WO2015010575A1

WO2015010575A1 - Infrared-absorbing material and preparation method thereof, and thermal insulation structure comprising same

Info

Publication number: WO2015010575A1
Application number: PCT/CN2014/082536
Authority: WO
Inventors: 陈俞君; 杨佩欣; 林晋庆; 陈怡真; 廖泓洲; 江美静
Original assignee: 财团法人工业技术研究院
Priority date: 2013-07-23
Filing date: 2014-07-18
Publication date: 2015-01-29
Also published as: TW201504157A; TWI522319B

Abstract

An infrared-absorbing material and preparation method thereof, and thermal insulation structure comprising the same; the infrared absorbent material comprises a tungsten bronze composite having a chemical formula as represented by M¹ _xM² _yWO_z, wherein 0.6≤x≤0.8, 0.2≤y≤0.33, 0.8≤x+y<l, and 2<z≤3, M¹ being Lithium (Li or Sodium (Na), M² being Potassium (K), Rubidium (Rb), or Cesium (Cs), and the tungsten bronze composite consisting of cubic tungsten bronze (CTB) and hexagonal tungsten bronze (HTB).

Description

Infrared absorbing material, method of manufacturing the same, and heat insulating structure containing the same

The present invention relates to an infrared absorbing material, a method of manufacturing the same, and a heat insulating structure comprising the same.

Background technique

In order to achieve the purpose of energy saving and carbon reduction, in the prior art, the heat of the building and the glass of the automobile is usually achieved by attaching a layer of heat insulating material. The physical properties of metal oxides have an insulating effect and have been widely used as materials for blocking infrared rays.

Therefore, it is a constant trend to develop transparent insulation materials that are more resistant to infrared rays.

Summary of the invention

The invention provides an infrared absorbing material, comprising: a tungsten bronze composite, having the chemical formula represented as follows:

Wherein 0.6 ≤ x ≤ 0.8, 0.2 ≤ y ≤ 0.33, 0.8 ≤ x + y < 1, and 2 < z ≤ 3, and M ¹ is lithium (Li), or sodium (Na), and M ² is potassium (K) , 铷 (Rb), or 铯 (Cs). Wherein, the tungsten bronze composite is composed of cubic tungsten bronze (CTB) and hexagonal tungsten bronze (HTB). The infrared absorbing material can be applied to a heat insulating structure, which meets the requirements of high light transmittance and high heat insulation.

An embodiment of the present invention provides a method for producing an infrared absorbing material, comprising: providing a ruthenium-containing precursor; providing a first alkali metal group metal salt and a second alkali metal group metal salt; mixing the first alkali metal group metal salt, The second alkali metal group metal salt and the ruthenium-containing precursor form a mixture; and the mixture is subjected to a heating process to obtain the infrared absorbing material, wherein the heating process comprises a first heating stage and a second heating stage.

Another embodiment of the present invention provides a thermal insulation structure including: a first functional layer, and a first substrate. Wherein, the first functional layer comprises the above infrared absorbing material.

DRAWINGS

1 is a flow chart showing steps of manufacturing an infrared absorbing material according to an embodiment of the present invention;

2 is a cross-sectional structural view of a heat insulating structure 10 according to an embodiment of the present invention;

3 is a cross-sectional structural view of a heat insulating structure 10 according to another embodiment of the present invention; 4 is a cross-sectional structural view of a thermal insulation structure 10 according to another embodiment of the present invention;

FIG. 5 is a cross-sectional structural view of a heat insulating structure 10 according to some embodiments of the present invention; FIG.

6 is an X-ray diffraction pattern of the tungsten bronze composite of Example 1;

Figure 7 is a penetrating light word of the product obtained in Example 1 and Comparative Examples 1 and 2;

Figure 8 is an absorption ray of the product obtained in Example 1 and Comparative Examples 1 and 2;

Figure 9 is a penetrating optical product of the products obtained in Examples 1 and 2 and Comparative Examples 3 and 5;

Figure 10 is a penetrating optical product of the product obtained in Example 3.

