a conductive material, and is used to control the reflectance by applying a voltage to the reflective dimming electrochromic element. A known material can be used as the material of the transparent conductive film. For example, indium-tin oxide, antimony-tin oxide or zinc oxide. Application of organic polymer materials is also possible. The surface resistance of the transparent conductive film layer is involved in the responsiveness of the electrochromic element, and its value is desirably low, and is preferably 50Ω / □ or less. In addition, in the case where a transparent conductive film layer is formed on a substrate, the higher the visible light transmittance, the better, and preferably 70% or more.

  The substrate 1 used in the first embodiment preferably has a function as a base for forming a member constituting the reflective dimming electrochromic element, and also has a function as a barrier that suppresses intrusion of water and oxygen. . The material for the substrate 1 is preferably glass or a resin film or sheet. In the case of a resin film or sheet, the magnesium / nickel-based alloy layer is formed under reduced pressure conditions, and therefore, one with less outgassing is preferable in terms of maintaining reduced pressure. Particularly suitable as the resin film or sheet include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), nylon, acrylic and the like from the viewpoints of price, transparency, heat resistance and the like. With respect to the substrate, it is more desirable to add a transparent conductive film layer in advance to the side on which the electrochromic element is formed, since this can be simplified from the viewpoint of the work process.

  The sealing layer 8 used in the first embodiment is preferably an organic material sealing material, for example, an epoxy resin. Moreover, it supplies with the dispenser to the said part.

  In the reflective dimming electrochromic device of the present invention, the magnesium / nickel alloy layer and the electrode are directly formed, and further, the electrode covers the magnesium / nickel alloy layer, so that it is electrically conductive. The effect is that the response speed from the mirror shape to the transparency is high.

(Manufacturing method of Embodiment 1)
The reflective dimming electrochromic device manufacturing method according to the present invention includes a transparent conductive film layer, a proton accumulation layer, a proton conductive electrolyte layer, a catalyst layer, a magnesium / nickel alloy layer, and an electrode layer in this order. The magnesium-nickel alloy layer and the electrode are formed under a reduced pressure atmosphere.

  Here, the “reduced atmosphere” is an atmosphere that is depressurized to a degree that can be formed by a known method such as vacuum vapor deposition and the magnesium / nickel alloy layer is not oxidized. There is no particular limitation.

  For example, when forming an electrode, a magnesium-nickel alloy layer, and a catalyst layer, the atmosphere is an argon gas atmosphere (including oxygen in the case of an electrode), and the degree of vacuum when forming these layers is, for example, The pressure is preferably 0.2 to 0.5 Pa, and 0.4 Pa is preferable when the catalyst layer is formed, and 0.2 Pa is preferable when the magnesium-nickel alloy layer is formed.

  By adopting such a method, oxidation of metals such as magnesium can be prevented during formation.

  Furthermore, in order to prevent oxidation, it is necessary to proceed continuously so as not to contact a gas containing oxygen such as air until the magnesium / nickel alloy layer is covered with an electrode.

  The manufacturing method of the reflection light control electrochromic element of this invention is demonstrated based on FIG. As a method of laminating each layer, a method known in this field can be adopted.

  The substrate 1 is made of PET on which a transparent conductive film layer 2 made of indium-tin oxide is formed in advance.

  Hereinafter, the method up to the formation of the electrode 7a is performed under reduced pressure using a vacuum apparatus unless otherwise specified. The substrate 1 is set in a vacuum apparatus. Reactive DC sputtering is performed in an atmosphere of argon and oxygen under a reduced pressure using metal tungsten as a target to form a tungsten oxide film on the transparent conductive film layer 2.

  After the formation, the substrate is taken out from the reduced-pressure atmosphere, and the tungsten oxide layer is subjected to protonation treatment in a 1N sulfuric acid solution to form the proton accumulation layer 3.

