Laminated structure and method for manufacturing laminated structure

Abstract

This laminated structure includes a first glass substrate, a first layer, a second layer, and a second glass substrate. The first layer includes one or more selected from tungsten oxide represented by the general formula WO3-x (0 ≤ x ≤ 0.28), silicon oxynitride represented by the general formula SiOaNb, and aluminum oxide. The second layer includes tungsten bronze. The first layer, the second layer, and the second glass substrate are arranged in the stated order from the position closest to the first glass substrate.

Description

Jointed structure, method for manufacturing a joined structure

[0001] This invention relates to a composite structure and a method for manufacturing a composite structure.

[0002] Sunlight entering through openings such as windows and doors in roofs and walls of various buildings, automobiles, railway cars, aircraft, and ships contains not only visible light but also ultraviolet and infrared rays. Of the infrared rays contained in sunlight, near-infrared rays with wavelengths of 800 nm to 2500 nm are called heat rays, and when they enter a room through openings such as windows, they cause the room temperature to rise. In order to reduce the rise in room temperature caused by heat rays, there has been a surge in demand in recent years for heat-shielding films that have a heat-shielding function that blocks heat rays while allowing sufficient visible light to enter, thereby reducing the rise in room temperature while maintaining brightness, and are used as components for windows of various buildings and vehicles, arcades, ceiling domes, carports, etc.

[0003] Therefore, various studies have been conducted on heat-shielding films.

[0004] For example, Patent Document 1 contains the general formula Cs ｘ W ｙ O ｚ A near-infrared shielding film is disclosed, which is composed of a continuous film of cesium composite tungsten oxide represented by (4.8 ≤ x ≤ 14.6, 20.0 ≤ y ≤ 26.7, 62.2 ≤ z ≤ 71.4, x + y + z = 100), wherein the continuous film includes one or more selected from orthorhombic, rhombohedral, and hexagonal crystal structures.

[0005] Japanese Patent Application Publication No. 2022-038474

[0006] Incidentally, when a heat-shielding film is formed by depositing tungsten bronze on a glass substrate, the haze of the heat-shielding film and the laminated structure containing the heat-shielding film sometimes becomes high. For use in window materials and the like, a laminated structure with low haze is required.

[0007] One aspect of the present invention aims to provide a composite structure with low haze.

[0008] A composite structure according to one aspect of the present invention comprises a first glass substrate, a first layer, a second layer, and a second glass substrate, wherein the first layer is of the general formula WO ３－ｘ Tungsten oxide represented by (0 ≤ x ≤ 0.28), general formula SiO ａ N ｂ The material comprises silicon oxynitride and one or more selected from aluminum oxide, the second layer comprises tungsten bronze, and the first layer, the second layer, and the second glass substrate are arranged in that order from the position closest to the first glass substrate.

[0009] According to one aspect of the present invention, a low-haze composite structure can be provided.

[0010] Figure 1 is an explanatory diagram of a jointed structure according to one aspect of the present disclosure. Figure 2 is an explanatory diagram of a jointed structure according to another aspect of the present disclosure. Figure 3 is an explanatory diagram of a jointed structure according to another aspect of the present disclosure. Figure 4 is a flowchart of a method for manufacturing a jointed structure according to one aspect of the present disclosure.

[0011] The embodiments for carrying out the present invention will be described below with reference to the drawings, but the present invention is not limited to the embodiments described below, and various modifications and substitutions can be made to the embodiments described below without departing from the scope of the present invention. [Jointed Structure] Figures 1 to 3 show explanatory diagrams of the jointed structure of this embodiment. Figures 1 to 3 are cross-sectional views of the jointed structure of this embodiment in a plane along the lamination direction of the first and second layers. Figures 2 and 3 represent other configuration examples of the jointed structure of this embodiment, so the explanation will mainly use Figure 1, and use Figures 2 and 3 as necessary.

[0012] In this specification, the names of components may be prefixed with "1st," "2nd," etc., such as "1st layer" and "2nd layer." However, this is merely to identify the component being described and to avoid confusion, and does not indicate its arrangement, priority, or anything of the sort.

[0013] A laminated structure refers to a structure having a heat-shielding film between two glass substrates. The heat-shielding film is a film that reduces transmittance in at least a portion of the wavelength range in the infrared region. Of the two glass substrates, at least one of them may be organic glass or organic-inorganic glass, as described in the section on the second glass substrate.

[0014] As shown in Figure 1, the composite structure 10 of this embodiment includes a first glass substrate 11, a first layer 12, a second layer 13, and a second glass substrate 15. Furthermore, the layers can be arranged in the order of the first layer 12, the second layer 13, and the second glass substrate 15, starting from a position close to the first glass substrate 11.

[0015] The layers of the composite structure of this embodiment will now be described. (1) Regarding each layer (1-1) First glass substrate The first glass substrate 11 is a substrate that supports the first layer 12, the second layer 13, and the second glass substrate 15.

[0016] The type of glass contained in the first glass substrate 11 is not particularly limited, and any glass can be used. The glass contained in the first glass substrate 11 may be one or more types selected from, for example, soda glass, soda-lime glass, borosilicate glass, aluminosilicate glass, chemically strengthened glass, alkali-free glass, etc. Examples of chemically strengthened glass include alkali aluminosilicate glass containing alkali metal oxides and soda glass containing alkali metal oxides.

[0017] The average thickness T11 of the first glass substrate 11 is not particularly limited, but may be, for example, 0.5 mm or more and 50.0 mm or less, or 0.5 mm or more and 1.0 mm or less. (1-2) First layer The inventors of the present invention investigated the cause of high haze in a laminated structure in which a tungsten bronze film is placed on a glass substrate.

[0018] As a result of the study, it was confirmed that in the laminated structure with high haze, a new phase that seems to be formed by the reaction between the components contained in the tungsten bronze and the components contained in the glass substrate was generated. Therefore, it was inferred that the reason for the high haze in the laminated structure was that when forming the tungsten bronze film, etc., the components contained in the glass substrate moved and reacted to generate a new compound phase.

[0019] Based on the mechanism of high haze in the above conventional laminated structure, the inventor of the present invention conducted further studies. As a result, by disposing a first layer 12 that can reduce the movement of components from the first glass substrate 11 to the second layer 13 between the first glass substrate 11 and the second layer 13 containing tungsten bronze, it was found that a laminated structure 10 with reduced haze can be formed, and the present invention was completed.

[0020] Therefore, in the laminated structure 10 of the present embodiment, a first layer 12 can be provided between the first glass substrate 11 and the second layer 13. That is, in this case, the first layer 12 is disposed in proximity to the surface of the first glass substrate 11. Particularly in the present embodiment, the first layer 12 is disposed on the side closer to the first glass substrate 11 than the second layer 13. And the first layer 12 contains one or more selected from tungsten oxide represented by the general formula WO ３－ｘ (0 ≤ x ≤ 0.28), silicon oxynitride represented by the general formula SiO ａ N ｂ and aluminum oxide. One or more compounds selected from tungsten oxide represented by the general formula WO ３－ｘ (0 ≤ x ≤ 0.28), silicon oxynitride represented by the general formula SiO ａ N ｂ and aluminum oxide may be contained in the first layer 12 as a film containing the selected compound. Hereinafter, tungsten oxide represented by the general formula WO ３－ｘ (0 ≤ x ≤ 0.28), silicon oxynitride represented by the general formula SiO ａ N ｂThe silicon oxynitride represented by these terms may also be simply referred to as tungsten oxide and silicon oxynitride, respectively. (1-2-1) Regarding the composition of the first layer, the glass used in the glass substrate contains additives to control various properties of the glass, such as the glass transition temperature. According to the inventors' research, elements such as additives contained in the glass mainly used in the glass substrate, such as Group 1 elements like alkali metals and Group 2 elements like alkaline earth metals, react with tungsten bronze to produce a different phase.

