TWI680946B - Infrared shielding body and infrared absorption material thereof - Google Patents

Abstract

An infrared absorption material includes composite-tungsten-oxide nanoparticles, the general expression of which is Cs_xSn_yGe_zWO₃, where X, Y and Z are less than 1, Cs refers to caesium, Sn refers to tin, Ge represents germanium, W refers to tungsten, and O refers to oxygen. The effect of absorption about an infrared light having a wavelength which is larger than 1500 nm can be improved by the composite-tungsten-oxide nanoparticles.

Description

Infrared shielding body and infrared absorbing material

Related application

The present invention is a division of Taiwan Patent Application No. 107119823 (application date: June 08, 2018), and its parent case is Taiwan Patent Application No. 103104032 (application date: February 07, 2014). The complete content of the application is included as part of the specification of the invention for reference.

The invention relates to a heat ray shielding body and its heat ray absorbing material, in particular to an infrared shielding body and its infrared absorbing material.

According to the press, the sun rays incident from the doors and windows of various buildings, vehicles, etc. include ultraviolet rays and infrared rays in addition to visible rays. Among them, near infrared rays with a wavelength of 800 to 2500 are also called heat rays, which cause the indoor temperature to rise. main reason.

To prevent this from happening, in recent years, we are actively developing shields that can fully absorb visible light and shield infrared rays at the same time to maintain brightness while suppressing indoor temperature rise. For example, early infrared blocking glass was mainly coated with metal (such as silver, aluminum) or metal oxide, and in order to effectively block infrared, this type of glass needs to be coated with a multi-layer film or using a sputtering method for coating, resulting in cost Not easy to lower.

Japanese Patent Application Publication No. 9-12338 reveals the use of sputtering method on the surface of transparent glass The composite tungsten oxide film is plated to achieve the effect of blocking infrared rays. However, when the sputtering method is used for coating, it needs to be operated under high temperature and vacuum conditions, resulting in a reduction in the yield of the coating on the glass and a reduction in manufacturing efficiency.

Japanese Patent Laid-Open No. 8-59300 discloses the use of composite tungsten oxide on glass to form glass with high visible light transmittance and high infrared blocking rate.

Japan's previous case No. 4110762 (B2) discloses the use of tungsten trioxide to make electrochromic elements. Tungsten trioxide is prepared by dissolving tungsten hexachloride in ethanol and directly evaporating ethanol and heating it at 100-500℃ .

Japan's previous case No. 2535790 (B2) disclosed that after dissolving ammonium metatungstate and water-soluble metal salts in water, it was first dried at 80-250°C, and then composite tungsten oxide was prepared at 300-700°C under a hydrogen atmosphere material. The composite tungsten oxide material can be applied to fuel cell electrode materials, catalyst materials and electrolytic device materials.

U.S. Patent No. 5,387,551 discloses that chemical vapor deposition is used to coat a transparent glass surface with an appropriate thickness of a tungsten oxide-doped fluorine film to achieve the effect of blocking infrared rays. However, this method not only has low production efficiency, but also requires high equipment costs.

U.S. Patent No. US20020090507 discloses an infrared film that can block infrared rays, which includes a UV-curable resin, metal nanoparticles that can absorb an irradiation wavelength of 1000-2500 nm, and metal nanoparticles that can absorb an irradiation wavelength of 700-1100 nm.

U.S. Pat. No. US20120138842 discloses a composite tungsten oxide microparticle, in which tungsten oxide is doped with a Group VIIIB metal to improve IR reflectance.

One object of the present invention is to provide a method for manufacturing composite tungsten oxide nanoparticles, which can uniformly dope a single element or multiple elements on tungsten oxide molecules, and pass a single Solution operation can produce uniform, high-quality nanoparticles in rapid industrial mass production.

Another object of the present invention is to provide an infrared absorbing material which, by doping a single element or multiple elements, distorts the spectrum of the composite molecule, and can fully absorb infrared rays with a wavelength greater than 1500 nm.

Still another object of the present invention is to provide an infrared shielding body that can fully absorb visible light and shield infrared rays, and has good optical and conductive properties.

Another technical solution adopted by the present invention is: an infrared absorbing material, which includes a plurality of composite tungsten oxide nanoparticles, and its general formula is: Cs _x Sn _y Ge _z WO ₃ ; wherein, X, Y and Z are less than 1. ; Cs means cesium; Sn means tin; Ge means germanium; W means tungsten; O means oxygen.

