TWM576534U - Composite insulation structure - Google Patents

Abstract

The invention provides a composite thermal insulation structure, which includes a first transparent substrate layer, a second transparent substrate layer, and a near-infrared layer disposed between the first transparent substrate layer and the second transparent substrate layer. The light-shielding layer and the near-infrared light-shielding layer are formed by fixing a plurality of tungsten oxide-containing nano particles distributed on polyethylene terephthalate. This heat-insulating structure does not darken in the sun, so it has both heat-insulation and lighting properties.

Description

Composite insulation structure

This creation is about a thermal insulation structure, and in particular a composite thermal insulation structure with a near infrared light shielding layer.

Glued glass is made by using high temperature and high pressure, sandwiching a strong and thermoplastic resin intermediate film between two pieces of glass. For example, glued glass can sandwich a strong and adhesive interlayer film in the middle, so it is not easy to be penetrated under impact, and its glass sheet is not easy to fly after being broken, so it has higher shock resistance than other types of glass Anti-theft, anti-explosion, anti-elastic.

Various properties can be added to the resin interlayer of glued glass. For example, the resin interlayer film can reduce the infrared rays in sunlight, which can save air-conditioning equipment and electricity, and increase the comfort of living environment.

In order to reduce the infrared rays in sunlight, the previous technology will use tungsten metal oxide to achieve the effect of heat insulation. However, tungsten metal oxide is not resistant to ultraviolet light in sunlight, which will cause valence electron transfer and discoloration, which causes discoloration of the prior art laminated glass, which causes troubles in use.

Low tungsten oxide (tungsten suboxide (WO _3-x )), tungsten bronze (tungsten bronze), or tungsten trioxide itself can block high heat. These tungsten compounds can be insulated in the sun after being mixed with organic resins, but organic resins easily decompose to generate electrons and hydrogen ions, and thus easily undergo redox reactions with tungsten compounds, causing the tungsten compounds to become darker in color. In an example, tungsten trioxide, a redox reaction as follows: WO ₃ ^{(transparent) + xH + + xe - →} H x WO 3 ( blue). Due to this phenomenon, these tungsten compounds cannot have both heat insulation and lighting properties, thereby reducing their application value in the heat insulation related industries.

The conventional manufacturing method of heat-insulating glued glass is mostly to directly add heat-insulating / heat-absorbing filler to PVB or EVA resin, or apply heat-insulating / heat-absorbing coating to PVB / EVA sheet, and then use two adhesive layers to glue on In the glass. In this kind of manufacturing method, it is necessary to add multiple and complicated light stabilizers, inhibitors, etc. in order to extend the life of the tungsten-containing heat insulation / endothermic filler.

Please refer to Chinese mainland patent application number CN200880101701.7, and propose a glass interlayer, which contains a polymer layer formed by tungsten oxide and benzotriazole groups. Although this glass interlayer has a thermal insulation effect, the color will darken for a long time in the sun and cannot provide lighting, which limits its applicability. According to the published information of this patent, in Table 1 of Example 1 on page 8 of the specification, after 500 hours of unadded light, the visible light change rate is 42.8%; if not added enough, the change rate is also 20% or more.

In addition, some methods are coated with silicon oxide on the surface of the tungsten-containing heat-insulating / endothermic filler particles.

Please refer to J. Mater. Chem. C, 2015, 3, 8050-8060. Xianzhe Zeng et al. Proposed that nano particles formed by coating SiO ₂ with Cs _x WO ₃ can be used as a coating. Although this coating has thermal insulation It is not easy to change color and light, but the coating method of nano particles is too complicated, which affects its applicability.

In addition, in the existing manufacturing method, a heavy metal magnesium salt is used as a stabilizer, which not only has environmental problems, but also requires more complicated processes to cover and protect the tungsten-containing heat insulation / endothermic filler, which has a high cost.

Therefore, it is one of the problems actively solved by those skilled in the art to improve the heat insulation structure containing the tungsten compound.

The purpose of this creation is to propose a composite thermal insulation structure that does not change color after a long period of time in the sun, and at the same time has both thermal insulation and lighting characteristics.

Another purpose of this creation is to provide a composite thermal insulation structure, which solves the problem that the tungsten metal oxide in the thermal insulation layer is not resistant to ultraviolet light in sunlight in the prior art, resulting in valence electron transfer and discoloration.

Another purpose of this creation is to provide a composite thermal insulation structure that is less likely to change color after sunlight.