[0021] Therefore, in this embodiment, the laminated structure 10 reduces the movement of elements such as additives contained in the glass from the first glass substrate 11 to the second layer 13 by arranging the first layer 12 between the first glass substrate 11 and the second layer 13, preventing them from reaching the second layer 13. As a result, it is possible to prevent the formation of different phases in the second layer 13 and the increase in haze of the laminated structure.

[0022] The first layer 12 is, as described above, the general formula WO ３－ｘ Tungsten oxide represented by (0 ≤ x ≤ 0.28), general formula SiO ａ N ｂ Silicon oxynitride and aluminum oxide (Al ２ O ３ It may contain one or more selected from the following. The first layer 12 may also consist of only one or more selected from tungsten oxide, silicon oxynitride, and aluminum oxide, but this does not exclude the inclusion of unavoidable impurities introduced during the manufacturing process.

[0023] Furthermore, the first layer 12 may also contain a continuous film. In this case, the continuous film may contain one or more selected from tungsten oxide, silicon oxynitride, and aluminum oxide. (Tungsten oxide) Tungsten oxide readily reacts with elements such as alkali metals and alkaline earth metals contained in the glass to form composite tungsten oxide, which is tungsten bronze. For tungsten oxide, it is WO2 in stoichiometric ratio. ３ In that case it is a transparent inert film, but when reduced it becomes WO ３－ｘBecause it has the property of absorbing and reflecting infrared rays when it is incorporated into the composition, it can exert the effect of reducing the infrared transmittance in the composite structure. Tungsten oxide has a monoclinic or tetragonal crystal structure, and because it is crystallized, it incorporates elements derived from additives such as alkali metals and alkaline earth metals contained in the glass into the gaps without changing the crystal structure, and does not cause distortion in the surroundings and increase haze. For this reason, when the first layer 12 contains tungsten oxide, it is preferable that at least a portion of the tungsten oxide contained in the first layer 12 is crystallized. The presence of crystallized tungsten oxide in the first layer 12 can be confirmed, for example, by measuring the X-ray diffraction pattern, which shows the occurrence of a diffraction peak corresponding to tungsten oxide.

[0024] Furthermore, tungsten oxide itself, when x (which indicates the amount of oxygen deficiency) is greater than 0, can generate a sufficient amount of free electrons to enhance the absorption and reflection properties in the near-infrared region, thereby contributing to the effect of reducing infrared transmittance in composite structures.

[0025] General formula for tungsten oxide: WO ３－ｘ It is preferable that x satisfies the condition 0 ≤ x ≤ 0.28.

[0026] As described above, when the first layer 12 contains tungsten oxide, the tungsten oxide can incorporate elements derived from alkali metals and alkaline earth metals contained in the glass into the voids to form a composite tungsten oxide.

[0027] Therefore, when the first layer 12 contains tungsten oxide, the composite structure of this embodiment shows in the X-ray diffraction pattern the tungsten oxide phase and M ｘ１ WO ｚ１ It is preferable to be able to identify the phase and the tungsten bronze phase.

[0028] The tungsten oxide phase is due to the tungsten oxide contained in the first layer 12. ｘ１ WO ｚ１ The phase is formed by the reaction of tungsten oxide with alkali metals and alkaline earth metals contained in the glass. Therefore, M ｘ１ WOｚ１ The phase element M is one or more elements selected from alkali metals and alkaline earth metals, and x1 can satisfy 0.01 ≤ x1 < 1. z1 is not particularly limited, but for example, it may satisfy 2.5 ≤ z1 ≤ 3.0.

[0029] Alkali metal elements include Li (lithium), Na (sodium), K (potassium), rubidium (Rb), cesium (Cs), and Fr (francium).

[0030] Alkaline earth metal elements refer to alkaline earth metal elements in a broad sense, and include Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), and Ra (radium).

[0031] The tungsten bronze phase is due to the tungsten bronze contained in the second layer.

[0032] When the first layer 12 contains tungsten oxide, the composite structure of this embodiment, in its X-ray diffraction pattern, shows the tungsten oxide phase and M as phases originating from the first layer 12 and the second layer 13. ｘ１ WO ｚ１ It may consist only of the phase and the tungsten bronze phase. (Silicon oxynitride, aluminum oxide) Silicon oxynitride and aluminum oxide have the function of preventing components in the glass used in the first glass substrate 11 from moving to the second layer 13.

[0033] The general formula for silicon oxynitride is SiO₂ ａ N ｂ In the expression, it is preferable that a and b satisfy 0 ≤ a ≤ 2 and 0 ≤ b ≤ 1.33. (1-2-2) Structure of the first layer As shown in Figure 1, the first layer 12 of the composite structure 10 of this embodiment can also be composed of a single film. In this case, the first layer 12 may contain one or more films selected from, for example, a tungsten oxide film, a silicon oxynitride film, and an aluminum oxide film.

[0034] As shown in Figure 2, the first layer 12 of the composite structure 20 of this embodiment may have a first film 121 containing one or more selected from, for example, silicon oxynitride or aluminum oxide, and a second film 122 containing tungsten oxide. In Figure 2, the first film 121 and the second film 122 are arranged in order from a position close to the first glass substrate 11, but the embodiment is not limited to this configuration. The second film 122 and the first film 121 may be arranged in order from a position close to the first glass substrate 11. In addition, the first film 121 and the second film 122 may be arranged alternately or continuously so that there are two or more layers of each. (1-2-3) Average film thickness of the first layer The average film thickness T12 of the first layer 12 is not particularly limited, but for example, the average film thickness of the first layer 12 may be 5 nm or more and 1200 nm or less, 10 nm or more and 1200 nm or less, or 30 nm or more and 600 nm or less.

[0035] By setting the average film thickness of the first layer 12 to 5 nm or more, the amount of components contained in the first glass substrate 11 that reach the second layer 13 can be particularly reduced. Therefore, the haze of the composite structure 10 in this embodiment can be particularly reduced.

[0036] By making the average film thickness of the first layer 12 1200 nm or less, the coloration of the first layer 12 and the composite structure 10 can be reduced, and the visible light transmittance can be increased. Also, by making the average film thickness of the first layer 12 1200 nm or less, the time required to form the first layer 12 can be shortened, and the productivity during the manufacturing of the composite structure 10 can be increased. (1-3) Second layer (1-3-1) Composition of the second layer The second layer 13 contains tungsten bronze. The tungsten bronze contained in the second layer 13 may be incorporated into the second layer 13 as a tungsten bronze film.

