Layered structure and method for producing layered structure

Abstract

This layered structure comprises a first glass substrate, a first layer, a second layer, a third layer, and a second glass substrate. The first layer contains tungsten oxide that is crystalline and is represented by the general formula WO3-x (O ≤ｘ≤ 0.28). The second layer contains tungsten bronze. The third layer contains one or more selected from the compound group consisting of SiO2, TiO2, WO3, Nb2O5, Al2O3, ZrO2, Ta2O5, SnO2, Si3N4, LaB6, and TiN. The first layer, second layer, third layer, and second glass substrate are disposed in order beginning from 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] One aspect of the bonding structure according to the present invention includes a first glass substrate, a first layer, a second layer, a third layer, and a second glass substrate. The first layer contains tungsten oxide represented by the general formula WO ３－ｘ (0 ≤ x ≤ 0.28) which has crystallinity. The second layer contains tungsten bronze. The third layer contains one or more selected from the group of compounds of 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 , TiN. The first layer, the second layer, the third layer, and the second glass substrate are arranged in this order from a position close to the first glass substrate.

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

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

[0011] Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments, and various modifications and substitutions can be made to the following embodiments without departing from the scope of the present invention. [Bonding Structure] FIGS. 1 and 2 show explanatory diagrams of the bonding structure of the present embodiment. FIGS. 1 and 2 are cross-sectional views of the bonding structure of the present embodiment in a plane along the stacking direction of the first glass substrate, the first layer, the second layer, the third layer, and the second glass substrate. Since FIG. 2 corresponds to another configuration example of the bonding structure of the present embodiment, the description will be mainly made using FIG. 1, and FIG. 2 will be used for the description as necessary.

[0012] In this specification, the names of components may be prefixed with "1st," "2nd," etc., such as "1st layer," "2nd layer," and "3rd layer." However, these prefixes are merely used to identify the component being described and to avoid confusion, and do 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, a third layer 14, and a second glass substrate 16. Furthermore, the layers can be arranged in the order of the first layer 12, the second layer 13, the third layer 14, and the second glass substrate 16, 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, the third layer 14, and the second glass substrate 16.

[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] The investigation revealed that in the composite structure with increased haze, a new phase was formed, likely due to a reaction between components in the tungsten bronze and components in the glass substrate. Therefore, it was inferred that the increased haze in the composite structure was due to the migration and reaction of components in the glass substrate during the deposition of the tungsten bronze film, resulting in the formation of a new compound phase.

[0019] Based on the mechanism by which haze increases in the conventional laminated structures described above, the inventors of the present invention conducted further investigations. As a result, they discovered that by placing a first layer 12 between the first glass substrate 11 and the second layer 13 containing tungsten bronze, which can reduce the movement of components from the first glass substrate 11 to the second layer 13, a laminated structure 10 with reduced haze can be created, thus completing the present invention.

[0020] Therefore, in the composite structure 10 of this embodiment, a first layer 12 can be provided between the first glass substrate 11 and the second layer 13. The first layer 12 is a crystalline material of general formula WO ３－ｘ It contains tungsten oxide represented by (0 ≤ x ≤ 0.28). General formula WO ３－ｘ Tungsten oxide represented by (0 ≤ x ≤ 0.28) may be included in the first layer 12 as a film containing the tungsten oxide. Below, the general formula WO ３－ｘ Tungsten oxide, expressed as (0 ≤ x ≤ 0.28), is sometimes simply referred to as tungsten oxide. (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, producing 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, and prevents 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 It can contain tungsten oxide represented by (0 ≤ x ≤ 0.28). Note that the first layer 12 can also be composed solely of tungsten 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 tungsten 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 in stoichiometric ratio WO ３ In that case it is a transparent inert film, but when reduced it becomes WO ３－ｘ Because 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 WO ｚ１ 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. (1-2-2) Regarding the average thickness of the first layer, the average thickness T12 of the first layer 12 is not particularly limited, but for example, the average 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.

[0033] 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.

[0034] 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 manufacture 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 included in the second layer 13 as a tungsten bronze film.

[0035] 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 ｚ２ It 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.

[0036] 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.

[0037] 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).