  Next, using a metallic tantalum as a target, reactive DC sputtering is performed under reduced pressure in an atmosphere of argon, oxygen, and hydrogen, and a tantalum oxide thin film is deposited on the proton storage layer to form a solid proton conductive electrolyte layer 4. Form.

Next, the catalyst layer 5 made of palladium, the magnesium / nickel alloy layer 6 made of Mg ₂ Ni, and the transparent conductive electrode 7a made of indium-tin oxide are successively formed in this order by sputtering. .

  On the substrate, a transparent conductive film layer, a proton accumulation layer, a proton conductive electrolyte layer, a catalyst layer, a magnesium / nickel alloy layer, and an electrode order (normal order) may be performed, or in reverse order. Also good. However, when performing in the reverse order, in addition to the conditions in the normal order, continuously between the magnesium / nickel alloy layer and the catalyst layer so as not to come into contact with oxygen such as air. is required.

  If necessary, the side surface of the element 10 is preferably covered with a sealing layer 8 for preventing water and oxygen from entering from the end.

  Next, one end of the external wiring with the power source 15 is attached to the electrode 7a, and the other end is attached to the electrode 7b using a known material such as silver paste.

  The reflective dimming electrochromic device of the present invention is obtained by the above method.

(Reflective dimming electrochromic element: Embodiment 2)
The reflective dimming electrochromic device of the present invention comprises a transparent conductive film layer, a proton accumulation layer, a proton conductive electrolyte layer, a catalyst layer, and a magnesium / nickel alloy layer laminated in this order. An electrode and an antioxidant layer are formed directly on the surface of the system alloy layer that is not in contact with the catalyst layer.

  FIG. 3 is a schematic view showing an example of the reflective dimming electrochromic element of the present invention.

  In FIG. 3, the reflective dimming electrochromic element 10 is formed in the order of a magnesium / nickel alloy layer 6, a catalyst layer 5, a proton conductive electrolyte layer 4, a proton accumulation layer 3, a transparent conductive film layer 2, and a substrate 1. . An electrode 7a and an antioxidant layer 11 are formed on the magnesium / nickel alloy layer 6, respectively.

  Furthermore, the side surface of the element 10 is preferably covered with a sealing layer 8 for preventing water and oxygen from entering from the end.

  One end of the external wiring from the power supply 15 is connected to the electrode 7a, and the other end is connected to a part on the right side of the transparent conductive film layer 2 secured in advance via the electrode 7b.

  In Embodiment 2, it is desirable to use a metal such as copper, silver, nickel, or tungsten, zinc oxide, indium tin oxide, tin oxide, or fluorine-doped tin oxide for the electrode 7a. By using metal, it is possible to supply a larger amount of power. The electrode 7b is made of a transparent conductive material. Specifically, it is desirable to use zinc oxide, indium tin oxide, tin oxide, or fluorine-doped tin oxide.

  The antioxidant layer used in the second embodiment is not particularly limited as long as it has a function of preventing oxidation of the magnesium / nickel alloy layer. Examples of the material for the antioxidant layer include magnesium fluoride, potassium fluoride, cerium fluoride, barium fluoride, resin, silicon monoxide, silicon dioxide, and aluminum oxide. As the resin, an olefin resin is more preferable. When silicon monoxide, silicon dioxide, or aluminum oxide is used, the oxide cannot be used as a material as it is. Therefore, after forming a layer in a metal state, the surface layer is made oxide by contacting with air.

  For example, a sputtering method, a vacuum evaporation method, an electron beam evaporation method, a chemical vapor deposition method (CVD), or a plating method can be employed for the antioxidant layer used in the second embodiment. Specifically, a vacuum deposition method, an ion plating method, or a sputtering method is preferable.

  The thickness of this layer is not particularly limited as long as it can prevent oxidation of the magnesium-nickel alloy layer, but is usually in the range of 20 nm to 200 nm. The visible light transmittance of the antioxidant layer is usually 40% or more.

  The same members or materials as those in Embodiment 1 can be used for other layers such as the transparent conductive film layer used in Embodiment 2.