[0037] The second layer 13 is, for example, general formula A ｘ２ W ｙ２ O ｚ２ It may contain tungsten bronze (composite tungsten oxide) represented by general formula A. ｘ２ W ｙ２ O ｚ２It is also possible to construct it solely from tungsten bronze, but even in this case, it does not eliminate the possibility of unavoidable impurities being introduced during the manufacturing process.

[0038] In the above general formula, it is preferable that x², y², and z² satisfy the following conditions: 0.05 ≤ x² / y² ≤ 0.5 and 2.5 ≤ z² / y² ≤ 3.0.

[0039] Element A may contain one or more alkali metal elements selected from K (potassium), Rb (rubidium), and Cs (cesium). Some of the alkali metal elements contained in element A may be substituted with one or more elements selected from Na (sodium), Tl (thallium), In (indium), Li (lithium), Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), Al (aluminum), and Ga (gallium).

[0040] In other words, element A includes one or more alkali metal elements selected from K, Rb, and Cs, and may further include one or more selected from Na, Tl, In, Li, Be, Mg, Ca, Sr, Ba, Al, and Ga as needed. (1-3-2) Regarding the crystal structure, the tungsten bronze contained in the second layer 13, by containing element A and oxygen vacancies, can generate a sufficient amount of free electrons to enhance the absorption and reflection characteristics in the near-infrared region. Therefore, the tungsten bronze contained in the second layer 13 can also contribute to the effect of reducing infrared transmittance in the composite structure. The crystal structure of tungsten bronze is not particularly limited and can have one or more crystal structures selected from, for example, tetragonal, monoclinic, cubic, hexagonal, and pseudohexagonal. Pseudohexagonal refers to a structure that deviates from perfect hexagonal symmetry due to defects in the prism plane or basal plane of the hexagonal crystal. In addition, tungsten bronze may contain amorphous parts.

[0041] The absorption position of infrared light tends to change depending on the crystal structure of tungsten bronze. This absorption position shifts to longer wavelengths for tetragonal and monoclinic crystals compared to cubic crystals, and further to longer wavelengths for hexagonal crystals. In addition, in conjunction with this variation in absorption position, hexagonal crystals absorb the least visible light, followed by tetragonal and monoclinic crystals, while cubic crystals absorb the most visible light among these. Therefore, for applications that transmit more visible light and block more infrared light, it is preferable to use tungsten bronze with a hexagonal crystal structure. For this reason, the tungsten bronze contained in the second layer 13 may have, for example, a hexagonal crystal structure. (1-3-3) Regarding film thickness, the average film thickness T13 of the second layer 13 is not particularly limited, but for example, the average film thickness T13 of the second layer 13 may be 5 nm or more and 1200 nm or less, 10 nm or more and 1200 nm or less, or 30 nm or more and 600 nm or less.

[0042] By setting the average film thickness T13 of the second layer 13 to 5 nm or more, the infrared transmittance of the composite structure 10 can be particularly reduced, resulting in a composite structure with particularly excellent heat shielding properties.

[0043] By setting the average film thickness T12 of the second layer 13 to 1200 nm or less, the coloration of the second layer 13 and the composite structure 10 can be reduced, and the visible light transmittance can be increased. In addition, by setting the average film thickness T12 of the second layer 13 to 1200 nm or less, the time required to form the second layer 13 can be shortened, thereby increasing the productivity during the manufacturing of the composite structure 10.

[0044] The laminated structure of this embodiment may have a first glass substrate, a first layer, a second layer, and a second glass substrate. The laminated structure of this embodiment may also have any additional layers as needed. A third layer and a protective layer, which the laminated structure of this embodiment may optionally have, will be described below. The laminated structure of this embodiment may further have only one of any third layer and a protective layer, or it may further have both the third layer and the protective layer. Also, the laminated structure of this embodiment may not have both the third layer and the protective layer. (1-4) Third layer (1-4-1) Regarding the configuration of the third layer, the second glass substrate 15 may be placed directly on the second layer 13, or the third layer 14 may be placed between the second layer 13 and the second glass substrate 15.

[0045] The third layer 14 may be a layer on which spacers or the like are placed, so that the distance between the second layer 13 and the second glass substrate 15 remains constant. Furthermore, if spacers or the like are placed in the third layer 14, the third layer 14 may be a region enclosed in a vacuum or a predetermined gas.

[0046] By placing a third layer 14, such as a vacuum, between the second glass substrate 15 and the first glass substrate 11, the thermal conductivity can be reduced and the heat insulation performance can be improved.

[0047] The third layer 14 may contain one or more resins selected from polyvinyl acetal resin, vinyl acetate copolymer, and ionomer resin.

[0048] The third layer 14 contains one or more resins selected from polyvinyl acetal resin, vinyl acetate copolymer, and ionomer resin, which allows the second glass substrate 15 to be fixed to the second layer 13 and the protective layer 16. The third layer 14 may also contain ultraviolet absorbing materials in addition to the above resins. By containing ultraviolet absorbing materials in the third layer 14, the wavelength range of light transmitted by the laminated structure 10 can be further controlled. (1-4-2) Film thickness The average film thickness T14 of the third layer 14 is not particularly limited, but for example, the average film thickness T14 of the third layer 14 may be 0.1 mm or more and 10.0 mm or less, 0.2 mm or more and 5.0 mm or less, or 0.3 mm or more and 1.0 mm or less. (1-5) Protective layer Figure 3 shows a laminated structure 30, which is another example of the configuration of this embodiment. The laminated structure of this embodiment may further have a protective layer 16 laminated on the second layer 13, as shown in the laminated structure 30 in Figure 3. When the laminated structure 30 has a protective layer 16, as shown in Figure 3, the layers can be stacked in the following order from the position closest to the first glass substrate 11: first layer 12, second layer 13, protective layer 16, and second glass substrate 15. Alternatively, as shown in Figure 3, a third layer 14 can be placed between the protective layer 16 and the second glass substrate 15.

[0049] The protective layer 16 may be directly laminated on the second layer 13, or there may be any layer between the second layer 13 and the protective layer 16.

[0050] The presence of a protective layer 16 in the composite structure 30 protects the composite structure 30 from the outside world and prevents damage. Depending on the application of the composite structure 30, the protective layer 16 may also have a function to improve optical properties such as visible light transmittance and infrared region reflectance by adjusting the refractive index. There may be multiple protective layers 16.

[0051] The material contained in the protective layer 16 is not particularly limited and can be selected according to the application of the composite structure 30 and the optical properties required for the composite structure 30. For example, the protective layer 16 may be SiO ２ , TiO ２ WO ３ , Nb ２ O ５ Al ２O ３ , ZrO ２ Ta ２ O ５ , SnO ２ Si ３ N ４ LaB ６ It may contain one or more compounds selected from the group of TiN compounds.

[0052] For example, SiO ２ Yes, Nb ２ O ５ Because these materials have high transparency and high dielectric constant, it is preferable to use them as the material for the protective layer 16 when the composite structure 30 is used in optical devices, displays, electronic devices, etc. For example, ZrO ２ Yes, Si ３ N ４ Al ２ O ３ For example, when the composite structure 30 is used in a device that requires mechanical strength and heat resistance, it is preferable to use it as the material for the protective layer 16. ２ Yes, LaB ６ It is preferable to use the laminated structure 30 as the material for the protective layer 16 when it is used in applications where transparency, chemical stability, and high conductivity are required. (1-6) Second glass substrate The laminated structure 10 of this embodiment may further have a second glass substrate 15 laminated on the second layer 13.