Another purpose of this creation is to provide a composite heat-insulating structure with infrared light absorption and good weather resistance. It can be used for transparent windows, curtain walls and skylights in buildings, agriculture and vehicles for a long time. And has the effect of greatly reducing the infrared heat source entering the room.

Another purpose of this creation is to provide a composite thermal insulation structure based on the applicant's patented polyethylene terephthalate (PET) film. Add to PET, and then glue with PVB or EVA to solve the problem of UV discoloration of tungsten-containing heat insulation / endothermic filler.

Another purpose of this creation is to provide a composite heat-insulating structure, extruding a three-layer structure by co-extrusion, and protecting the heat-insulating PET with pure PET, in order to carry out a simple, fast and industrial production method.

Therefore, the present invention proposes a composite thermal insulation structure, which includes a first transparent substrate layer, a second transparent substrate layer, and a first transparent substrate layer and a second transparent substrate layer. The near-infrared light shielding layer is formed by a plurality of tungsten oxide-containing nano particles distributed and fixed on polyethylene terephthalate (PET).

In an embodiment of the present invention, the composite heat-insulating structure further includes: a first adhesive layer disposed between the first transparent substrate layer and the near-infrared light shielding layer; and a second The adhesive layer is disposed between the second transparent substrate layer and the near-infrared light shielding layer.

In an embodiment of the present invention, the composite heat-insulating structure further includes: a first protective layer disposed between the first transparent substrate layer and the near-infrared light shielding layer; and a second The protective layer is disposed between the second transparent substrate layer and the near-infrared light shielding layer.

In an embodiment of the present invention, the composite heat-insulating structure, wherein the first transparent substrate layer is selected from a glass, a polycarbonate plate, and a polymethyl methacrylate (PMMA) plate. In the formed group, the second transparent substrate layer is selected from the group consisting of a glass, a polycarbonate plate, and a polyacrylate plate.

In an embodiment of the present invention, the composite heat-insulating structure, wherein the first adhesive layer is selected from the group consisting of a polyvinyl butyral (PVB) film and an ethylene-vinyl acetate copolymer. A group consisting of an acetate (EVA) film and a polyurethane (PU) film. The second adhesive layer is selected from the group consisting of a polyvinyl butyral film, an ethylene-vinyl acetate copolymer film, and a polyamino group. A group of formate films.

In an embodiment of the present invention, in the composite thermal insulation structure, the first protective layer is a polyethylene terephthalate layer, and the second protective layer is a polyethylene terephthalate layer.

In an embodiment of the present invention, in the composite heat-insulating structure, the first protective layer, the second protective layer, and the near-infrared light shielding layer are formed together by a co-extrusion method.

In an embodiment of the present invention, the composite thermal insulation structure, wherein the near-infrared light shielding layer includes the polyethylene terephthalate in an amount of 80% to 99.99% by weight, and 0.01% To 20% of the plurality of nano-particles of tungsten-containing oxide.

In an embodiment of the present invention, the composite heat-insulating structure, wherein the near-infrared light shielding layer includes a plurality of nano-particles containing tungsten oxide, which are dispersed and fixed at a weight of 0.01 to 10 grams. Square meters of this polyethylene terephthalate.

In an embodiment of the present invention, the composite heat-insulating structure, wherein the nano particles of the tungsten-containing oxide are selected from the group consisting of low tungsten oxide nano particles, tungsten trioxide nano particles, and tungsten bronze nano particles. A group of rice particles; the low tungsten oxide is represented by WO _x , W represents tungsten, O represents oxygen, x represents the number of atoms of oxygen, 2.2 ≦ x <3; the tungsten bronze is represented by A _y WO _z , A represents the main group element, W represents the tungsten element, O represents the oxygen element, y represents the number of atoms of the main group element, 0.1 ≦ y ≦ 1, z represents the number of atoms of the oxygen element, and 2.2 ≦ x ≦ 3.

In an embodiment of the present invention, the composite thermal insulation structure described in item, wherein the main group elements are lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), aluminum (Al), gallium (Ga), carbon (C), silicon (Si), tin (Sn), antimony (Sb), fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

In an embodiment of the present invention, the composite thermal insulation structure, wherein the chemical formula of the low tungsten oxide is WO _2.72 .

In an embodiment of the present invention, the composite thermal insulation structure, wherein the chemical formula of the tungsten bronze is Cs _0.33 WO ₃ .

In an embodiment of the present invention, in the composite heat-insulating structure, a thickness of the near-infrared light shielding layer is 1 to 1000 μm.