(Manufacturing method of Embodiment 2)
The manufacturing method of the reflective dimming electrochromic device according to the present invention includes a transparent conductive film layer, a proton accumulation layer, a proton conductive electrolyte layer, a catalyst layer, and a magnesium / nickel alloy layer laminated in this order on a substrate. When forming an electrode and an antioxidant layer for energizing from the outside of the element directly on the surface of the magnesium / nickel alloy layer that is not in contact with the catalyst layer, the magnesium / nickel alloy layer, The antioxidant layer and the electrode are formed under a reduced pressure atmosphere.

  As a method of laminating each layer, a method known in this field can be adopted. During formation, the atmosphere is reduced. In particular, when forming the magnesium / nickel alloy layer, the electrode in contact with the magnesium / nickel alloy layer, and the antioxidant layer, it is essential to form them under a reduced pressure atmosphere. This is because it is possible to prevent oxidation of magnesium by forming under such conditions. Further, in order to prevent oxidation, it is necessary to proceed continuously so as not to contact a gas containing oxygen such as air until the magnesium / nickel alloy layer is covered with an antioxidant layer or the like.

  The manufacturing method of the reflection light control electrochromic element of this invention is demonstrated based on FIG.

  The substrate 1 is made of PET on which a transparent conductive film layer 2 made of indium-tin oxide is formed in advance.

  Hereinafter, unless otherwise specified, the method up to the electrode is performed under reduced pressure using a vacuum apparatus.

  The proton accumulation layer 3 and the proton conductive electrolyte layer 4 can be produced by the same method as described in the first embodiment.

  A catalyst layer 5 made of palladium is formed on the proton conductive electrolyte layer 4 by sputtering.

After the magnesium-nickel alloy layer 6 made of Mg ₂ Ni is formed by sputtering, the electrode 7a made of indium-tin oxide and the antioxidant layer 11 are continuously formed under reduced pressure by the magnesium-nickel alloy layer 6 respectively. Form on top. Masking is performed so that they do not overlap each other when the antioxidant layer 11 and the electrode 7a are formed. That is, when forming the antioxidant layer 11 for the first time, the portion of the electrode 7a is first masked, the antioxidant layer 11 is formed, and then the first masking is removed. Next, after the second masking on the antioxidant layer 11, the electrode 7a is formed, and then the second masking is removed.

  In this case, the masking employs a known method such as a printing mask.

  A transparent conductive film layer, a proton accumulation layer, a proton conductive electrolyte layer, a catalyst layer, a magnesium / nickel alloy layer, an antioxidant layer, or an electrode order (normal order) may be performed on the substrate, or in reverse order. May be formed. However, when performing in the reverse order, in addition to the conditions in the normal order, continuously between the magnesium / nickel alloy layer and the catalyst layer so as not to come into contact with oxygen such as air. is required. Of course, the order of forming the magnesium / nickel alloy layer and the antioxidant layer is not particularly limited.

  Furthermore, the side surface of the element 10 is preferably covered with a sealing layer 8 for preventing water and oxygen from entering from the end.

  One end of the external wiring from the power supply 15 is connected to the electrode 7a, and the other end is connected to the electrode 7b.

  The reflective dimming electrochromic device of the present invention is obtained by the above method.

(Reflective dimming electrochromic element: Embodiment 3)
The reflective dimming electrochromic device of the present invention comprises a transparent conductive film layer, a proton accumulation layer, a proton conductive electrolyte layer, and a catalyst layer, which are laminated in this order, and is formed on the proton conductive electrolyte layer of the catalyst layer. An insulating layer and an electrode for energizing from the outside of the element are laminated on a part of the non-contact surface, and a magnesium / nickel alloy layer is directly formed on the remaining part of the catalyst layer. An antioxidant layer is formed directly on at least a part of the surface of the nickel-based alloy layer that is not in contact with the catalyst layer and the surface of the electrode that is not in contact with the insulating layer. .