[0053] A third layer 14 or a protective layer 16 can also be placed between the second layer 13 and the second glass substrate 15.

[0054] The second glass substrate 15 may be made of the same glass materials as described for the first glass substrate 11. Furthermore, the second glass substrate 15 may be organic glass, or an inorganic-organic glass.

[0055] As the organic glass, one or more resins selected from, for example, acrylic resin, polycarbonate resin, polyurethane resin, and polyimide resin can be used.

[0056] As inorganic or organic glass, one or more types selected from, for example, polymethyl methacrylate, polycarbonate, soda-lime glass, borosilicate glass, and quartz glass can be used.

[0057] The average thickness T15 of the second glass substrate 15 is not particularly limited, but may be, for example, 0.5 mm or more and 50.0 mm or less, or 0.5 mm or more and 1.0 mm or less. (2) Physical properties, etc. The physical properties of the laminated structure of this embodiment are not particularly limited, but it is preferable that they satisfy the characteristics described below, for example. (2-1) Haze The haze of the laminated structure of this embodiment is preferably 6.0% or less, and more preferably 0.01% or more and 6.0% or less.

[0058] By reducing the haze of the composite structure of this embodiment to 6.0% or less, particularly clear transparency can be obtained, thereby improving visibility when used in openings such as window materials.

[0059] The productivity of the composite structure can be increased by setting the haze of the composite structure of this embodiment to 0.01% or more. (2-2) Visible light transmittance The visible light transmittance of the composite structure of this embodiment is preferably 20% or more and 90% or less, and more preferably 50% or more and 90% or less.

[0060] By setting the visible light transmittance of the laminated structure of this embodiment to 20% or more, visibility through the laminated structure of this embodiment can be improved when used in openings such as window materials. Furthermore, by setting the visible light transmittance of the laminated structure of this embodiment to 90% or less, the first layer 12 and the second layer 13 can be made to a sufficient thickness, and the heat shielding ability of the laminated structure of this embodiment can be particularly enhanced. (2-3) Solar radiation transmittance The solar radiation transmittance of the laminated structure of this embodiment is preferably 50% or less, and more preferably 10% or more and 50% or less.

[0061] By setting the solar transmittance of the laminated structure of this embodiment to 50% or less, the temperature rise on the indoor side can be sufficiently reduced when used in openings such as window materials. By setting the solar transmittance of the laminated structure of this embodiment to 10% or more, the productivity of the laminated structure can be increased. [Method for Manufacturing the Laminated Structure] Next, an example of the method for manufacturing the laminated structure of this embodiment will be described. According to the method for manufacturing the laminated structure of this embodiment, a laminated structure according to one aspect of the present disclosure can be manufactured. For this reason, some explanations of matters already described will be omitted. Note that the method for manufacturing the laminated structure according to one aspect of the present disclosure is not limited to the method for manufacturing the laminated structure described below.

[0062] The manufacturing method of the composite structure of this embodiment may include a first layer formation step, a second layer formation step, and a second glass substrate installation step.

[0063] Then, in the first layer formation process, the general formula WO ３－ｘ Tungsten oxide represented by (0 ≤ x ≤ 0.28), general formula SiO ａ N ｂ A first layer can be formed containing one or more selected from silicon oxynitride and aluminum oxide.

[0064] In the second layer formation process, a second layer containing tungsten bronze can be formed on the first layer.

[0065] In the second glass substrate installation process, the second glass substrate can be installed on the second layer.

[0066] The manufacturing method of the composite structure of this embodiment may further include a third layer formation step after the second layer formation step.

[0067] The manufacturing method of the composite structure of this embodiment may further include a heat treatment step for heat treating the first layer formed in the first layer formation step and the second layer formed in the second layer formation step.

[0068] The manufacturing process for the composite structure of this embodiment may include, for example, a first layer formation step S1 and a second layer formation step S2, as shown in the flow diagram 40 in Figure 4. The manufacturing process for the composite structure of this embodiment may also include a heat treatment step S3 after the second layer formation step S2 and before the second glass substrate installation step S4, as shown in the flow diagram 40.

[0069] Furthermore, the manufacturing process for the composite structure in this embodiment may also include a forming step and a heat treatment step for each of the first and second layers. For this reason, instead of the heat treatment step S3, the first layer heat treatment step may be included between the first layer forming step S1 and the second layer forming step S2, and the second layer heat treatment step may be included after the second layer forming step S2. However, if the desired composite structure can be formed by omitting any of the steps, it is not necessary to go through all of the above steps.

[0070] The following describes each process. (1) First layer formation process and second layer formation process In the first layer formation process and the second layer formation process, raw material particles can be attached to the substrate by using, for example, a physical or chemical film formation method to form a film (for example, a thin film). In the first layer formation process and the second layer formation process, the first layer and the second layer can be formed using one or more methods selected from, for example, vacuum deposition, sputtering, ion plating, ion beam sputtering, pulsed laser deposition (PLD), and chemical vapor deposition (CVD).

[0071] As for the sputtering method, one or more methods selected from high-frequency sputtering, pulsed sputtering, dual magnetron sputtering, etc., may be used. (1-1) First layer formation process The first layer formation process will be described below.

[0072] In the first layer formation process, the first layer can be formed on the first glass substrate. The first glass substrate has already been described, so its explanation will be omitted here.

[0073] In the first layer formation process, the substrate temperature during the formation of the first layer is not particularly limited, and the process may be carried out at room temperature, i.e., without heating. However, depending on the characteristics required for the first layer or the composite structure, the substrate may be heated during the first layer formation process. For example, if the substrate is heated and sputtering film deposition is performed, the first layer will be formed on the substrate while crystal growth occurs. This makes it possible to obtain a first layer film (e.g., a thin film) with aligned crystal orientation. When heating the substrate during the first layer formation process, the substrate temperature is not particularly limited, and the substrate temperature can be selected according to the composition of the first layer to be deposited, for example.

[0074] In the first layer formation step, a first layer can be formed containing one or more selected from tungsten oxide, silicon oxynitride, and aluminum oxide. In the first layer formation step, a first layer may be formed containing a film (e.g., a thin film) containing one or more selected from tungsten oxide, silicon oxynitride, and aluminum oxide.

[0075] The first layer formation process and the second layer formation process can also be carried out in the manufacturing process of the first glass substrate. For example, when the first glass substrate is manufactured by the float process, the first layer formation process and the second layer formation process can be carried out by sequentially supplying the raw materials for the first layer and the raw materials for the second layer onto the surface of the float glass that has been formed in the float tank and unloaded. Since the glass plate immediately after being unloaded from the float tank is at a sufficiently high temperature, a heat treatment process will also be carried out in conjunction with the first layer formation process and the second layer formation process. (1-2) Second layer formation process The second layer formation process will now be explained.

[0076] The second layer formation process can be carried out using the first layer formed on the first glass substrate as the substrate.