Another technical solution adopted by the present invention is: an infrared shielding body, which is made by mixing a nano slurry with a media resin, wherein the nano slurry includes the infrared absorption material and a dispersant.

In order to further understand the features and technical contents of the present invention, please refer to the following detailed description and drawings of the present invention. However, the drawings provided are for reference and explanation only, and are not intended to limit the present invention.

FIG. 1 is a schematic flow chart of the method for manufacturing composite tungsten oxide nanoparticles of the present invention.

2 is an X-ray diffraction pattern of composite tungsten oxide nanoparticles of the present invention.

FIG. 3 is a transmission spectrum chart of composite tungsten oxide nanoparticles of the present invention.

4 is a graph showing the life test trend of composite tungsten oxide nanoparticles of the present invention.

In view of the problem that tungsten oxide has the ability to absorb infrared light but is not easy to form nanoparticles, the present invention provides a simple and rapid method for preparing composite tungsten oxide nanoparticles. The composite tungsten oxide nanoparticles manufactured by this method can Has excellent infrared absorption characteristics and high visible light penetration.

The following is a description of the embodiments of the "infrared shielding body and its infrared absorbing material" disclosed by the present invention through specific specific examples. Those skilled in the art can understand the advantages and effects of the present invention from the contents disclosed in this specification. Through the implementation or application of other different specific embodiments, various details in this specification can also be based on different views and applications, without departing from the concept of the present invention to make various modifications and changes. In addition, the drawings of the present invention For the sake of simple illustration, not the actual size, it is stated in advance. The following embodiments will further describe the relevant technical content of the present invention, but the disclosed content is not intended to limit the scope of protection of the present invention.

Please refer to FIG. 1, which is a schematic flowchart of a method for manufacturing composite tungsten oxide nanoparticles according to an embodiment of the present invention. The method for manufacturing composite tungsten oxide nanoparticles of the present invention includes the following steps: Step S102, preparing a sol solution; Step S104, adjusting the pH value of the sol solution; Step S106, separating the gel by hypergravity; and Step S108 : Heat-treating the gel in a reducing atmosphere.

In step S102, a tungsten precursor and at least one metal precursor are dissolved in a solvent, and the temperature is stirred for a predetermined time to form the sol solution. When actually performing this step, the tungsten precursor can be dissolved in the solvent, and then the metal precursor can be added and stirred to completely dissolve it.

In this embodiment, the tungsten precursor may be, but not limited to, tungstic acid, ammonium metatungstate, tungsten tetrachloride, tungsten tetrabromide, tungsten hexachloride, tungsten dichloride, tungsten hexafluoride Or tungsten oxyfluoride. The metal precursor may be, but not limited to, IA-IIIA group (such as H, He, alkali metal, alkaline earth or rare earth elements) hydroxide, chloride, sulfate or nitrate and transition metal hydrogen Oxides, chlorides, sulfates or nitrates. The solvent may be, but not limited to, ether, methanol, ethanol, Isopropyl alcohol, n-butanol, 2-butanol, acetone or butanone.

In step S104, a modifier such as an organic or inorganic base is added dropwise to the sol solution until a gel is produced, wherein the tungsten precursor is hydrolyzed, condensed, polymerized, etc. in the sol state (sol) After the reaction, a gel state is gradually formed, so that the gel body includes a continuous network skeleton formed by tungsten oxide and IA-IIIA group metal ions and/or transition metal ions filled in the voids of the skeleton .

In step S106, the gel is separated by supergravity. In this step, the solvent and unreacted impurities are removed by centrifugation to obtain a mud-like gel. In a variant embodiment, this step can also use a vacuum oven or vacuum concentrator to evaporate all the solvent.

In step S108, the gel system is heated from room temperature to 400-600°C at a heating rate of 1-10°C per minute (preferably 3-5°C per minute) under a mixed atmosphere containing hydrogen and passive gas. (Preferably 580°C), and sintering at a temperature for 2-8 hours to make a crystalline phase.