  The reflective dimming electrochromic device of the present invention will be described with reference to the drawings.

  FIG. 4 is a schematic view showing an example of the reflective dimming electrochromic element of the present invention. In FIG. 4, the reflective dimming electrochromic element 10 is laminated in the order of a catalyst layer 5, a proton conductive electrolyte layer 4, a proton accumulation layer 3, a transparent conductive film layer 2, and a substrate 1.

  An insulating layer 9 is formed on a part of the surface of the catalyst layer 5 where the proton conductive electrolyte layer 4 is not formed, and a magnesium / nickel alloy layer 6 is formed on the remaining part of the catalyst layer 5.

  The insulating layer used in Embodiment 3 is preferably a silicon nitride layer formed by a catalytic chemical vapor deposition method or an aluminum nitride layer formed by a sputtering method or an ion plating method.

  An electrode 7 a is formed on the surface of the insulating layer 9 that is not in contact with the catalyst layer 5.

  An antioxidant layer 11 is formed on a part of the surface of the electrode 7a that is not in contact with the insulating layer 9 and the surface of the magnesium / nickel alloy layer 6 that is not in contact with the catalyst layer 5.

  It is preferable to provide sealing layers 8a and 8b on the side surfaces of the element 10 for preventing water and oxygen from entering from the end portions.

  One end of the external wiring from the power supply 15 is connected to the electrode 7a, and the other end is connected to a part of the right side of the transparent conductive film layer 2 secured in advance via the electrode 7b.

  In Embodiment 3, the electrode 7a is made of a transparent conductive material, and it is desirable to use a metal such as copper, silver, nickel, or tungsten, zinc oxide, indium tin oxide, tin oxide, or fluorine-doped tin oxide. By using metal, it is possible to supply a larger amount of power. The electrode 7b is made of a transparent conductive material, and it is desirable to use zinc oxide, indium tin oxide, tin oxide, or fluorine-doped tin oxide.

  The same member or material as in Embodiment 2 can be used for a layer such as the transparent conductive film layer used in Embodiment 3.

  As another form, the insulating layer 9 is laminated not on the catalyst layer 5 but on a part of the proton conductive electrolyte layer 4, and further, an electrode 7 a is laminated on the insulating layer 9, and the proton The catalyst layer 5 and the magnesium / nickel alloy layer 6 may be stacked on the remaining portion of the conductive electrolyte layer 4, and the antioxidant layer 11 may be stacked thereon. In this case, it is necessary to design so that the catalyst layer 5 does not short-circuit with the electrode 7a.

(Manufacturing method of Embodiment 3)
In the method for producing a reflective dimming electrochromic device of the present invention, a transparent conductive film layer, a proton accumulation layer, a proton conductive electrolyte layer, and a catalyst layer are laminated in this order, and the proton conductive electrolyte layer of the catalyst layer An insulating layer and an electrode for energizing from the outside of the element are sequentially stacked on a part of the surface not in contact with the element. On the other hand, when the magnesium / nickel alloy layer and the antioxidant layer are sequentially laminated on the remaining portion of the catalyst layer that is not in contact with the proton conductive electrolyte layer, the magnesium / nickel alloy layer and the antioxidant The layer is formed under a reduced pressure atmosphere.

  As a method of laminating each layer, a method known in this field can be adopted. At the time of formation, the atmosphere is preferably reduced in pressure. In particular, when forming an antioxidant layer from a magnesium / nickel alloy layer, it is essential to perform the formation atmosphere under reduced pressure. This is because it is possible to prevent oxidation of magnesium by forming under such conditions.

  The manufacturing method of the reflection light control electrochromic element of this invention is demonstrated based on FIG.

  The substrate 1 is made of PET on which a transparent conductive film layer 2 made of indium-tin oxide is formed in advance.

  Hereinafter, the manufacturing method up to the electrodes is performed under reduced pressure using a vacuum apparatus unless otherwise specified.