[0077] In the second layer formation process, the substrate temperature during second layer formation is not particularly limited; for example, the second layer formation process may be carried out at room temperature, i.e., without heating. However, depending on the characteristics required of the second layer or the composite structure, the substrate may be heated during the second layer formation process.

[0078] In the second layer formation step, a second layer containing tungsten bronze can be formed. In the second layer formation step, a second layer containing a film (e.g., a thin film) containing tungsten bronze may be formed. (2) Heat treatment step In the heat treatment step, the first layer and the second layer formed in the first layer formation step and the second layer can be heat treated. The heat treatment step may be performed individually for the first layer and the second layer, or it may be performed together. When the heat treatment of the first layer and the second layer is performed together after the second layer formation step, it may be performed, for example, under the conditions described in the second layer heat treatment step below.

[0079] The atmosphere in the heat treatment process is not particularly limited, but it is preferably a non-oxidizing atmosphere, and may be selected from, for example, a vacuum atmosphere, an inert gas atmosphere, and a reducing gas atmosphere such as hydrogen. In the heat treatment process, the heat treatment can be carried out at a heat treatment temperature of 300°C to 1000°C under the above atmosphere. (2-1) First layer heat treatment process The first layer heat treatment process will be described below.

[0080] The atmosphere for the first layer heat treatment process is not particularly limited, but may be selected from, for example, a vacuum atmosphere, an inert gas atmosphere, and a reducing gas atmosphere such as hydrogen.

[0081] For the inert gas, for example, noble gases such as helium or argon, or nitrogen gas can be used, but argon gas is preferable because it is commonly used, readily available, and reduces the generation of by-products.

[0082] To avoid contamination with impurities, the purity of the gas used in the first layer heat treatment step is preferably 99% or higher. Furthermore, it is preferable to select the type and ratio of the gas atmosphere in order to control the degree of oxidation-reduction based on the amount of oxygen deficiency in the target product.

[0083] The heat treatment temperature in the first layer heat treatment process is not particularly limited, but it is preferably 1000°C or lower considering the heat resistance of the glass substrate. In particular, the material contained in the first layer may be heat-treated near the phase transition temperature of the desired crystal structure in order to achieve the desired crystal structure.

[0084] While there are no particular limitations on the heating rate and heat treatment time in the first layer heat treatment process, it is preferable that the heating rate be 1°C / min or more in order to promote crystal growth in the first layer, and furthermore, it is preferable to hold the material at the heat treatment temperature for 30 minutes or more after it has reached the heat treatment temperature.

[0085] In the first layer formation process, if the substrate heating temperature is high and the crystals of the first layer are growing, this heat treatment process may be omitted. (2-2) Second layer heat treatment process The second layer heat treatment process will now be described.

[0086] The atmosphere in the second heat treatment process is not particularly limited, but may be selected from, for example, a vacuum atmosphere, an inert gas atmosphere, and a reducing gas atmosphere such as hydrogen.

[0087] For the inert gas, for example, noble gases such as helium or argon, or nitrogen gas can be used, but argon gas is preferable because it is commonly used, readily available, and reduces the generation of by-products.

[0088] To avoid contamination with impurities, the purity of the gas used in the second heat treatment step is preferably 99% or higher. Furthermore, it is preferable to select the type and ratio of the gas atmosphere in order to control the degree of oxidation-reduction depending on the composition of the target product, the amount of oxygen deficiency, etc.

[0089] In the second layer heat treatment process, the heat treatment temperature is not particularly limited, but it is preferably between 300°C and 1000°C. By setting the heat treatment temperature to 300°C or higher, crystallization can be promoted and the transparency of the film can be improved.

[0090] While there are no particular limitations on the heating rate and heat treatment time in the second layer heat treatment process, it is preferable that the heating rate be 1°C / min or more in order to promote crystal growth in the second layer, and furthermore, it is preferable to maintain the temperature at the heat treatment temperature for 30 minutes or more after it has been raised to the heat treatment temperature.

[0091] In the second layer formation step, if the desired second layer has already been obtained, this heat treatment step may be omitted. (3) Second glass substrate installation step In the second glass substrate installation step, the second glass substrate 15 can be installed on the second layer 13.

[0092] Since the types of glass substrates that can be suitably used as the second glass substrate have already been described, the explanation will be omitted here.

[0093] In the second glass substrate installation step, the second glass substrate 15 may be placed on the third layer 14 that has been pre-formed on the second layer 13, or on the protective layer 16, and then fixed by the third layer 14, etc.

[0094] Furthermore, if the third layer 14 is to be evacuated or sealed with a predetermined gas, the third layer 14 can be made to a predetermined atmosphere and sealed in the second glass substrate installation step. (4) The manufacturing method of the laminated structure of this embodiment may also include a protective layer formation step, a protective layer heat treatment step, and a third layer formation step as needed.

[0095] The protective layer deposition process can be carried out using the same procedure as the first layer formation process, except that the material used is appropriate for the material of the protective layer to be deposited.

[0096] Furthermore, regarding the protective layer heat treatment process, although the heat treatment conditions can be selected according to the composition of the protective layer, etc., it can be carried out using the same procedure as described in the first layer heat treatment process, for example. Note that the protective layer does not need to be crystallized, so the protective layer heat treatment process does not need to be performed, and the heat treatment may be carried out at a lower temperature than the first layer heat treatment process, etc.

[0097] The third layer formation process can be performed after the second layer formation process or the protective layer formation process, and before the second glass substrate installation process.

[0098] In the third layer formation step, spacers may be placed on top of the second layer or the protective layer, or a third layer containing a predetermined resin may be formed.

[0099] Specifically, in the third layer formation step, for example, a third layer 14 containing one or more resins selected from polyvinyl acetal resin, vinyl acetate copolymer, and ionomer resin may be formed on the second layer 13.

[0100] In the third layer formation process, when forming a third layer 14 containing resin, a sheet of resin that has been pre-processed into a sheet shape may be placed on the second layer 13 or the protective layer 16, and the third layer 14 may be formed by heat pressing or other means as necessary. Alternatively, in the third layer formation process, the third layer 14 may be formed by applying resin to the second layer 13 or the protective layer 16.

[0101] The third layer formation process and the second glass substrate installation process can be carried out together. For example, the third layer 14 and the second glass substrate 15 can be laminated on the second layer 13, and then the third layer and the second glass substrate can be formed by thermocompression bonding or the like.

[0102] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. 1. Evaluation Method (1) X-ray diffraction pattern The X-ray diffraction pattern (XRD pattern) of the obtained composite structure was measured using Cu-Kα rays with a D2PHASER X-ray diffractometer from BRUKER AXS. (2) Visible light transmittance, solar transmittance, solar heat gain coefficient, and maximum reflectance at wavelengths of 780 nm to 2600 nm In measuring the optical properties of the obtained composite structure, the transmittance and 8° incident diffuse reflectance were measured using a spectrophotometer V-670 (manufactured by JASCO Corp.), and the transmittance spectrum and reflectance spectrum were obtained. Then, using the spectral data of transmittance and reflectance, the visible light transmittance (VLT), solar radiation transmittance (ST) for wavelengths between 300 nm and 2500 nm, and solar heat gain coefficient (η) were determined in accordance with JIS R 3106 (2019). In addition, as an evaluation of reflectance, the maximum reflectance value for wavelengths between 780 nm and 2600 nm was determined. (3) Haze The haze value was measured using a haze meter (HM-150N manufactured by Murakami Color Technology Laboratory Co., Ltd.) and calculated based on JIS K 7136 (2000). (4) Average film thickness The average film thickness was measured at a total of 5 locations at 1 μm intervals along the surface of the glass substrate in an SEM image taken at any one location on the cross-section of the sample, and the arithmetic mean was taken. 2. Manufacturing conditions and evaluation results of laminated structures [Example 1] In Example 1, as shown in Figure 2, a laminated structure was fabricated by sequentially stacking a first layer 12, a second layer 13, a third layer 14, and a second glass substrate 15 on a first glass substrate 11, and the structure was evaluated. The first layer 12 was a layer having a first film 121 and a second film 122.