It is worth noting that in a variant embodiment, the gel may be first mixed in a mixed atmosphere containing a precursor gas of IA-IIIA group and a passive gas at 1-10°C per minute (preferably per minute 3-5 ℃) heating rate from room temperature to 100-400 ℃ (preferably 400 ℃), and keep the temperature sintering for 1 hour, after doping the IVA-VIIA group element tungsten oxide molecules, and then the same temperature Continue heating to 400-600 ℃ (preferably 580 ℃), and sinter at a temperature of 2-8 hours in a mixed atmosphere containing hydrogen and passive gas, so as to obtain a crystalline composite oxide doped with single or multiple elements Tungsten nanoparticles.

The present invention also provides an infrared absorbing material, which includes crystalline composite tungsten oxide nanoparticles obtained through the above steps, and its general formula is: M1 _x M2 _y WO ₃ R _z or M1 _x WO ₃ R _y S _z . In the formula, W represents tungsten; O represents oxygen; M1, M2 represent IA-IIIA group or transition metal elements, M1, M2 are preferably K, Rb, Cs or Ba, but M1 is not equal to M2; R, S represents IVA-VIIA Group elements, R and S are preferably C, Si, Ge, Sn, N or Sb, but R is not equal to S; X, Y and Z are less than 1. It is worth noting that the doped elements can complement the absorption effect of tungsten oxide on infrared rays with a wavelength greater than 1500 nm.

Further, the present invention further proposes an infrared shielding body, which is made by mixing a nano slurry with a media resin, wherein the nano slurry includes the infrared absorption material and a dispersant.

In this embodiment, the method for preparing the infrared shielding body may include the following steps. First, the external absorption material and the dispersant are mixed in an appropriate solvent, wherein the dispersant may be a polymer acidic, polymer basic or polymer neutral dispersant. Next, the mixture obtained in the previous step is subjected to wet pulverization to form the nano slurry; then, after mixing the nano slurry with the media resin, the mixture obtained in the previous step is coated on A substrate surface, in which the media resin can be used alone or in combination with thermosetting resin, ultraviolet curing resin, electron beam curing resin, room temperature curing resin, thermoplastic resin, etc.

In order to enable those skilled in the art to easily understand the specific advantages or effects of the present invention, and make various modifications and changes without departing from the spirit of the present invention in order to implement or apply the present invention, a few are specifically listed below The experimental examples are used to explain in detail the manufacturing method of the composite tungsten oxide nanoparticles of the present invention, but the present invention is not limited thereto.

Embodiment 1: Dissolve tungsten hexachloride, cesium hydroxide, and potassium hydroxide in an aqueous ethanol solution, and add an appropriate amount of water in a dropwise manner until precipitation occurs. The chemical reaction formula is as follows: WCl ₆ +H ₂ O+CsOH+KOH → WOCl ₄ +K ⁺ +Cs ⁺ +HCl+H ₂ O

WOCl ₄ +Cs ⁺ +K ⁺ +HCl → WO ₃ (↓)+Cs ⁺ +K ⁺ +6HCl

Then use supergravity to separate most of the solution from the precipitate to obtain a muddy precipitate (gel) and then extract the solvent into a dry powder in a vacuum oven. Place the dried tungsten oxychloride cesium powder in a high-temperature furnace and use A certain proportion of bluff gas and hydrogen reduce its composite tungsten oxychloride potassium cesium to tungsten potassium cesium oxide. The process conditions are as follows: in a high-temperature furnace at a heating rate of 3-5 °C per minute, from room temperature to 580 °C, sintering at 580 °C for 2 hours. Thus, crystalline composite tungsten oxide nanoparticles can be obtained, and the chemical reaction formula is as follows: WOCl ₄ +WO ₂ Cl ₂ +Cs ⁺ +K ⁺ +3H ₂ O

→ Cs _x K _y WO ₃ +6HCl(↑)(X, Y<1)

Please refer to FIG. 2, it can be seen from XRD that it is a composite tungsten oxide crystal containing cesium and potassium. Finally, the appropriate proportion of solvent, dispersant and composite tungsten oxide powder is milled to nanoparticles with a particle size of less than 100 nm, and then a transparent resin is used to make a coating solution.