  The proton accumulation layer 3, the proton conductive electrolyte layer 4, and the catalyst layer 5 can be manufactured by the same method as described in the first embodiment. At that time, if necessary, a part on the right side of the surface of the transparent conductive film layer 2 on which the proton accumulation layer 3 is formed is left for installation of the sealing layer 8b and the electrode 7b.

  Masking is used in the formation of the insulating layer 9. That is, when the insulating layer 9 is first formed, the portion of the catalyst layer 5 on which the magnesium-nickel alloy layer 6 is laminated is subjected to the third masking, and then the insulating layer 9 and the electrode 7a are sequentially laminated, and then the third layer Remove the masking. Next, fourth masking is performed on the insulating layer 9 and the electrode 7a to form the magnesium / nickel alloy layer 6, and then the fourth masking is removed. An antioxidant layer 11 is formed on a part of the surface of the electrode 7a that is not in contact with the insulating layer and the surface of the magnesium / nickel alloy layer that is not in contact with the catalyst layer 5.

  In this case, the masking employs a known method such as a printing mask.

  The manufacturing method may be formed in the reverse order. However, when performing in the reverse order, in addition to the conditions in the normal order, continuously between the magnesium / nickel alloy layer and the catalyst layer so as not to come into contact with oxygen such as air. is required.

  Both sides of the element 10 are preferably covered with sealing layers 8a and 8b for preventing water and oxygen from entering from the ends.

  One end of the external wiring of the power supply 15 is connected to the electrode 7a, and the other end is connected to the electrode 7b.

  The reflective dimming electrochromic device of the present invention is obtained by the above method.

(Light control member)
The present invention relates to a light control member using the reflection light control electrochromic element. Such a member can be used for a building member, a vehicle part or the like because of the function of the element.

  In an electrochromic element suitable for glass for buildings and automobiles, it is desirable that all of the material constituting the element is a solid such as tungsten oxide. An electrochromic element can be partially liquefied, but it is necessary to prevent leakage of the liquid. Buildings and automobiles are premised on long-term use, and it is possible to prevent leakage for a long time, but it is difficult in terms of cost.

(Vehicle parts)
The present invention relates to a vehicle component using the member. Such vehicle parts can be used as a window glass, a sunroof, an outer plate, and an interior for controlling the transmittance of sunlight in the vehicle.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by the Example.

(Example 1)
A reflective dimming electrochromic device shown in FIG. 2 was prepared.

  An indium-tin oxide layer, which is a transparent conductive film layer 2, is formed in advance on the substrate 1 and has a surface resistance of 10Ω / □. As the substrate 1, a glass plate having a thickness of 1 mm was used. After cleaning this, it was set in a vacuum apparatus and evacuated.