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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, and the productivity during the manufacturing of the composite structure 10 can be increased. (1-4) Third layer (1-4-1) Composition of the third layer The composite structure 10 of this embodiment may further have a third layer 14 laminated on the second layer 13.

[0042] The third layer 14 may be directly laminated on the second layer 13, or there may be any layer between the second layer 13 and the third layer 14.

[0043] The presence of a third layer 14 in the composite structure 10 protects the first layer 12 and the second layer 13, preventing damage to them. Depending on the application of the composite structure 10, the third layer 14 may also have a function to improve optical properties such as visible light transmittance and infrared reflectance by adjusting the refractive index.

[0044] Furthermore, because the composite structure 10 has a third layer 14, the diffusion of oxygen to the first layer 12 and the second layer 13 can be controlled when heat treatment is performed during the manufacturing process of the composite structure 10. For this reason, the heat treatment can be performed in an oxidizing atmosphere such as air. Even when heat treatment is performed in an oxidizing atmosphere such as air, the degree of oxidation of the tungsten bronze in the second layer 13 can be kept within an appropriate range, thereby reducing the haze of the composite structure 10.

[0045] The material contained in the third layer 14 is not particularly limited and can be selected according to the application of the composite structure 10 and the optical properties required for the composite structure 10. For example, the third layer 14 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 , containing one or more compounds selected from the TiN compound group. For example, SiO contained in the third layer 14. 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 ６One or more compounds selected from the TiN compound group may be included in the third layer 14 as a film containing these compounds.

[0046] 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 third layer 14 when the composite structure 10 is used in optical devices, displays, electronic devices, etc. For example, ZrO ２ Yes, Si ３ N ４ Al ２ O ３ For example, it is preferable to use the composite structure 10 as the material for the third layer 14 when the composite structure 10 is used in a device that requires mechanical strength and heat resistance. ２ Yes, LaB ６ It is preferable to use the composite structure 10 as the material for the third layer 14 when it is used in applications where transparency, chemical stability, and high conductivity are required. There may be multiple third layers. (1-4-2) Regarding 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 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.

[0047] By setting the average film thickness T14 of the third layer 14 to 5 nm or more, the first layer 12 and the second layer 13 can be particularly protected, resulting in a composite structure with particularly excellent durability.

[0048] Furthermore, by setting the average film thickness T14 of the third layer 14 to 1200 nm or less, the time required to form the third layer 14 can be shortened, thereby increasing the productivity of manufacturing the laminated structure 10. (1-5) Second glass substrate The laminated structure 10 of this embodiment may further have a second glass substrate 16 laminated on the third layer 14.

[0049] The second glass substrate 16 may be made of the same glass materials as described for the first glass substrate 11. Furthermore, the second glass substrate 16 may be organic glass, or an inorganic-organic glass.

[0050] As the organic glass, one or more resins selected from, for example, acrylic resin, polycarbonate resin, polyurethane resin, and polyimide resin can be used.

[0051] 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.

[0052] The average thickness T16 of the second glass substrate 16 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.

[0053] The laminated structure of this embodiment may have the first glass substrate, the first layer, the second layer, the third layer, and the second glass substrate as described above. The laminated structure of this embodiment may also have any additional layers as needed. A fourth layer and a base 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 the arbitrary layers, the fourth layer and the base layer, or it may further have both the fourth layer and the base layer. Also, the laminated structure of this embodiment may not have both the fourth layer and the base layer. (1-6) Fourth layer (1-6-1) Regarding the configuration of the fourth layer, the second glass substrate 16 may be placed directly on the third layer 14, but the laminated structure 10 of this embodiment may have a fourth layer 15 between the third layer 14 and the second glass substrate 16.

[0054] The fourth layer 15 may be a layer on which spacers or the like are placed, so that the distance between the third layer 14 and the second glass substrate 16 remains constant. Furthermore, if spacers or the like are placed in the fourth layer 15, the fourth layer 15 may be a region enclosed in a vacuum or a predetermined gas.

[0055] By placing a fourth layer 15 in a predetermined atmosphere such as a vacuum between the second glass substrate 16 and the first glass substrate 11, the thermal conductivity can be reduced and the heat insulation performance can be improved.

[0056] The fourth layer 15 may contain one or more resins selected from polyvinyl acetal resin, vinyl acetate copolymer, and ionomer resin.