[0103] Specifically, in the first layer deposition process, a first film 121 was deposited using an aluminum oxide target, and then a second film 122 was deposited using a tungsten oxide target. (1) Fabrication of composite structure (1-1) Fabrication of aluminum oxide target for first layer formation An aluminum oxide target was fabricated by machining an aluminum oxide sintered body (manufactured by Canon Optron Co., Ltd.) to a diameter of 20 mm and a thickness of 4 mm. (1-2) Fabrication of tungsten oxide target for first layer formation A tungsten oxide sintered body was fabricated by placing tungsten oxide powder into a discharge plasma sintering apparatus (NJS Co., Ltd.) under the conditions of a vacuum atmosphere, a temperature of 870°C, and a pressure of 50 MPa. A tungsten oxide target was fabricated by machining this sintered body to a diameter of 20 mm and a thickness of 4 mm. (1-3) Preparation of a cesium tungsten oxide target for second layer formation A cesium tungsten oxide powder (YM-01, manufactured by Sumitomo Metal Mining Co., Ltd.) with a Cs / W atomic ratio of 0.33 was introduced into a discharge plasma sintering apparatus (NJS Corporation) under conditions of a vacuum atmosphere, a temperature of 870°C, and a pressure of 50 MPa to produce a cesium tungsten oxide sintered body. Chemical analysis of the sintered body composition revealed that the Cs / W ratio, which is the ratio of the amount of substance of Cs to W, was 0.32. This oxide sintered body was machined to a diameter of 20 mm and a thickness of 4 mm to produce a CsWO target.

[0104] Using the above target, a composite structure was manufactured according to the flow diagram 40 shown in Figure 4. (1-4) First layer formation process (Formation of the first film) The aluminum oxide target was placed in the vacuum chamber of a pulsed laser deposition apparatus (Pascal PAC-LMBE). The maximum vacuum pressure was 1 × 10⁻⁶ －５The vacuum pressure was kept below Pa, and during film deposition, oxygen gas was introduced into the vacuum chamber to a gas pressure of 0.5 Pa to deposit the first film on a soda glass substrate, which would serve as the first glass substrate. During film deposition, a KrF laser (wavelength 248 nm, pulse width 25 ns) was used as the irradiation laser, with a laser power of 150 mJ, a laser frequency of 4 Hz, and a laser irradiation time of 10 minutes, under room temperature deposition conditions (no substrate heating). (Formation of the second film) The target used was replaced with a tungsten oxide target. The maximum vacuum pressure was 1 × 10⁻⁶. －５ The pressure was kept below Pa, and during film deposition, oxygen gas was introduced into the vacuum chamber to achieve a gas pressure of 6.8 Pa to deposit the second film.

[0105] During film deposition, a KrF laser (wavelength 248 nm, pulse width 25 ns) was used for irradiation, with an exposure laser power of 150 mJ, a laser frequency of 4 Hz, and a laser irradiation time of 10 minutes. The heater temperature for substrate heating was set to 400°C.

[0106] Under the above conditions, a second continuous film of tungsten oxide was deposited on top of the first film, an aluminum oxide film, which was deposited on a soda glass substrate. (1-5) Second layer formation process The target used was replaced with a cesium tungsten oxide target. The maximum vacuum pressure was 1 × 10⁻⁶ －５The pressure was kept below Pa, and during film deposition, oxygen gas was introduced into the vacuum chamber to a gas pressure of 6.8 Pa to deposit the second layer. During film deposition, a KrF laser (wavelength 248 nm, pulse width 25 ns) was used as the irradiation laser, with an exposure laser power of 150 mJ, a laser frequency of 4 Hz, and a laser irradiation time of 10 minutes. Under room temperature deposition conditions (no substrate heating), in the first layer deposition process, a continuous film of cesium tungsten oxide was deposited on top of the first layer, which consisted of an aluminum oxide film and a tungsten oxide film, deposited on a soda glass substrate, which was the first glass substrate. (1-6) Heat treatment process After the completion of the second layer formation process, the introduction of oxygen gas was stopped, and under a vacuum atmosphere, the heater for heating the substrate inside the vacuum chamber was raised at 20°C / min so that the substrate reached 500°C, and after being held for 30 minutes, a heat treatment process was carried out, followed by slow cooling to room temperature at 50°C / min. (1-7) Third layer formation process, second glass substrate installation process Polyvinyl butyral (PVB) was stretched in advance with a roll and molded into a sheet with a thickness of 0.76 mm to prepare an interlayer.

[0107] In the third layer formation process and the second glass substrate placement process, the fabricated interlayer and the second glass substrate, a soda glass substrate approximately 2 mm thick, were placed on the surface of the second layer 13 in that order. Then, after heating to 80°C for temporary bonding, the bonding was performed at 140°C and 14 kg / cm². ２ The bonding was performed by autoclaving to create the composite structure. (2) Evaluation results The composite structure obtained in Example 1 was evaluated according to the procedure described in "1. Evaluation method". (2-1) X-ray diffraction pattern The X-ray diffraction pattern was measured for the composite structure of Example 1 using the measurement method described in "(1) X-ray diffraction pattern". The compounds identified from the X-ray diffraction pattern are listed in the "Substances detected from XRD" column of Table 1.

[0108] As shown in Table 1, the compound contained in the composite structure is tungsten oxide (o-WO) contained in the second film 122 of the first layer 12. ３ ) and the Cs contained in the second layer 13 ０．３３ WO ３ And was identified. Furthermore, Na ０．０２ WO ２．８ Na was observed.０．０２ WO ２．８ Na that has moved from the first glass substrate 11 is in the WO of the first layer 12. ３ It is thought to have been produced by a reaction with Na. ０．０２ WO ２．８ Since it is a tungsten bronze compound, it does not increase the haze of the composite structure 10, and is rather thought to have the effect of improving the heat shielding properties.

[0109] Al contained in the first film 121 of the first layer 12 ２ O ３ Regarding this, no peak was observed because it is amorphous. (2-1) Optical properties As shown in Table 1, the visible light transmittance was 62.4%, the solar transmittance was 29.6%, the maximum reflectance at wavelengths of 780 nm to 2600 nm was 64.7%, and the solar heat gain coefficient was 0.48. Therefore, it was confirmed that the composite structure obtained in Example 1 has excellent transmittance in the visible light region, excellent reflectivity in the near-infrared region, and also excellent heat shielding properties.