In an embodiment of the present invention, the composite thermal insulation structure, wherein the thickness of the near-infrared light shielding layer is 12 to 250 μm.

In an embodiment of the present invention, in the composite heat-insulating structure, a particle diameter of the nano-particles of the tungsten-containing oxide is 1 to 800 nm.

In an embodiment of the present invention, the thickness of the first adhesive layer is 0.38 to 1.52 mm, and the thickness of the second adhesive layer is 0.38 to 1.52 mm. In particular, there are four thicknesses of 0.38, 0.76, 1.14, and 1.52 mm.

In an embodiment of the present invention, the composite heat-insulating structure, wherein the composite heat-insulating structure is irradiated with ultraviolet light having a wavelength of 310 nm and an intensity of 0.63 W / m ² for 8 hours at a temperature of 60 ° C. or lower, and then After 50 hours of water condensing treatment for 4 hours and repeated cycle treatment for more than 500 hours, the composite thermal insulation structure is substantially transparent.

In an embodiment of the present invention, the composite heat-insulating structure, wherein the composite heat-insulating structure is irradiated with ultraviolet light having a wavelength of 310 nm and an intensity of 0.63 W / m ² for 8 hours at a temperature of 60 ° C. or lower, and then After 50 hours of water condensation treatment for 4 hours, after repeated cycle treatment for more than 500 hours, the discoloration rate of the composite thermal insulation structure is less than 1%.

According to this creation, polyethylene terephthalate can prevent redox reactions between tungsten-containing oxides and electrons and hydrogen ions so that the color does not darken. In this way, when the tungsten-containing oxide provides a thermal insulation effect, the proposed thermal insulation product can still provide lighting, thereby increasing the industrial application value of the thermal insulation product.

In order to make the above and / or other purposes, effects, and characteristics of this creation more comprehensible, the following describes the preferred embodiments in detail:

As shown in FIG. 1, it is a composite thermal insulation structure according to one embodiment of the creation. It has the characteristics of preventing high heat and light from discoloring at the same time, so it has both thermal insulation and lighting properties. In addition, the heat-insulating structure of this embodiment includes at least a first transparent substrate layer (11), a second transparent substrate layer (12), a near-infrared light shielding layer (13), and a first adhesive layer (14). ), And a second adhesive layer (15).

The first transparent substrate layer (11) and the second transparent substrate layer (12) can impart structural support to the heat-insulating structure, and examples thereof can be, but are not limited to, glass, polycarbonate plates, or polymers. Poly (methyl methacrylate) (PMMA) board. In addition, the thicknesses of the first transparent substrate layer (11) and the second transparent substrate layer (12) are preferably 2 to 19 mm individually.

The near-infrared light shielding layer (13) is arranged between the first transparent substrate layer (11) and the second transparent substrate layer (12), and the distribution of nano particles of a plurality of tungsten-containing oxides is fixed to the polymer pair. Formed by ethylene phthalate. Polyethylene terephthalate can avoid the oxidation-reduction reaction of nano particles of tungsten-containing oxides in contact with electrons and hydrogen ions, so nano particles of tungsten-containing oxides can be made without causing darkening of the color Gives heat-insulating structure the effect of blocking high heat. In addition, the thickness of the near-infrared light shielding layer (13) is preferably 12 to 250 μm, and more preferably 18 to 100 μm; based on the total weight of the near-infrared light shielding layer (13), nano particles containing tungsten oxide. It is preferably 0.01 to 20% by weight, and polyethylene terephthalate is preferably 80 to 99.99% by weight. Moreover, the polyethylene terephthalate contains 0.01 to 10 g of nano particles of tungsten-containing oxide per square meter of the total volume of the polyethylene terephthalate. In addition, examples of nano particles of tungsten-containing oxides can be, but are not limited to, low tungsten oxide nano particles, tungsten trioxide nano particles, or tungsten bronze nano particles; low tungsten oxide can be represented by WO _x , and W represents tungsten Element, O represents oxygen element, x represents the number of atoms of oxygen element, 2.2 ≦ x <3; tungsten bronze can be represented by A _y WO _z , and A represents main group elements, such as lithium (Li), sodium (Na), and potassium (K ), Rubidium (Rb), cesium (Cs), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), aluminum (Al), gallium (Ga), carbon (C), silicon (Si ), Tin (Sn), antimony (Sb), fluorine (F), chlorine (Cl), bromine (Br), or iodine (I), W represents tungsten, O represents oxygen, and y represents atoms of main group elements Number, 0.1 ≦ y ≦ 1, z represents the number of atoms of the oxygen element, and 2.2 ≦ x ≦ 3.