[0057] The fourth layer 15 contains one or more resins selected from polyvinyl acetal resin, vinyl acetate copolymer, and ionomer resin, which allows the second glass substrate 16 to be fixed to the third layer 14. The fourth layer 15 may also contain ultraviolet absorbing materials in addition to the above resins. By containing ultraviolet absorbing materials in the fourth layer 15, the wavelength range of light transmitted by the laminated structure 10 can be further controlled. (1-6-2) Film thickness The average film thickness T15 of the fourth layer 15 is not particularly limited, but for example, the average film thickness T15 of the fourth layer 15 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. (1-7) Underlayment (1-7-1) Underlayment configuration Figure 2 shows a laminated structure 20, which is another configuration example of this embodiment. As shown in Figure 2, the laminated structure of this embodiment may have an underlayment 17 between the first glass substrate 11 and the second layer 13.

[0058] Figure 2 shows an example in which the underlayment 17 is placed between the first glass substrate 11 and the first layer 12, but the underlayment 17 may also be placed between the first layer 12 and the second layer 13.

[0059] Substrate 17 is made of general formula SiO ａ N ｂ It may contain one or more selected from silicon oxynitride represented by and aluminum oxide. The general formula SiO contained in the base layer 17 ａ N ｂOne or more compounds selected from silicon oxynitride and aluminum oxide, represented by , may be included in the substrate layer 17 as a film containing these compounds. (1-7-2) Composition of the substrate As explained in "(1-2) First layer", the glass used in the glass substrate contains additives. According to the inventors' research of the present invention, elements such as additives contained in the glass mainly used in the glass substrate, such as Group 1 elements such as alkali metals and Group 2 elements such as alkaline earth metals, react with tungsten bronze to produce a different phase.

[0060] Therefore, the laminated structure 10 of this embodiment has a first layer 12, which reduces the movement of elements such as additives contained in the glass from the first glass substrate 11 to the second layer 13, preventing them from reaching the second layer 13. Furthermore, as in the laminated structure 20 of this embodiment, by having an additional underlayer 17, the movement of elements such as additives contained in the glass from the first glass substrate 11 to the second layer 13 can be further reduced, and the possibility of them reaching the second layer 13 can be further reduced. For this reason, the presence of the underlayer 17 in the laminated structure 20 particularly prevents the formation of different phases in the second layer 13 and increases the haze of the laminated structure.

[0061] Silicon oxynitride and aluminum oxide have the function of preventing components in the glass used in the first glass substrate 11 from migrating to the second layer 13.

[0062] The general formula for silicon oxynitride is SiO₂ ａ N ｂ In the expression, a and b preferably satisfy 0 ≤ a ≤ 2 and 0 ≤ b ≤ 1.33. (2) Physical properties, etc. The physical properties of the composite 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 composite structure of this embodiment is preferably 6.0% or less, and more preferably 0.01% or more and 6.0% or less.

[0063] 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.

[0064] 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.

[0065] 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, the second layer 13, and the third layer 14 can be made to a sufficient thickness, thereby particularly improving the heat shielding ability and durability of the laminated structure of this embodiment. (2-3) Regarding solar transmittance, the solar transmittance of the laminated structure of this embodiment is preferably 50% or less, and more preferably 10% or more and 50% or less.

[0066] 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.

[0067] The manufacturing method of the composite structure of this embodiment may include a laminate formation step and a second glass substrate installation step.

[0068] The laminate formation process includes a first layer formation process, a second layer formation process, and a third layer formation process, and can form a laminate in which the first layer, second layer, and third layer are laminated on a first glass substrate.

[0069] Then, in the first layer formation process, the general formula WO ３－ｘA first layer containing tungsten oxide represented by (0 ≦ x ≦ 0.28) can be formed.

[0070] In the second layer forming step, a second layer containing tungsten bronze can be formed on the first layer.

[0071] In the third layer forming step, on the second layer, 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 , a third layer containing one or more selected from the group of compounds of TiN can be formed.

[0072] In the second glass substrate installation step, the second glass substrate can be installed on the third layer.

[0073] The manufacturing method of the combined structure of the present embodiment can have, for example, as shown in the flow chart 30 shown in FIG. 3, for example, a first layer forming step S1, a second layer forming step S2, a third layer forming step S, and a second glass substrate installation step S5.