First, a tungsten oxide layer was formed by reactive DC sputtering in an argon and oxygen atmosphere using metallic tungsten as a target. The tungsten oxide layer was formed under the condition that the thickness was 1000 nm. After the formation, the sample was taken out from the reduced-pressure atmosphere, and the tungsten oxide layer was subjected to proton treatment in a 1N sulfuric acid aqueous solution to form a proton accumulation layer 3.
<Tungsten oxide formation conditions>
Formed by reactive DC sputtering method Target: Tungsten Ar: 50 sccm
O ₂ : 5 sccm
P _tot (total pressure): 0.9 Pa
Current control: 100 mA (fixed)
<Hydrogenation treatment of tungsten oxide>
Colored by immersing in 1N sulfuric acid aqueous solution Applied voltage: ± 3V up 0.05V / 2sec down 0.05V / 5sec
Next, a tantalum oxide thin film as the solid electrolyte layer 4 was deposited by reactive DC sputtering in a argon, oxygen, hydrogen atmosphere using a metal tantalum as a target. The thickness of the tantalum oxide thin film was 300 nm.
<Tantalum oxide formation conditions>
Formed by reactive DC sputtering method Target: Tantalum (metal)
Ar: 7 sccm
O ₂ : 1 sccm
H ₂ : 10 sccm
P _tot (total pressure): 0.2 Pa
Power: 60W
Furthermore, the formation of the catalyst layer 5 made of palladium, the magnesium / nickel alloy layer 6 made of Mg ₂ Ni, and the electrode 7a was successively performed in this order. A transparent conductive indium-tin oxide was formed on the magnesium / nickel alloy layer 6 as the electrode 7a to obtain a sample 1 of a reflective dimming electrochromic device.
<Palladium formation conditions>
Formed by DC sputtering method Target: Palladium P _tot (Total pressure): 0.4 Pa (Argon gas pressure)
Power: 40W
<Magnesium / nickel alloy layer>
Formed by DC sputtering method Target: Magnesium, nickel P _tot (total pressure): 0.2 Pa (argon gas pressure)
Power: 40W (magnesium), 8W (nickel)
<Indium-tin oxide layer (electrode) formation conditions>
Film formation by DC magnetron sputtering method Target: Indium-tin oxide sintered body (tin oxide 5 mass%)
Ar: 50 sccm
O ₂ : 5 sccm
P _tot (total pressure): 0.5 Pa
Power: About 2kW
The thicknesses of the catalyst layer 5, the magnesium / nickel alloy layer 6 and the electrode 7a were 4, 40 and 150 nm, respectively.
A sealing layer was applied to the side surface of the obtained reflective dimming electrochromic element, and wiring from the power source was further performed.

(Example 2)
In Example 1, a sample 2 of a reflective dimming electrochromic device having the configuration of FIG. 3 was obtained by replacing a part of the electrode 7a with an antioxidant layer 11 made of insulating magnesium fluoride. The electrode 7a was formed by applying Ni paste. Thickness is 100 nm.

(Example 3)
In Example 2, instead of magnesium fluoride as the antioxidant layer 11, metal aluminum was formed on the magnesium / nickel alloy layer 6 by sputtering so that alumina was formed, and then the film was released to the atmosphere and oxidized. In the same manner, Sample 3 of the reflective dimming electrochromic device was obtained.

Example 4
In Example 2, a sample 4 of a reflective dimming electrochromic device was obtained in the same manner except that polypropylene was deposited on the magnesium / nickel alloy layer instead of magnesium fluoride as the antioxidant layer 11. It was.

(Example 5)
A reflective dimming electrochromic device shown in FIG. 4 was prepared.

In Example 1, after forming the solid electrolyte layer 4, the catalyst layer 5, the insulating layer 9 made of Al · N, and the electrode 7 a made of nickel were provided, and then the magnesium / nickel alloy layer 6 made of Mg ₂ Ni and the transparent layer The anti-oxidation layer 11 was provided to obtain a sample 5 of a reflective dimming electrochromic device.
<Insulating layer deposition conditions>
Sputtering method Pressure: 4 Pa (N ₂ + Ar gas)
Target: AL (aluminum)
(Comparative Example 1)
In Example 1, a sample A of a reflective dimming electrochromic element was prepared in the same manner except that an electrode composed of an indium-tin oxide layer was not provided.

(Evaluation of the rate of change from mirror to transparent)
Samples 1 to 5 and A were wired and driven at a voltage of 7.5 V, and the rate of change from mirror-like to transparent was examined.

  For the change in light transmittance, a measurement system combining a semiconductor laser having a wavelength of 670 nm and a silicon photodiode was used. Between the semiconductor laser and the silicon photodiode, the sample was placed with the substrate surface of the sample on the silicon photodiode side and the antioxidant layer on the semiconductor laser side (see FIG. 5). The transmittance and reflectance at a wavelength of 670 nm were measured every 10 seconds, and the change with time was examined. The reflectance was measured from the side close to the magnesium / nickel alloy layer.

  The time until the transmittance became 1% to 50% was examined. The results are shown in Table 1.

  From Table 1, it was confirmed that the performance of Samples 1 to 5 was significantly improved with respect to Sample A.