The first adhesive layer (14) is disposed between the first transparent substrate layer (11) and the near-infrared light shielding layer (13), and it imparts the near-infrared light shielding layer (13) to the first transparent substrate layer (11). On the adhesion. The thickness of the first adhesive layer (14) is preferably 0.38 to 0.76 mm, and examples thereof may be, but are not limited to, a polyvinyl butyral (PVB) film or an ethylene vinyl acetate copolymer (ethylene vinyl acetate (EVA) film and polyurethane (PU). It should be noted that in addition to improving the adhesion between the layers, polyvinyl butyral has other characteristics such as heat resistance, cold resistance, humidity resistance, and high mechanical strength, so it can improve the overall application of the thermal insulation structure. Sex.

The second adhesive layer (15) is disposed between the second transparent substrate layer (12) and the near-infrared light shielding layer (13). It can be understood that the efficacy and related features are as described in the first adhesive layer (14), and will not be repeated here.

As shown in FIG. 2, it is a composite thermal insulation structure according to another embodiment of the present invention. The efficacy and related features are as described in the previous embodiment, but the differences are as follows:

A first protective layer (16) is disposed between the first transparent substrate layer (11) and the near-infrared light shielding layer (13), and a second transparent substrate layer (12) and the near-infrared light shielding layer (13) A second protective layer (17) is provided, and these protective layers can ensure that the nanoparticles of tungsten-containing oxide in the near-infrared light shielding layer (13) do not contact with electrons and hydrogen ions to cause a redox reaction. In this way, the characteristics of the heat-insulating structure without discoloration can be more stabilized. More specifically, the first protective layer (16) is disposed between the first adhesive layer (14) and the near-infrared light shielding layer (13), and the second protective layer (17) is disposed on the second adhesive layer (15) And the near-infrared light shielding layer (13). Examples of the first protective layer (16) and the second protective layer (17) may be, but are not limited to, a polyethylene terephthalate layer. The advantage of using a polyethylene terephthalate layer is that it can be used with near infrared The light shielding layer (13) is formed together by a co-extrusion method, thereby achieving the purpose of rapid process.

The following examples are given to illustrate this creation:

The near-infrared light shielding layer composed of nano particles of tungsten-containing oxide and polyethylene terephthalate mixed and fixed in the following examples was prepared by the creator, and can refer to the Republic of China Invention Patent Application No. 103120233; Vinyl butyral and ethylene-vinyl acetate copolymers are commercially available and can be purchased from Solutia, Trosifol, Sekesui, Dupont, Jiantao, Formosa, Deyuan; glass is commercially available and can be purchased from Taiwan Glass, Asahi Glass (AGC). Table 1 shows the structural combinations of different examples, and the layers are sequentially stacked. Table 1. Composition and optical characteristics of the thermal insulation structure of each example         <TABLE border = "1" borderColor = "# 000000" width = "85%"> <TBODY> <tr> <td> </ td> <td> Structure composition </ td> <td> Change rate of penetration ( %) </ Td> </ tr> <tr> <td> Example 1 </ td> <td> 2mm glass / 0.38mm polyvinyl butyral layer / 18μm near infrared light shielding layer (including WO <sub > 2.72 </ sub> nano particles) /0.38mm polyvinyl butyral layer / 2mm glass </ td> <td> 0.2 </ td> </ tr> <tr> <td> Example 2 </ td> <td> 3mm glass / 0.38mm ethylene-vinyl acetate copolymer layer / 18μm near infrared light shielding layer (including WO <sub> 2.72 </ sub> nano particles) /0.38mm ethylene-vinyl acetate copolymer Layer / 3mm glass </ td> <td> 0.1 </ td> </ tr> <tr> <td> Example 3 </ td> <td> 5mm glass / 0.38mm polyvinyl butyral layer / 23μm Near-infrared light shielding layer (including Cs <sub> 0.33 </ sub> WO <sub> 3 </ sub> nano particles) /0.38mm polyvinyl butyral layer / 5mm glass </ td> <td> 0.3 </ td> </ tr> <tr> <td> Example 4 </ td> <td> 6mm glass / 0.38mm ethylene-vinyl acetate copolymer layer / 23μm near-infrared light shielding layer (including WO <sub> 2.72 </ sub> nano particles) /0.38mm ethylene-vinyl acetate copolymer layer / 6mm glass </ td> <td> 0.4 </ td> </ tr> <tr> <td> Example 5 </ td> <td> 10mm glass / 0.76mm polyvinyl butyral layer / 50μm near infrared light shielding layer (including Cs <sub> 0.33 </ sub> WO <sub> 3 </ sub> Nano particles) /0.76mm polyvinyl butyral layer / 10mm glass </ td> <td> 0.5 </ td> </ tr> <tr> <td> Example 6 </ td> <td > 12mm glass / 1.14mm ethylene-vinyl acetate copolymer layer / 50μm near infrared light shielding layer (including Cs <sub> 0.33 </ sub> WO <sub> 3 </ sub> nanoparticles) /1.14mm ethylene- Vinyl acetate copolymer layer / 12mm glass </ td> <td> 0.4 </ td> </ tr> <tr> <td> Example 7 </ td> <td> 15mm glass / 1.52mm polyvinyl alcohol Butyraldehyde layer / 100μm near infrared light shielding layer (including Cs <sub> 0.33 </ sub> WO <sub> 3 </ sub> nano particles) /1.52mm polyvinyl butyral layer / 15mm glass </ td > <td> 0.8 </ td> </ tr> <tr> <td> Example 8 </ td> <td> 19mm glass / 1.52mm ethylene-vinyl acetate copolymer layer / 188μm near infrared light shielding layer ( Cs <sub> 0.33 </ sub> WO <sub> 3 </ sub> nano particles) /1.52mm ethylene-vinyl acetate copolymer layer / 19mm glass </ td> <td> 0.6 </ td> < / tr> <tr> <td> Comparative Example 1 </ td> <td> 5mm glass / 0.76mm polyvinyl butyral layer (containing 0.2wt% Cs <sub> 0.3 3 </ sub> WO <sub> 3 </ sub> nanometer particles) / 5mm glass </ td> <td> 27.3 </ td> </ tr> <tr> <td> Comparative Example 2 </ td> <td> 6mm glass / 0.76mm ethylene-vinyl acetate copolymer layer (containing 0.2wt% WO <sub> 2.72 </ sub> nano particles) / 6mm glass </ td> <td> 36.8 </ td> < / tr> </ TBODY> </ TABLE>