[0110] Furthermore, it was confirmed that the haze was also extremely low at 0.7%. [Example 2] (1) Fabrication of a laminated structure In Example 2, the aluminum oxide film, which is the first film 121 of the first layer 12, was not formed. Therefore, in this example, the first layer 12 consists of the first film 121, and the first film 121 is a tungsten oxide film. Also, a polycarbonate plate was used as the second glass substrate 15. For this reason, as shown in Figure 1, a laminated structure was fabricated by sequentially laminating the first layer 12, the second layer 13, the third layer 14, and the second glass substrate, which is polycarbonate, on a soda glass substrate, which is the first glass substrate 11, and the structure was evaluated.

[0111] Except for the above points, each layer was formed under the same conditions as in Example 1 to obtain the average film thickness shown in Table 1, and a composite structure was fabricated. (2) Regarding the evaluation results, the composite structure obtained in Example 2 was evaluated according to the procedure described in "1. Evaluation method". (2-1) X-ray diffraction pattern For the composite structure of Example 2 for which the X-ray diffraction pattern was prepared, the X-ray diffraction pattern was measured by the measurement method described in "(1) X-ray diffraction pattern". The compounds identified from the X-ray diffraction pattern are listed in the column of "Substances detected by XRD" in Table 1.

[0112] As shown in Table 1, as the compounds contained in the composite structure, tungsten oxide (o-WO ３ ) contained in the first layer 12 and Cs ０．３３ WO ３ contained in the second layer 13 were identified. Further, Na ０．０２ WO ２．８ was observed. Na ０．０２ WO ２．８ is considered to be formed by the reaction of Na transferred from the first glass substrate 11 with WO ３ in the first layer 12. Since Na ０．０２ WO ２．８ is a tungsten bronze compound, it is considered that it does not increase the haze of the composite structure 10, but rather has the effect of enhancing the heat ray shielding property. (2-2) Optical properties As shown in Table 1, the visible light transmittance was 57.9%, the solar radiation transmittance was 28.1%, the maximum reflectance in the wavelength range of 780 nm to 2600 nm was 65.0%, and the solar heat gain factor was 0.47. Therefore, it was confirmed that the composite structure obtained in Example 2 has excellent transparency in the visible light region, excellent reflection characteristics in the near infrared region, and excellent heat ray shielding characteristics.

[0113] Also, it was confirmed that the haze was extremely low at 0.9%. [Example 3] (1) Fabrication of composite structure In Example 3, as shown in FIG. 1, a composite structure in which a first layer 12, a second layer 13, a third layer 14, and a second glass substrate 15 were sequentially laminated on a first glass substrate 11 was fabricated and evaluated.

[0114] Specifically, in the first layer deposition process, a silicon oxynitride target was used instead of a tungsten oxide target to deposit the first layer 12.

[0115] Except for the points mentioned above, each layer was deposited under the same conditions as in Example 2 to achieve the film thickness shown in Table 1, and a composite structure was fabricated. (2) Evaluation Results The composite structure obtained in Example 3 was evaluated according to the procedure described in "1. Evaluation Method". (2-1) X-ray Diffraction Pattern The X-ray diffraction pattern of the composite structure of Example 3 with deposited film was measured using the measurement method described in "(1) X-ray Diffraction Pattern". Compounds identified from the X-ray diffraction pattern are listed in the "Substances Detected from XRD" column of Table 1.

[0116] As shown in Table 1, the compound contained in the composite structure is Cs contained in the second layer 13. ０．３３ WO ３ It was identified.

[0117] No peak was observed for the silicon oxynitride contained in the first layer 12 because it is amorphous.

[0118] Furthermore, the Na observed in Examples 1 and 2 was ０．０２ WO ２．８ This was not observed. This is thought to be because the first layer 12 does not contain tungsten oxide and the first layer 12 containing silicon oxynitride prevents components from migrating from the first glass substrate 11. (2-2) Optical properties As shown in Table 1, the visible light transmittance was 64.3%, the solar transmittance was 33.5%, the maximum reflectance at wavelengths of 780 nm to 2600 nm was 66.2%, and the solar heat gain coefficient was 0.49. Therefore, it was confirmed that the composite structure obtained in Example 3 has excellent transmittance in the visible light region, excellent reflectivity in the near-infrared region, and excellent heat shielding properties.

[0119] Also, it was confirmed that the haze was extremely low at 1.3%. [Comparative Example 1] (1) Fabrication of the combined structure In Comparative Example 1, the first layer formation process was not carried out, and a second layer containing tungsten bronze was directly formed on a soda glass substrate which is the first glass substrate 11. The combined structure was fabricated under the same conditions and procedures as in Example 1 except for the above points. (2) Regarding the evaluation results The combined structure obtained in Comparative Example 1 was evaluated according to the procedure described in "1. Evaluation method". (2-1) X-ray diffraction pattern For the combined structure of Comparative Example 1 fabricated, the X-ray diffraction pattern was measured by the measurement method described in "(1) X-ray diffraction pattern". The compounds identified from the X-ray diffraction pattern are described in the column of "Substances detected from XRD" in Table 1.

[0120] As shown in Table 1, as compounds contained in the combined structure, in addition to Cs ０．３３ WO ３ contained in the second layer 13, Na ０．０２ WO ２．８ and Na ２ W ２ O ７ were identified.

[0121] Na ０．０２ WO ２．８ and Na ２ W ２ O ７ are considered to be generated by the reaction of the components contained in the glass substrate and Cs ０．３３ WO ３ contained in the second layer 13. (2-2) Optical properties As shown in Table 1, the visible light transmittance was 68.2%, the solar radiation transmittance was 55.7%, the maximum reflectance value in the wavelength range of 780 nm to 2600 nm was 46.1%, and the solar heat gain factor was 0.59. Therefore, it was confirmed that the combined structure obtained in Comparative Example 1 had excellent permeability in the visible light region, but the reflection characteristics deteriorated and the heat ray shielding effect weakened. Also, it was confirmed that the haze was as high as 6.8%. The decrease in reflectance and the increase in haze are considered to be due to the reaction between the first glass substrate 11 and the tungsten bronze contained in the second layer 13 in the combined structure of Comparative Example 1 which has no first layer 12, and the products generated by this reaction.