Example 2: Dissolve tungsten hexachloride, cesium hydroxide and rubidium hydroxide in an aqueous ethanol solution, and add an appropriate amount of water in a dropwise manner until precipitation occurs. The chemical reaction formula is as follows: WCl ₆ +H ₂ O+CsOH+RbOH → WOCl ₄ +Rb ⁺ +Cs ⁺ +HCl

WOCl ₄ +Cs ⁺ +Rb ⁺ +HCl → WO ₃ (↓)+Cs ⁺ +Rb ⁺ +6HCl

Then, use supergravity to separate most of the solution from the precipitate to obtain a muddy precipitate. Then extract the solvent into a dry powder in a vacuum oven. Place the dry tungsten oxychloride cesium powder in a high-temperature furnace and passivate it in a certain proportion Gas and hydrogen reduce its composite tungsten oxychloride rubidium cesium to tungsten rubidium cesium oxide. The process conditions are as follows: in a high-temperature furnace at a heating rate of 3-5 °C per minute, from room temperature to 580 °C, sintering at 580 °C for 2 hours. Thus, a composite tungsten oxide crystal containing cesium and rubidium can be obtained, and the chemical reaction formula is as follows: WOCl ₄ +WO ₂ Cl ₂ +Cs ⁺ +Rb ⁺ +3H ₂ O

→ Cs _x Rb _y WO ₃ +6HCl(↑)(X，Y<1)

Afterwards, the solvent, dispersant and composite tungsten oxide powder with appropriate formulation ratio are ground to nanoparticles with a particle size of less than 100 nm, and then a transparent resin is used to prepare a coating solution.

Embodiment 3: Dissolve tungsten hexachloride, cesium hydroxide, and barium hydroxide in an aqueous ethanol solution, and add an appropriate amount of water in a dropwise manner until precipitation occurs. The chemical reaction formula is as follows: WCl ₆ +H ₂ O+CsOH+B _a (OH) ₂ → WOCl ₄ +Ba ²⁺ +Cs ⁺ +HCl

WOCl ₄ +Cs ⁺ +Ba ²⁺ +HCl+H ₂ O → WO ₃ (↓)+Cs ⁺ +Ba ²⁺ +6HCl

Then use supergravity to separate most of the solution from the precipitate to obtain a muddy precipitate. Then extract the solvent into a dry powder in a vacuum oven, place the dry tungsten oxychloride powder in a high temperature furnace, and pass a certain proportion of inert gas With hydrogen, its composite tungsten cesium barium oxide is reduced to tungsten cesium barium oxide The process conditions are as follows: in a high-temperature furnace at a heating rate of 3-5 °C per minute, from room temperature to 580 °C, sintering at 580 °C for 2 hours. Thus, a composite tungsten oxide crystal containing cesium and barium can be obtained, and the chemical reaction formula is as follows: WOCl ₄ +WO ₂ Cl ₂ +Cs ⁺ +Ba ²⁺ +3H ₂ O

→ Cs _x Ba _y WO ₃ +6HCl(↑)(X, Y<1)

It can be seen from XRD that it is a composite tungsten oxide crystal containing cesium and barium. Finally, the appropriate proportion of solvent, dispersant and composite tungsten oxide powder is milled to nanoparticles with a particle size of less than 100 nm, and then a transparent resin is used to make a coating solution.

Example 4: Dissolve tungsten hexachloride, tin tetrachloride and cesium hydroxide directly in an aqueous ethanol solution, and add an appropriate amount of ammonia water in a dropwise manner until precipitation occurs. The chemical reaction formula is as follows: WCl ₆ +H ₂ O+C _s OH+SnCl ₄ → WOCl ₄ +C _s ⁺ +Sn ⁴⁺ +HCl

WOCl ₄ +Cs ⁺ +Sn ⁴⁺ +2HCl+NH ₃ (aq)

_{→ WO 3 (↓) + Cs} + + Sn 4+ + 6N + H 4 Cl -

Then use supergravity to separate most of the solution from the precipitate to obtain a muddy precipitate, wash off the ammonium salt with deionized water, then extract the solvent into a dry powder in a vacuum oven, and place the dry tungsten oxychloride cesium powder at high temperature In the furnace, with a certain proportion of inert gas and hydrogen, the composite tungsten cesium tin oxychloride is reduced to composite tungsten cesium tin oxide. The process conditions are as follows: in a high-temperature furnace at a heating rate of 3-5 °C per minute, from room temperature to 580 °C, sintering at 580 °C for 2 hours. Thus, crystalline composite tungsten oxide nanoparticles can be obtained, and the chemical reaction formula is as follows: WOCl ₄ +WO ₂ Cl ₂ +Cs ⁺ +Sn ⁴⁺ +3H ₂ O

→ Cs _x Sn _y WO ₃ +6HCl(↑)(X，Y<1)

It can be seen from XRD that it is a composite tungsten oxide crystal containing cesium and tin. Finally, the appropriate proportion of solvent, dispersant and composite tungsten oxide powder is milled to nanoparticles with a particle size of less than 100 nm, and then a transparent resin is used to make a coating solution.