[0074] The manufacturing method of the combined structure of the present embodiment may further have a heat treatment step S4. In the heat treatment step S4, the laminate obtained in the laminate forming step can be heat treated in an oxygen-containing atmosphere.

[0075] In addition, when the target combined structure can be formed even if any of the steps is omitted, the manufacturing method of the combined structure of the present embodiment does not need to go through all the above steps.

[0076] The following describes each process. (1) Laminate formation process In the laminate formation process, raw material particles can be attached to the substrate by, for example, a physical or chemical film formation method to form a thin film. In the laminate formation process, the first layer, second layer, and third 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).

[0077] As for the sputtering method, one or more methods selected from high-frequency sputtering, pulsed sputtering, dual magnetron sputtering, etc., may be used. The materials contained in the first layer 12, the second layer 13, and the third layer 14 have already been described, so the explanation will be omitted. Each layer can be formed by selecting raw materials so as to form a layer with the desired composition according to the film formation method. (1-1) First layer formation process The first layer formation process will be described below.

[0078] In the first layer deposition 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.

[0079] 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 first glass substrate, for example, 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 formed, for example.

[0080] In the first layer formation step, a first layer containing tungsten oxide can be formed. In the first layer formation step, a first layer containing a film (e.g., a thin film) containing tungsten oxide may be formed. (1-2) Second layer formation step The second layer formation step will be described below.

[0081] The second layer formation process can be carried out using the first layer formed on the first glass substrate as the substrate.

[0082] 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.

[0083] 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. (1-3) Third layer formation step The third layer formation step will be described below.

[0084] The third layer formation process can be carried out using the second layer formed on the first glass substrate as the substrate.

[0085] In the third layer formation process, the substrate temperature during third layer formation is not particularly limited; for example, the third layer formation process may be carried out at room temperature, i.e., without heating. However, depending on the characteristics required of the third layer or the composite structure, the substrate may be heated during the third layer formation process.

[0086] In the third layer formation process, 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, a third layer can be formed containing one or more compounds selected from the TiN compound group. In the third layer formation step, a third layer containing a film (e.g., a thin film) containing one or more compounds selected from the above compound group may be formed. (2) Heat treatment step The manufacturing method of the composite structure of this embodiment may further include a heat treatment step S4. In the heat treatment step, the laminate in which the first layer 12, second layer 13, and third layer 14 formed in the first layer formation step, second layer formation step, and third layer formation step are laminated can be heat treated.

[0087] The atmosphere in the heat treatment process is not particularly limited, but may be selected from, for example, a vacuum atmosphere, an inert gas atmosphere, a reducing gas atmosphere such as hydrogen, and an oxidizing gas atmosphere such as oxygen. However, according to the manufacturing method of the composite structure of this embodiment, the heat treatment process can be carried out after the formation of the third layer 14, and the diffusion of oxygen to the first layer 12 and the second layer 13 can be controlled by the third layer 14. For this reason, the atmosphere in the heat treatment process can be an oxygen-containing atmosphere. The heat treatment process is preferably carried out in an atmospheric atmosphere that can be easily formed and controlled. In the heat treatment process, the heat treatment can be carried out at a heat treatment temperature of, for example, 300°C to 1000°C.

[0088] The heat treatment temperature in the heat treatment process is not particularly limited, but it is preferable to be 1000°C or lower considering the heat resistance of the glass substrate. In particular, the material contained in the first layer 12 may be heat-treated near the phase transition temperature of the desired crystal structure in order to achieve the desired crystal structure.

[0089] The heating rate and heat treatment time in the heat treatment process are not particularly limited, but in order to grow crystals in the first layer 12, it is preferable that the heating rate be 1°C / min or more, and further, after heating to the heat treatment temperature, it is preferable to hold it at the heat treatment temperature for 30 minutes or more. (3) Second glass substrate installation process In the second glass substrate installation process, the second glass substrate 16 can be installed on the third layer 14.

[0090] 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.

[0091] In the second glass substrate installation step, the second glass substrate 16 may be placed on the fourth layer 15 that has been pre-formed on the third layer 14 and fixed by the fourth layer 15, etc.