[0122] Examples of embodiments of the present disclosure are as follows: <1> A first glass substrate, a first layer, a second layer, and a second glass substrate, wherein the first layer is of the general formula WO ３－ｘ Tungsten oxide represented by (0 ≤ x ≤ 0.28), general formula SiO ａ N ｂ A composite structure comprising one or more selected from silicon oxynitride and aluminum oxide, wherein the second layer comprises tungsten bronze, and the first layer, the second layer, and the second glass substrate are arranged in that order from a position close to the first glass substrate. <2> The composite structure according to <1>, further comprising a third layer between the second layer and the second glass substrate, wherein the third layer comprises one or more resins selected from polyvinyl acetal resin, vinyl acetate copolymer, and ionomer resin. <3> The composite structure according to <1> or <2>, wherein the average film thickness of the first layer is 5 nm or more and 1200 nm or less, and the average film thickness of the second layer is 5 nm or more and 1200 nm or less. <4> The composite structure according to any one of <1> to <3>, wherein the first layer comprises tungsten oxide, and at least a portion of the tungsten oxide is crystallized. <5> The first layer comprises tungsten oxide, and the composite structure, in the X-ray diffraction pattern, comprises a tungsten oxide phase and M ｘ１ WO ｚ１ A composite structure according to any one of <1> to <4>, wherein a phase (where element M is one or more elements selected from alkali metals and alkaline earth metals, and x1 satisfies 0.01 ≤ x1 < 1) and a tungsten bronze phase are confirmed. <6> A composite structure according to any one of <1> to <5>, further comprising a protective layer laminated on the second layer. <7> The protective layer is SiO ２ , TiO ２ WO ３ , Nb ２ O ５ Al ２ O ３ , ZrO ２ Ta ２ O ５ , SnO ２ Si ３N ４ LaB ６ , a composite structure according to <6>, comprising one or more compounds selected from the group of TiN compounds. <8> A composite structure according to any one of <1> to <7>, wherein the haze is 0.01% or more and 6.0% or less. <9> A composite structure according to any one of <1> to <8>, wherein the visible light transmittance is 20% or more and 90% or less. <10> A composite structure according to any one of <1> to <9>, wherein the solar radiation transmittance is 50% or less. <11> A method comprising a first layer formation step, a second layer formation step, and a second glass substrate installation step, wherein in the first layer formation step, a general formula WO is formed on the first glass substrate. ３－ｘ Tungsten oxide represented by (0 ≤ x ≤ 0.28), general formula SiO ａ N ｂ A method for manufacturing a composite structure, comprising: forming a first layer comprising one or more selected from silicon oxynitride and aluminum oxide; forming a second layer comprising a thin film of tungsten bronze on the first layer in the second layer formation step; and placing a second glass substrate on the second layer in the second glass substrate placement step. <12> A method for manufacturing a composite structure according to <11>, further comprising a third layer formation step after the second layer formation step, wherein a third layer comprising one or more resins selected from polyvinyl acetal resin, vinyl acetate copolymer, and ionomer resin is formed on the second layer in the third layer formation step. <13> A method for manufacturing a composite structure according to <11> or <12>, wherein the first layer and the second layer are formed using one or more methods selected from vacuum deposition, sputtering, ion plating, ion beam sputtering, pulsed laser deposition (PLD), and chemical vapor deposition (CVD), respectively. <14> A method for manufacturing a composite structure according to any one of <11> to <13>, further comprising a heat treatment step of heat treating the first layer formed in the first layer formation step, the first layer formed in the second layer formation step, and the second layer. <15> A method for manufacturing a composite structure according to claim <14>, wherein the heat treatment step is performed in an atmosphere selected from a vacuum atmosphere, an inert gas atmosphere, or a reducing gas atmosphere, at a heat treatment temperature of 300°C or more and 1000°C or less.

[0123] This application claims priority based on Japanese Patent Application No. 2024-210765, filed with the Japan Patent Office on December 3, 2024, and the entire contents of Japanese Patent Application No. 2024-210765 are incorporated herein by reference.

[0124] 10 Laminated structure 20 Laminated structure 30 Laminated structure 11 First glass substrate T11 Average thickness 12 First layer 121 First film 122 Second film T12 Average film thickness 13 Second layer T13 Average film thickness 14 Third layer 15 Second glass substrate T15 Average thickness 16 Protective layer 40 Flowchart S1 First layer formation process S2 Second layer formation process S3 Heat treatment process S4 Second glass substrate installation process

Claims

1. The material comprises a first glass substrate, a first layer, a second layer, and a second glass substrate, wherein the first layer is of the general formula WO ３－ｘ Tungsten oxide represented by (0 ≤ x ≤ 0.28), general formula SiO ａ N ｂ A composite structure comprising one or more selected from silicon oxynitride and aluminum oxide, wherein the second layer comprises tungsten bronze, and the first layer, the second layer, and the second glass substrate are arranged in that order from the position closest to the first glass substrate.

2. The composite structure according to claim 1, further comprising a third layer between the second layer and the second glass substrate, wherein the third layer comprises one or more resins selected from polyvinyl acetal resin, vinyl acetate copolymer, and ionomer resin.

3. The composite structure according to claim 1 or claim 2, wherein the average film thickness of the first layer is 5 nm or more and 1200 nm or less, and the average film thickness of the second layer is 5 nm or more and 1200 nm or less.

4. The composite structure according to claim 1 or claim 2, wherein the first layer comprises tungsten oxide, and at least a portion of the tungsten oxide is crystallized.

5. The first layer contains the tungsten oxide, and the composite structure, in the X-ray diffraction pattern, has the tungsten oxide phase and M ｘ１ WO ｚ１ A composite structure according to claim 1 or claim 2, wherein a phase (where element M is one or more elements selected from alkali metals and alkaline earth metals, and x1 satisfies 0.01 ≤ x1 < 1) and a tungsten bronze phase are confirmed.

6. The composite structure according to claim 1 or claim 2, further comprising a protective layer laminated on the second layer.

7. The protective layer is SiO ２ , TiO ２ , WO ３ , Nb ２ O ５ , Al ２ O ３ , ZrO ２ , Ta ２ O ５ , SnO ２ , Si ３ N ４ , LaB ６ , The combined structure according to claim 6, comprising one or more selected from the group of compounds of TiN.

8. The composite structure according to claim 1 or claim 2, wherein the haze is 0.01% or more and 6.0% or less.

9. The composite structure according to claim 1 or claim 2, wherein the visible light transmittance is 20% or more and 90% or less.

10. The composite structure according to claim 1 or claim 2, wherein the solar radiation transmittance is 50% or less.

11. The process comprises a first layer formation step, a second layer formation step, and a second glass substrate installation step, wherein in the first layer formation step, a general formula WO is applied to the first glass substrate. ３－ｘ Tungsten oxide represented by (0 ≤ x ≤ 0.28), general formula SiO ａ N ｂ A method for manufacturing a laminated structure, comprising: forming a first layer containing one or more selected from silicon oxynitride and aluminum oxide; forming a second layer containing a thin film of tungsten bronze on the first layer in the second layer formation step; and placing a second glass substrate on the second layer in the second glass substrate placement step.

12. The method for producing a composite structure according to claim 11, further comprising a third layer formation step after the second layer formation step, wherein in the third layer formation step, a third layer comprising one or more resins selected from polyvinyl acetal resin, vinyl acetate copolymer, and ionomer resin is formed on the second layer.

13. A method for manufacturing a composite structure according to claim 11 or claim 12, wherein in the first layer formation step and the second layer formation step, the first layer and the second layer are formed using one or more methods selected from vacuum deposition, sputtering, ion plating, ion beam sputtering, pulsed laser deposition (PLD), and chemical vapor deposition (CVD), respectively.

14. A method for manufacturing a composite structure according to claim 11 or claim 12, further comprising a heat treatment step of heat treating the first layer formed in the first layer formation step, the first layer formed in the second layer formation step, and the second layer.

15. The method for manufacturing a composite structure according to claim 14, wherein the heat treatment step is performed in an atmosphere selected from a vacuum atmosphere, an inert gas atmosphere, or a reducing gas atmosphere, at a heat treatment temperature of 300°C or more and 1000°C or less.

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