In the fifth embodiment, tungsten hexachloride and cesium hydroxide are dissolved in an aqueous ethanol solution, and an appropriate amount of ammonia water is added dropwise until precipitation occurs. The chemical reaction formula is as follows: WCl ₆ +H ₂ O+CsOH → WOCl ₄ +Cs ⁺ +HCl+H ₂ O

WOCl ₄ +Cs ⁺ +6HCl+NH ₃ (aq)

→ WO ₃ (↓)+Cs ⁺ +6N ⁺ H ₄ Cl

Extract the solvent into a dry powder in a vacuum oven, place the powder of dry tungsten cesium oxychloride in a high-temperature furnace, and reduce the compound tungsten oxychloride cesium oxychloride to cesium tungsten oxide with a certain proportion of inert gas and hydrogen. The process conditions are as follows: in a high-temperature furnace at a heating rate of 3-5 °C per minute, from room temperature to 580 °C, sintering at 580 °C for 2 hours. Thus, crystalline composite tungsten oxide nanoparticles can be obtained, and the chemical reaction formula is as follows: WOCl ₄ +WO ₂ Cl ₂ +Cs ⁺ +N ⁺ H ₄ Cl+H ₂ O

→ Cs _x N _y WO ₃ +6HCl(↑)(X, Y<1)

It can be seen from elemental analysis that it is a composite tungsten oxide crystal containing cesium and nitrogen. Finally, the appropriate proportion of solvent, dispersant and composite tungsten oxide powder is milled to nanoparticles with a particle size of less than 100 nm, and then a transparent resin is used to make a coating solution.

Embodiment 6: Dissolve tungsten hexachloride, antimony chloride and cesium hydroxide in an aqueous ethanol solution, and add an appropriate amount of ammonia water in a dropwise manner until precipitation occurs. The chemical reaction formula is as follows: WCl ₆ +H ₂ O+CsOH+SbCl ₃ → WOCl ₄ +Cs ⁺ +Sb ³⁺ +HCl+H ₂ O

WOCl ₄ +Cs ⁺ +Sb ³⁺ +2HCl+NH ₃ (aq)

_{→ WO 3 (↓) + Cs} + + Sb 3+ + 6N + H 4 Cl -

Then use supergravity to separate most of the solution from the precipitate to obtain a muddy precipitate, wash off the ammonium salt with deionized water, and then extract the solvent into a dry powder in a vacuum oven. Place the dry tungsten oxychloride cesium antimony powder in In a high-temperature furnace, with a certain proportion of bluff gas and hydrogen, its composite tungsten oxychloride cesium antimony is reduced to tungsten cesium antimony oxide. The process conditions are as follows: in a high-temperature furnace at a heating rate of 3-5 °C per minute, from room temperature to 580 °C, sintering at 580 °C for 2 hours. Thus, crystalline composite tungsten oxide nanoparticles can be obtained, and the chemical reaction formula is as follows: WOCl ₄ +WO ₂ Cl ₂ +Cs ⁺ +Sb ³⁺ +3H ₂ O

→ Cs _x Sb _y WO ₃ +6HCl(↑)(X，Y<1)

It can be seen from XRD that it is a composite tungsten oxide crystal containing cesium and antimony. Finally, the appropriate proportion of solvent, dispersant and composite tungsten oxide powder is milled to nanoparticles with a particle size of less than 100 nm, and then a transparent resin is used to make a coating solution.