[0092] Furthermore, if the fourth layer 15 is to be evacuated or sealed with a predetermined gas, the fourth layer 15 can be made to a predetermined atmosphere and sealed in the second glass substrate installation process. (4) Other The manufacturing method of the laminated structure of this embodiment may also include a base layer formation process and a fourth layer formation process as needed. (4-1) Base layer formation process The base layer formation process can be carried out in the same procedure as the first layer formation process, etc., except that a material corresponding to the material of the base layer to be formed is used. The base layer formation process can be carried out before the second layer formation process. (4-2) Fourth layer formation process The fourth layer formation process can be carried out after the heat treatment process and before the second glass substrate installation process.

[0093] In the fourth layer formation step, a spacer may be placed on the third layer, or a fourth layer containing a predetermined resin may be formed.

[0094] Specifically, in the fourth layer formation step, for example, a fourth layer 15 containing one or more resins selected from polyvinyl acetal resin, vinyl acetate copolymer, and ionomer resin may be formed on the third layer 14.

[0095] In the fourth layer formation process, when forming the fourth layer 15 containing resin, a sheet of resin that has been pre-processed into a sheet shape may be placed on the third layer 14 and the fourth layer 15 may be formed by heat pressing or other means as necessary. Alternatively, in the fourth layer formation process, the fourth layer 15 may be formed by coating the third layer 14 with resin or the like.

[0096] 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, and maximum reflectance at wavelengths of 780 nm to 2600 nm In measuring the optical properties of the obtained composite structure, transmittance and 8° incident diffuse reflectance were measured using a spectrophotometer V-670 (manufactured by JASCO Corp.), and transmittance spectra and reflectance spectra were obtained. Then, using the spectral data of transmittance and reflectance, the visible light transmittance (VLT) and solar transmittance (ST) at wavelengths of 300 nm to 2500 nm were determined in accordance with JIS R 3106 (2019). Furthermore, as an evaluation of reflectance, the maximum reflectance value in the wavelength range of 780 nm to 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 in 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 1, a laminated structure was fabricated by sequentially stacking a first layer 12, a second layer 13, a third layer 14, a fourth layer 15, and a second glass substrate 16 on a first glass substrate 11, and the evaluation was performed. (1) Fabrication of composite structure (1-1) Fabrication of tungsten oxide target for first layer formation Tungsten oxide powder was placed in a discharge plasma sintering apparatus (NJS Corporation) under vacuum conditions, temperature 870°C, and pressure 50 MPa to produce a tungsten oxide sintered body. This sintered body was machined to a diameter of 20 mm and a thickness of 4 mm to produce a tungsten oxide target.(1-2) Preparation of a cesium tungsten oxide target for the second layer Cesium tungsten oxide powder (YM-01, manufactured by Sumitomo Metal Mining Co., Ltd.) with a Cs / W atomic ratio of 0.33 was placed in 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. (1-3) Preparation of an aluminum oxide target for the third layer An aluminum oxide sintered body (manufactured by Canon Optron Co., Ltd.) was machined to a diameter of 20 mm and a thickness of 4 mm to produce an aluminum oxide target.

[0097] Using the above target, a composite structure was deposited according to the flow diagram 30 shown in Figure 3. (1-4) First layer formation process The tungsten oxide target was placed in the vacuum chamber of the pulsed laser deposition apparatus (Pascal PAC-LMBE). The maximum vacuum pressure was 1 × 10⁻⁶ －５ The pressure was kept below Pa, and during film formation, oxygen gas was introduced into the vacuum chamber to a gas pressure of 6.8 Pa, and the first layer 12 was formed on the soda glass substrate, which was the first glass substrate 11.

[0098] A KrF laser (wavelength 248 nm, pulse width 25 ns) was used for irradiation, with a laser power of 150 mJ, a laser frequency of 4 Hz, and a laser irradiation time of 10 minutes. The first layer 12 was formed under conditions where the heater temperature for heating the substrate reached 400°C.