  Further, the magnesium / nickel alloy layers of Sample 1 and Sample A were analyzed by EDX. As a result, in Sample 1, it was confirmed that the entire layer was in a metal state, and in Sample A, the presence of an oxide was confirmed.

It is a schematic diagram which shows an example of the conventional reflective dimming electrochromic element. 1B is an enlarged view of a circled portion in FIG. 1A. It is a schematic diagram which shows an example of the reflection light control electrochromic element of this invention. It is a schematic diagram which shows another example of the reflection light control electrochromic element of this invention. It is a schematic diagram which shows the other example of the reflection light control electrochromic element of this invention. It is drawing which shows arrangement | positioning of the apparatus and sample for measuring evaluation of the change speed from mirror shape to transparent.

Explanation of symbols

1 substrate,
2 transparent conductive film,
3 proton storage layer,
4 solid electrolyte layer,
5 catalyst layer,
6 Magnesium-nickel alloy layer,
7 electrodes,
8 Sealing layer,
9 Insulating layer,
10 All-solid-state reflective dimmer,
11 Transparent antioxidant layer,
12 External wiring,
15 power supply,
6A Interface of magnesium / nickel alloy layer.

Claims (12)

  A transparent conductive film layer, a proton accumulation layer, a proton conductive electrolyte layer, a catalyst layer, and a magnesium / nickel alloy layer are laminated in this order, and directly on at least a part of the magnesium / nickel alloy layer. A reflective dimming electrochromic device comprising an electrode for energizing from outside the device formed on the substrate.   2. The reflective dimming electrochromic device according to claim 1, wherein a part of the magnesium-nickel alloy layer on which the electrode is formed is a surface not in contact with the catalyst layer. A part of the magnesium-nickel alloy layer on which the electrode is formed is an interlayer between the catalyst layer and the magnesium-nickel alloy layer,
The reflective dimming electrochromic device according to claim 1, wherein an insulating layer is formed between the electrode and the catalyst layer.   The reflection control according to any one of claims 1 to 3, further comprising an antioxidant layer directly formed on a surface portion of the magnesium-nickel alloy layer on which the electrode is not formed. Photoelectrochromic device.   The antioxidant layer includes zinc oxide, indium tin oxide, tin oxide, fluorine-doped tin oxide, magnesium fluoride, potassium fluoride, cerium fluoride, barium fluoride, resin, silicon monoxide, silicon dioxide and aluminum oxide. The reflective dimming electrochromic device according to claim 4, comprising at least one selected from the group consisting of:   The reflective dimming electrochromic device according to claim 1, wherein the electrode includes at least one selected from the group consisting of a transparent conductive material and a metal.   The reflective dimming electrochromic device according to claim 4, wherein the transparent conductive material includes at least one selected from the group consisting of zinc oxide, indium tin oxide, and tin oxide fluorine-doped tin oxide. . When laminating each layer of the transparent conductive film layer, proton accumulation layer, proton conductive electrolyte layer, catalyst layer, magnesium / nickel alloy layer and electrode in this order,
A method for producing a reflective dimming electrochromic element, wherein the magnesium / nickel alloy layer and the electrode are formed under a reduced pressure atmosphere. A transparent conductive film layer, a proton accumulation layer, a proton conductive electrolyte layer, a catalyst layer and a magnesium / nickel alloy layer are laminated in this order, and on the surface of the magnesium / nickel alloy layer not in contact with the catalyst layer, When forming the electrode and antioxidant layer directly,
A method for producing a reflective dimming electrochromic element, wherein the magnesium / nickel alloy layer, the electrode, and the antioxidant layer are formed under a reduced pressure atmosphere.   The said formation is a manufacturing method of Claim 8 or 9 performed by the method of any one of vacuum evaporation, ion plating, or sputtering.   The light control member characterized by including the said reflection light control electrochromic element of any one of Claims 1-7.   A vehicle component using the light control member according to claim 11.

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