Embodiment 7: Dissolve tungsten hexachloride and cesium hydroxide in an ethanol aqueous solution, and add an appropriate amount of ammonia water in a dropwise manner until precipitation occurs. The chemical reaction formula is as follows: WCl ₆ +H ₂ O+CsOH → WOCl ₄ +Cs ⁺ +HCl+H ₂ O

WOCl ₄ +Cs ⁺ +2HCl+NH ₃ (aq)

→ WO ₃ (↓)+Cs ⁺ +6N ⁺ H ₄ Cl

Then use supergravity to separate most of the solution from the precipitate to obtain a muddy precipitate, wash off the ammonium salt with deionized water, then extract the solvent into a dry powder in a vacuum oven, and place the dry tungsten oxychloride cesium powder at high temperature In the furnace, at a heating rate of 3-5 ℃ per minute, firstly maintain the temperature at 400 ℃ for 1 hour and pass it in a certain ratio of inert gas and methane, and then in a certain ratio of inert gas and hydrogen to reduce the composite tungsten oxychloride cesium Tungsten oxide cesium. The process conditions are as follows: from room temperature to 580 ℃, sintering at 580 ℃ for 2 hours. Thus, crystalline composite tungsten oxide nanoparticles can be obtained, and the chemical reaction formula is as follows: WOCl ₄ +WO ₂ Cl ₂ +Cs ⁺ +CH ₄ +3H ₂ O

→ Cs _x C _y WO ₃ +6HCl(↑)+H ₂ O(X，Y<1)

It can be seen from elemental analysis that it is a composite tungsten oxide crystal containing cesium. Finally, the appropriate proportion of solvent, dispersant and composite tungsten oxide powder is milled to nanoparticles with a particle size of less than 100 nm, and then a transparent resin is used to make a coating solution.

Embodiment 8: Dissolve tungsten hexachloride, germanium tetrachloride and cesium hydroxide in an aqueous ethanol solution, and add an appropriate amount of ammonia water in a dropwise manner until precipitation occurs. The chemical reaction formula is as follows: WCl ₆ +H ₂ O+CsOH+GeCl ₄ → WOCl ₄ +Cs ⁺ +Ge ⁴⁺ +HCl+H ₂ O

WOCl ₄ +Cs ⁺ +Ge ⁴⁺ +2HCl+NH ₃ (aq)

_{→ WO 3 (↓) + Cs} + + Ge 4+ + 6N + H 4 Cl -

Then use supergravity to separate most of the solution from the precipitate to obtain a muddy precipitate, wash off the ammonium salt with deionized water, then extract the solvent into a dry powder in a vacuum oven, and place the dry tungsten oxychloride cesium powder at high temperature In the furnace, and with a certain proportion of bluff gas and hydrogen, the composite tungsten oxychloride cesium is reduced to cesium tungsten oxide. The process conditions are as follows: in a high-temperature furnace at a heating rate of 3-5 °C per minute, from room temperature to 580 °C, sintering at 580 °C for 2 hours. Thus, crystalline composite tungsten oxide nanoparticles can be obtained, and the chemical reaction formula is as follows: WOCl ₄ +WO ₂ Cl ₂ +Cs ⁺ +Ge ⁴⁺ +3H ₂ O

→ Cs _x Ge _y WO ₃ +6HCl(↑)(X，Y<1)

It can be seen from XRD that it is a composite tungsten oxide crystal containing cesium and germanium. Finally, the appropriate proportion of solvent, dispersant and composite tungsten oxide powder is milled to nanoparticles with a particle size of less than 100 nm, and then a transparent resin is used to make a coating solution.

Example 9: Dissolve tungsten hexachloride, tetraethylsiloxane and cesium hydroxide in an aqueous ethanol solution, and add an appropriate amount of ammonia water in a dropwise manner until precipitation occurs. The chemical reaction formula is as follows: WCl ₆ +H ₂ O+CsOH+Si(OEt) ₄ → WSi _y OCl ₄ +Cs ⁺ +HCl+H ₂ O

WSi _y OCl ₄ +Cs ⁺ +2HCl+NH ₃ (aq)

→ WSi _y O ₃ (↓)+Cs ⁺ +6N ⁺ H ₄ Cl

Then use supergravity to separate most of the solution from the precipitate to obtain a muddy precipitate, wash off the ammonium salt with deionized water, then extract the solvent into a dry powder in a vacuum oven, and place the dry tungsten oxychloride silicon powder at high temperature In the furnace, with a certain proportion of passive gas and hydrogen, the composite tungsten silicon oxychloride is reduced to tungsten silicon oxide. The process conditions are as follows: in a high-temperature furnace at a heating rate of 3-5 °C per minute, from room temperature to 580 °C, sintering at 580 °C for 2 hours. Thus, crystalline composite tungsten oxide nanoparticles can be obtained, and the chemical reaction formula is as follows: WSi _y OCl ₄ +WSi _y O ₂ Cl ₂ +Cs ⁺ +3H ₂ O