[0099] Under the above conditions, in the first layer formation process, a continuous film of tungsten oxide was formed on the first glass substrate. (1-5) In the second layer formation process, the target used was replaced with a cesium tungsten oxide target. The maximum vacuum pressure was 1 × 10⁻⁶. －５The vacuum pressure was kept below Pa, and during film formation, oxygen gas was introduced into the vacuum chamber to a gas pressure of 6.8 Pa to form the second layer. During second layer formation, 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 film formation conditions (no substrate heating). In the first layer formation process, a continuous film of cesium tungsten oxide was further formed on top of the tungsten oxide film, which was the first layer formed on the first glass substrate. (1-6) In the third layer formation process, the target used was changed to an aluminum oxide target. The maximum vacuum pressure was 1 × 10⁻⁶ －５ The pressure was kept below Pa, and during film formation, oxygen gas was introduced into the vacuum chamber to a gas pressure of 0.5 Pa to form the third layer. During the formation of the third layer, 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 film formation conditions (no substrate heating). In the second layer formation process, a continuous aluminum oxide film was further formed on top of the cesium tungsten oxide film, which was the second layer formed on the first glass substrate. (1-7) Heat treatment process After the completion of the third layer formation process, the introduction of oxygen gas was stopped, and under an atmospheric 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 raising the temperature, it was held for 30 minutes to perform a heat treatment process, after which it was cooled down at 50°C / min to slowly cool to room temperature (heat treatment process). (1-8) Fourth 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.

[0100] In the fourth 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 third layer 14 in that order. Then, after heating to 80°C for temporary bonding, the bonding was performed at 140°C and 14 kg / cm². ２The bonding was performed using an autoclave, and the fourth layer 15 and the second glass substrate 16 were laminated to create a 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 with the deposited film using the measurement method described in "(1) X-ray diffraction pattern". Compounds identified from the X-ray diffraction pattern are listed in the column for substances detected from XRD in Table 1.

[0101] As shown in Table 1, the compound contained in the composite structure is tungsten oxide (o-WO) contained in the first layer 12. ３ ) and the Cs contained in the second layer 13 ０．３３ WO ３ It was identified as Cs ０．３３ WO ３ Since it was identified, it was confirmed that the third layer 14 suppressed the oxidative degradation of the second layer 13 by atmospheric oxygen. 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 WO of the Matrix ３ Since it has the same crystal system and nearly equivalent lattice constants, it does not create a large strain field in its surroundings, and therefore does not increase the haze of the composite structure 10. Rather, it is thought to have the effect of improving the heat shielding properties.

[0102] The third layer 14 contains Al ２ O ３ Regarding this, no peak was observed because it is amorphous. (2-2) Optical properties As shown in Table 1, the visible light transmittance was 60.32%, the solar transmittance was 32.01%, and the maximum reflectance at wavelengths from 780 nm to 2600 nm was 59.69%. 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 excellent heat shielding properties.

[0103] Furthermore, it was confirmed that the haze was also extremely low at 1.3%. [Example 2] (1) Fabrication of a laminated structure In Example 2, as shown in Figure 2, a laminated structure was fabricated by sequentially stacking a base layer 17, a first layer 12, a second layer 13, a third layer 14, a fourth layer 15, and a second glass substrate 16 on a first glass substrate 11, and the structure was evaluated.

[0104] Specifically, in the base layer formation process, an aluminum oxide target was used to form the base layer 17.

[0105] The subsoil formation process was carried out under the following conditions and procedures.

[0106] An aluminum oxide target was placed inside the vacuum chamber of a pulsed laser deposition system (Pascal PAC-LMBE). The maximum vacuum pressure was 1 × 10⁻¹⁶. －５ The pressure was kept below Pa, and during film formation, oxygen gas was introduced into the vacuum chamber to a gas pressure of 0.5 Pa, and a base layer 17 was formed on the first glass substrate 11 made of soda glass.

[0107] The irradiation laser used was a KrF laser (wavelength 248 nm, pulse width 25 ns), with a laser power of 150 mJ, a laser frequency of 4 Hz, and a laser irradiation time of 10 minutes, under room temperature film deposition conditions (no substrate heating).

[0108] Under the above conditions, in the underlayer formation process, a continuous film of aluminum oxide was formed on the first glass substrate (underlayer formation process).