Each of the above thermal insulation structures was irradiated with UV at a wavelength of 310 nm and an intensity of 0.63 W / m ² at 60 ° C. for 8 hours, and then treated with water at 50 ° C. for 4 hours. After repeated cycles of more than 500 hours, each test The rate of change in visible light penetration of a heat-insulating structure is less than 1%. The results are shown in Table 1. It can be seen that the examples have almost no photochromic properties compared to the comparative examples, which means that they are substantially transparent.

In summary, the thermal insulation structure of this creation is not easy to change color in the sun, so it can be called a thermal insulation structure with lighting properties. In this way, it can be applied to objects that need to be insulated, such as automobiles and buildings.

This creation has been disclosed using the above preferred embodiments, but it is not intended to limit this creation. Those with ordinary knowledge in the technical field to which this creation belongs should clearly understand that this creation is not limited to the details of the above illustrative implementations. This creation It can be implemented in other specific forms without departing from the basic spirit of the creation. The implementation is only to explain the creation, not to limit the creation. This creation is based on the scope of patent application, not the above description. The significance of the scope of patent application And all variations in the equal range are within the scope of this creation.

(11) ‧‧‧ the first transparent substrate layer

(12) ‧‧‧ second transparent substrate layer

(13) ‧‧‧Near infrared light shielding layer

(14) ‧‧‧ the first adhesive layer

(15) ‧‧‧Second Adhesive Layer

(16) ‧‧‧ the first protective layer

(17) ‧‧‧Second protective layer

The embodiment of the present invention will be described later with a brief description in combination with the drawings: FIG. 1 is a schematic cross-sectional view illustrating a composite thermal insulation structure according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view illustrating a composite thermal insulation structure according to another embodiment of the present invention.