→ Cs _x Si _y WO ₃ +6HCl(↑)(X, Y<1)

It can be seen from XRD that it is a composite tungsten oxide crystal containing cesium and silicon. Finally, the appropriate proportion of solvent, dispersant and composite tungsten oxide powder is milled to nanoparticles with a particle size of less than 100 nm, and then a transparent resin is used to make a coating solution.

Example 10: Dissolve tungsten hexachloride, tin tetrachloride, germanium tetrachloride, and cesium hydroxide in an aqueous ethanol solution, and add an appropriate amount of ammonia water in a dropwise manner until precipitation occurs. The chemical reaction formula is as follows: WCl ₆ +H ₂ O+CsOH+GeCl ₄ +SnCl ₄ → WOCl ₄ +Cs ⁺ +Sn ⁴⁺ +HCl

WOCl ₄ +Cs ⁺ +Ge ⁴⁺ +Sn ⁴⁺ +2HCl+NH ₃ (aq)

_{→ WO 3 (↓) + Cs} + + Ge 4+ + Sn 4+ + 6N + H 4 Cl -

Then use supergravity to separate most of the solution from the precipitate to obtain a muddy precipitate, wash off the ammonium salt with deionized water, then extract the solvent into a dry powder in a vacuum oven, and place the dry tungsten oxychloride cesium powder at high temperature In the furnace, with a certain proportion of passive gas and hydrogen, the composite tungsten cesium tin germanium oxychloride is reduced to composite tungsten cesium tin germanium oxide. The process conditions are as follows: in a high-temperature furnace at a heating rate of 3-5 °C per minute, from room temperature to 580 °C, sintering at 580 °C for 2 hours. Thus, crystalline composite tungsten oxide nanoparticles can be obtained, and the chemical reaction formula is as follows: WOCl ₄ +WO ₂ Cl ₂ +Cs ⁺ +Ge ⁴⁺ +Sn ⁴⁺ +3H ₂ O

→ Cs _x Sn _y Ge _z WO ₃ +6HCl(↑)(X，Y<1)

It can be seen from XRD that it is a composite tungsten oxide crystal containing cesium, tin and germanium. Finally, the appropriate proportion of solvent, dispersant and composite tungsten oxide powder is milled to nanoparticles with a particle size of less than 100 nm, and then a transparent resin is used to make a coating solution.

In Comparative Example 1, tungsten hexachloride was dissolved in ethanol to obtain solution A; and cesium chloride was dissolved in water to obtain solution B. Then, the methyl ethyl solution is mixed and then an alkaline aqueous solution is added to obtain a deep black blue precipitate of composite tungsten oxychloride cesium. Then use supergravity to separate most of the solution from the precipitate to obtain a muddy precipitate. Then extract the solvent into a dry powder in a vacuum oven, place the dry tungsten oxychloride powder in a high temperature furnace, and pass a certain proportion of inert gas With hydrogen, its composite tungsten oxychloride is reduced to tungsten cesium oxide. The process conditions are as follows: in a high-temperature furnace at a heating rate of 3-5 °C per minute, from room temperature to 580 °C, sintering at 580 °C for 2 hours. It can be seen from XRD that it is a composite tungsten oxide crystal containing cesium. Finally, the solvent, dispersant and composite tungsten oxide powder of appropriate formulation ratio are ground to nanoparticles with a particle size of less than 100nm, and then a transparent resin is formulated into a coating solution, which can be coated on various transparent, translucent and opaque substrates It can be used for various purposes such as absorption, blocking, heat preservation and infrared detection. It can also be used in textile spinning, spray adhesion, immersion in various surface treatments for heat preservation, heat storage and solar energy absorption.