[0109] The first layer formation process was carried out under the same conditions as in Example 1, except that instead of the first glass substrate, the first layer was formed on top of the aluminum oxide film, which was the underlayer formed on the first glass substrate in the underlayer formation process. The second layer formation process, third layer formation process, heat treatment process, fourth layer formation process, and second glass substrate installation process were also carried out under the same conditions as in Example 1 to produce the composite structure, so the explanation is omitted. (2) 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 The X-ray diffraction pattern was measured for the composite structure of Example 2 with the X-ray diffraction pattern formed, according to 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.

[0110] As shown in Table 1, the compound contained in the composite structure is tungsten oxide (o-WO) contained in 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 WO of the Matrix ３ Since it has the same crystal system and nearly equivalent lattice constants, it does not create a large strain field in its surroundings, and therefore does not increase the haze of the composite structure 10. Rather, it is thought to have the effect of improving the heat shielding properties.

[0111] Al contained in the base layer 17 and the third layer 14 ２ O ３Regarding this, no peak was observed because it is amorphous. (2-2) Optical properties As shown in Table 1, the visible light transmittance was 61.84%, the solar transmittance was 39.58%, and the maximum reflectance at wavelengths from 780 nm to 2600 nm was 64.53%. Therefore, it was confirmed that the composite structure obtained in Example 2 has excellent transmittance in the visible light region, excellent reflectivity in the near-infrared region, and excellent heat shielding properties.

[0112] Furthermore, it was confirmed that the haze was also extremely low at 0.9%. [Comparative Example 1] (1) Fabrication of the composite structure In Comparative Example 1, the third layer formation process was not performed, and the heat treatment process was performed after the second layer formation process. Except for the above, the composite structure was manufactured under the same conditions and procedures as in Example 1. (2) Evaluation results The composite structure obtained in Comparative 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 Comparative Example 1 with the X-ray diffraction pattern deposited, 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.

[0113] As shown in Table 1, the compound contained in the composite structure is o-WO contained in the first layer 12. ３ Besides Na ０．０２ WO ２．８ And, Na ２ W ２ O ７ It was identified.

[0114] o-WO ３ And, Na ０．０２ WO ２．８ And, Na ２ W ２ O ７ This refers to the oxygen in the atmosphere and the components contained in the glass substrate, and the WO contained in the first layer 12. ３ and Cs contained in the second layer 13 ０．３３ WO ３ It is thought that it was produced by a reaction between and . Because there is no third layer, oxidation of the second layer proceeds, and Cs ０．３３ WO ３It is thought that the substance could not be identified. (2-2) Optical properties As shown in Table 1, the visible light transmittance was 88.19%, the solar transmittance was 85.32%, and the maximum reflectance in the wavelength range of 780 nm to 2600 nm was 25.92%. Therefore, it was confirmed that the composite structure obtained in Comparative Example 1 had excellent transmittance in the visible light region, but its reflectivity was degraded and its heat shielding effect was weakened. It was also confirmed that the haze was high at 7.5%. The decrease in reflectance and increase in haze is thought to be due to the reaction between oxygen in the atmosphere, the first glass substrate 11, and the tungsten bronze contained in the second and first layers, as the heat shielding film of Comparative Example 1 does not have a third layer, and the products produced by this reaction.