Claims (19)

A composite thermal insulation structure includes: a first transparent substrate layer; a second transparent substrate layer; and a near-infrared light shielding layer disposed on the first transparent substrate layer and the second transparent substrate Between the material layers, a plurality of tungsten oxide-containing nano particles are distributed and fixed to polyethylene terephthalate (PET). The composite heat-insulating structure according to claim 1, further comprising: a first adhesive layer disposed between the first transparent substrate layer and the near-infrared light shielding layer; and a second adhesive layer Is disposed between the second transparent substrate layer and the near-infrared light shielding layer. The composite heat insulation structure according to claim 1, further comprising: a first protective layer disposed between the first transparent substrate layer and the near-infrared light shielding layer; and a second protective layer Is disposed between the second transparent substrate layer and the near-infrared light shielding layer. The composite heat-insulating structure according to claim 1, wherein the first transparent substrate layer is selected from the group consisting of glass, polycarbonate plates, and polymethyl methacrylate (PMMA) plates. Group, the second transparent substrate layer is selected from the group consisting of glass, polycarbonate plate, and polyacrylate plate. The composite heat-insulating structure according to item 2 of the claim, wherein the first adhesive layer is selected from the group consisting of a polyvinyl butyral (PVB) film and an ethylene-vinyl acetate copolymer (ethylene vinyl acetate, EVA) film and polyurethane (PU) group, the second adhesive layer is selected from the group consisting of polyvinyl butyral film, ethylene-vinyl acetate copolymer film, and polyurethane (polyurethane, PU). The composite thermal insulation structure according to claim 3, wherein the first protective layer is a polyethylene terephthalate layer, and the second protective layer is a polyethylene terephthalate layer. The composite thermal insulation structure according to claim 6, wherein the first protective layer, the second protective layer, and the near-infrared light shielding layer are formed together by a co-extrusion method. The composite thermal insulation structure according to claim 1, wherein the near-infrared light shielding layer includes the polyethylene terephthalate in an amount of 80 to 99.99% by weight, and 0.01 to 20% in an amount of The plurality of nano particles of tungsten-containing oxide. The composite heat-insulating structure according to claim 8, wherein the near-infrared light shielding layer comprises nano-particles of the plurality of tungsten-containing oxides dispersed in a weight of 0.01 to 10 grams and fixed at a square centimeter. In the polyethylene terephthalate. The composite heat-insulating structure according to claim 1, wherein the nano particles of the tungsten-containing oxide are selected from the group consisting of low tungsten oxide nano particles, tungsten trioxide nano particles, and tungsten bronze nano particles. The group consisting of: the low tungsten oxide is represented by WOx, W represents tungsten, O represents oxygen, x represents the number of atoms of oxygen, 2.2 ≦ x <3; the tungsten bronze is represented by AyWOz, and A represents the main group element , W represents tungsten, O represents oxygen, y represents the number of atoms of the main group element, 0.1 ≦ y ≦ 1, z represents the number of atoms of the oxygen element, and 2.2 ≦ x ≦ 3. The composite thermal insulation structure as described in claim 10, wherein the main group elements are lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), magnesium (Mg) , Calcium (Ca), strontium (Sr), barium (Ba), aluminum (Al), gallium (Ga), carbon (C), silicon (Si), tin (Sn), antimony (Sb), fluorine (F) , Chlorine (Cl), bromine (Br), or iodine (I). The composite thermal insulation structure according to claim 10, wherein the chemical formula of the low tungsten oxide is WO _2.72 . The composite heat insulation structure according to claim 11, wherein the chemical formula of the tungsten bronze is Cs _0.33 WO ₃ . The composite heat-insulating structure according to claim 1, wherein the thickness of the near-infrared light shielding layer is 1 to 1000 μm. The composite thermal insulation structure according to claim 14, wherein the thickness of the near-infrared light shielding layer is 12 to 250 μm. The composite thermal insulation structure according to claim 1, wherein the particle size of the nano particles of the tungsten-containing oxide is 1 to 800 nm. The composite thermal insulation structure according to item 2 of the claim, wherein the thickness of the first adhesive layer is 0.38 to 1.52 mm, and the thickness of the second adhesive layer is 0.38 to 1.52 mm. The composite thermal insulation structure according to item 1 of the claim, wherein the composite thermal insulation structure is irradiated with ultraviolet light having a wavelength of 310 nm and an intensity of 0.63 W / m ² for 8 hours at a temperature of 60 ° C or lower, and then at a temperature of 50 The water-condensation treatment at 4 ° C for 4 hours, and the repeated heat treatment for more than 500 hours, the composite heat-insulating structure is substantially transparent. The composite thermal insulation structure according to item 1 of the claim, wherein the composite thermal insulation structure is irradiated with ultraviolet light having a wavelength of 310 nm and an intensity of 0.63 W / m ² for 8 hours at a temperature of 60 ° C or lower, and then at a temperature of 50 After 4 hours of water condensing treatment at ℃, and after more than 500 hours of repeated cycle treatment, the discoloration rate of the composite thermal insulation structure is less than 1%.