In Comparative Example 2, tungsten hexachloride was dissolved in ethanol to obtain solution A; and potassium chloride was dissolved in water to obtain solution B. Then, the methyl ethyl solution is mixed and then an alkaline aqueous solution is added to obtain a deep black and blue precipitate of composite potassium tungsten oxychloride. Then use supergravity to separate most of the solution from the precipitate to obtain a muddy precipitate and then extract the solvent into a dry powder in a vacuum oven. Place the dry powder of potassium tungsten oxychloride in a high-temperature furnace and pass a certain proportion of inert gas With hydrogen, the compound of potassium tungsten oxychloride is reduced to potassium tungsten oxide. The process conditions are as follows: in a high-temperature furnace at a heating rate of 3-5 °C per minute, from room temperature to 580 °C, sintering at 580 °C for 2 hours. It can be seen from XRD that it is a compound oxidation containing potassium Tungsten crystals. Finally, the solvent, dispersant and composite tungsten oxide powder with appropriate formulation ratio are ground to nanoparticles with a particle size of less than 100nm, and then a transparent resin is formulated into a coating solution, which can be coated on various transparent, translucent and opaque substrates .

In Comparative Example 3, tungsten hexachloride was dissolved in ethanol to obtain solution A; and barium chloride was dissolved in water to obtain solution B. Then, the methyl ethyl solution is mixed and then an alkaline aqueous solution is added to obtain a deep black-blue precipitate of compound tungsten oxychloride barium. Then use supergravity to separate most of the solution from the precipitate to obtain a muddy precipitate. Then extract the solvent into a dry powder in a vacuum oven, place the dry barium tungsten oxychloride powder in a high temperature furnace, and pass a certain proportion of inert gas With hydrogen, its composite barium tungsten oxychloride is reduced to barium tungsten oxide. The process conditions are as follows: in a high-temperature furnace at a heating rate of 3-5 °C per minute, from room temperature to 580 °C, sintering at 580 °C for 2 hours. It can be seen from XRD that it is a composite tungsten oxide crystal containing barium. Finally, the solvent, dispersant and composite tungsten oxide powder with appropriate formulation ratio are ground to nanoparticles with a particle size of less than 100nm, and then a transparent resin is formulated into a coating solution, which can be coated on various transparent, translucent and opaque substrates .

Please refer to Table 1 for a summary description of the steps and conditions of the above-mentioned comparative examples and examples, as well as the particle size of the composite tungsten oxide, visible light transmittance and infrared blocking rate.

Please refer to FIG. 3, in order to use the wavelength of the penetrating light on the horizontal axis and the graph of the light transmittance (%) on the vertical axis; as shown in the figure, the infrared shielding body of the present invention does allow the wavelength to be between 400-700nm visible light penetration, while blocking infrared rays with a wavelength of about 1000nm or higher that are invisible to the eyes, it can be seen that the composite tungsten oxide nanoparticles of the present invention have excellent visible light (400-700nm) transmission characteristics And infrared absorption (1000-2500nm) characteristics.

Please refer to FIG. 4 for the life test trend diagram of the composite tungsten oxide nanoparticles of the present invention. As shown in the figure, the composite tungsten oxide nanoparticles of the present invention have undergone a 1000-hour long-time illumination test, and the blocking rate of the infrared band and the ultraviolet band has changed less than 10%.

The content disclosed above is only a preferred and feasible embodiment of the present invention, and therefore does not limit the scope of the patent application of the present invention, so any equivalent technical changes made by using the description and drawings of the present invention are included in the application of the present invention. Within the scope of the patent.

The designated representative diagram is a flowchart, so there is no symbol for a simple explanation

Claims (4)

An infrared absorbing material, including composite tungsten oxide nanoparticles composed of cesium, tin and germanium, the general formula is: Cs _x Sn _y Ge _z WO ₃ ; wherein, X, Y and Z are less than 1; Cs Means cesium; Sn means tin; Ge means germanium; W means tungsten; O means oxygen. An infrared shielding body is made by mixing a nano slurry with a media resin, wherein the nano slurry includes the infrared absorption material and a dispersant as described in item 1 of the patent application scope. The infrared shielding body as described in item 2 of the patent application range, wherein the dispersant is a polymer acidic, polymer basic or polymer neutral dispersant. The infrared shielding body as described in item 2 of the patent application range, wherein the media resin includes one or more of thermosetting resin, ultraviolet curing resin, electron beam curing resin, room temperature curing resin and thermoplastic resin combination.

Images