[0115] Examples of embodiments of the present disclosure are as follows: <1> A first glass substrate, a first layer, a second layer, a third layer, and a second glass substrate, wherein the first layer is crystalline and has the general formula WO ３－ｘ The second layer contains tungsten oxide represented by (0 ≤ x ≤ 0.28), the third layer contains tungsten bronze, and the third layer contains 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<1> A composite structure comprising one or more compounds selected from the TiN group, arranged in the order of the first layer, the second layer, the third layer, and the second glass substrate from a position close to the first glass substrate. <2> The composite structure according to <1>, further comprising a fourth layer between the third layer and the second glass substrate, wherein the fourth 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, the average film thickness of the second layer is 5 nm or more and 1200 nm or less, and the average film thickness of the third layer is 5 nm or more and 1200 nm or less. <4> A base layer comprising the first glass substrate and the second layer, wherein the base layer is of the general formula SiO ａ N ｂ A composite structure according to any one of <1> to <3>, comprising silicon oxynitride represented by and one or more selected from aluminum oxide. <5> A composite structure according to any one of <1> to <4>, wherein the haze is 0.01% or more and 6.0% or less. <6> A composite structure according to any one of <1> to <5>, wherein the visible light transmittance is 20% or more and 90% or less. <7> A composite structure according to any one of <1> to <6>, wherein the solar transmittance is 50% or less. <8> A laminate formation step comprising a first layer formation step, a second layer formation step, and a third layer formation step, wherein a laminate is formed by laminating a first layer, a second layer, and a third layer on a first glass substrate, and a second glass substrate installation step is set on the third layer, wherein in the first layer formation step, a laminate of the general formula WO ３－ｘ A first layer containing tungsten oxide represented by (0 ≤ x ≤ 0.28) is formed, and in the second layer formation step, a second layer containing tungsten bronze is formed on the first layer, and in the third layer formation step, SiO is formed on the second layer. ２ , TiO ２ WO ３ , Nb ２ O ５ Al ２ O ３ , ZrO ２ Ta ２ O５ , SnO ２ Si ３ N ４ LaB ６ A method for manufacturing a composite structure, comprising forming a third layer containing one or more compounds selected from the group of TiN compounds. <9> The method for manufacturing a composite structure according to <8>, wherein in the laminate formation step, the first layer, the second layer, and the third 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). <10> The method for manufacturing a composite structure according to <8> or <9>, further comprising a heat treatment step of heat treating the laminate in an oxygen-containing atmosphere. <11> The method for manufacturing a composite structure according to <10>, wherein the heat treatment step is performed at a heat treatment temperature of 300°C or more and 1000°C or less.

[0116] This application claims priority based on Japanese Patent Application No. 2024-210766, filed with the Japan Patent Office on December 3, 2024, and the entire contents of Japanese Patent Application No. 2024-210766 are incorporated herein by reference.

[0117] 10 Laminated structure 20 Laminated structure 11 First glass substrate T11 Average thickness 12 First layer T12 Average film thickness 13 Second layer T13 Average film thickness 14 Third layer T14 Average film thickness 15 Fourth layer T15 Average film thickness 16 Second glass substrate T16 Average thickness 17 Underlayer 30 Flow diagram S1 First layer formation process S2 Second layer formation process S3 Third layer formation process S4 Heat treatment process S5 Second glass substrate installation process

Claims

1. It has a first glass substrate, a first layer, a second layer, a third layer, and a second glass substrate, and the first layer contains tungsten oxide represented by the general formula WO ３－ｘ (0 ≤ x ≤ 0.28), the second layer contains tungsten bronze, and the third layer contains 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 , TiN, and contains one or more selected from the group of compounds, and is an assembled structure arranged in the order of the first layer, the second layer, the third layer, and the second glass substrate from a position close to the first glass substrate.

2. The composite structure according to claim 1, further comprising a fourth layer between the third layer and the second glass substrate, wherein the fourth 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, the average film thickness of the second layer is 5 nm or more and 1200 nm or less, and the average film thickness of the third layer is 5 nm or more and 1200 nm or less.

4. The first glass substrate and the second layer have an underlayer, the underlayer being of the general formula SiO ａ N ｂ The composite structure according to claim 1 or claim 2, comprising silicon oxynitride represented by and one or more selected from aluminum oxide.

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

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

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

8. A laminate formation step comprising a first layer formation step, a second layer formation step, and a third layer formation step, wherein a laminate is formed by laminating a first layer, a second layer, and a third layer on a first glass substrate, and a second glass substrate installation step is set on the third layer, wherein in the first layer formation step, a general formula WO ３－ｘ A first layer containing tungsten oxide represented by (0 ≤ x ≤ 0.28) is formed, and in the second layer formation step, a second layer containing tungsten bronze is formed on the first layer, and in the third layer formation step, SiO is formed on the second layer. 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 A method for producing a composite structure, comprising forming a third layer containing one or more compounds selected from the group of TiN compounds.

9. The method for manufacturing a laminated structure according to claim 8, wherein in the laminate formation step, the first layer, the second layer, and the third 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).

10. A method for manufacturing a laminated structure according to claim 8 or 9, further comprising a heat treatment step of heat-treating the laminate in an oxygen-containing atmosphere.

11. The method for manufacturing a composite structure according to claim 10, wherein the heat treatment step is performed at a heat treatment temperature of 300°C or more and 1000°C or less.

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