Symbol Description

10 insulation structure;

11 infrared absorbing materials;

12 first functional layer;

13 binder;

14 first substrate;

16 second substrate;

18 support structure;

20 cavities;

22 third substrate;

24 second functional layer;

26 fourth substrate;

100 method for producing infrared absorbing material;

101, 102, 103, 104 steps. detailed description

An embodiment of the invention provides an infrared absorbing material comprising a beryllium bronze composite. The tungsten bronze composite consists of cubic tungsten bronze (CTB) and hexagonal tungsten bronze (HTB).

According to an embodiment of the invention, the invention provides an infrared absorbing material. The infrared absorbing material comprises: a tungsten bronze composite having the chemical formula as follows:

Wherein 0.6 ≤ x ≤ 0.8, 0.2 ≤ y ≤ 0.33, 0.8 ≤ x + y < 1, and 2 < z ≤ 3, and M ¹ is lithium (Li), or sodium (Na), and M ² is potassium (K) , 铷 (Rb), or 铯 (Cs). The tungsten bronze composite is composed of cubic tungsten bronze (CTB) and hexagonal tungsten bronze (HTB). According to an embodiment of the invention, when the tungsten bronze composite conforms to the chemical composition, the ratio of the cubic tungsten bronzes (CTB) and the hexagonal tungsten bronze (HTB) is about Between 0.995 mol%: 99.005 mol% to 5.05 mol%: 94.995 mol%, the infrared absorbing material can absorb more than 60% of infrared rays (750~2500 nm) and can make most of visible light (380~750 nm) Penetration (average visible light transmittance is about 65% or more).

According to some embodiments of the present invention, the tungsten bronze composite has the chemical formula represented as follows: Na _x K _y WO _z , wherein 0.6≤x≤0.8, 0.2≤y≤0.33, 0.8≤x+y<l, and 2< z ≤ 3. Further, according to other embodiments of the present invention, the tungsten bronze composite has the chemical formula as follows: Na _x Cs _y WO _z , wherein 0.6 _{≤ x} _≤ 0.8, 0.2 ≤ y ≤ 0.33, 0.8 ≤ x + y < 1, and 2 <z ≤ 3. The tungsten bronze composite has an average particle diameter of between about 20 nm and 200 nm (for example, between about 20 nm and 150 nm).

According to other embodiments of the present invention, the present invention also provides a method of producing an infrared absorbing material for preparing the above infrared absorbing material. Referring to FIG. 1, the method 100 for manufacturing an infrared absorbing material includes providing a tungsten-containing precursor (step 101), such as ammonium metatungstate, ammonium orthotungstate, and secondary ammonium urate ( Ammonium paratungstate), alkali metal tungstate, tungstic acid ^ tungsten silicide, tungsten sulfide, tungsten Oxy chloride) ^ tungsten alkoxide, tungsten hexachloride, tungsten tetrachloride, : tungsten bromide, tungsten fluoride ), tungsten carbide, tungsten oxycarbide, or a combination thereof. Next, a first alkali metal group metal salt and a second alkali metal group metal salt are provided (step 102). Next, the cerium-containing precursor is mixed with the first alkali metal group metal salt and the second alkali metal group metal salt to form a mixture (step 103). It is noted that the antimony-containing precursor may be further dissolved in water to form an aqueous solution having a hafnium-containing precursor prior to mixing with the first and second alkali metal group metal salts. In addition, the first and second alkali metal group metal salts may be further dissolved in water to form the first and the second precursor metal before being mixed with the first and second alkali metal group metal salts. An aqueous solution of a second alkali metal group metal salt. Finally, the mixture is subjected to a heating process to obtain an infrared absorbing material according to the present invention (step 104). Wherein the first alkali metal group metal salt is a lithium metal salt, or a sodium metal salt, such as lithium sulfate, lithium carbonate, lithium chloride, sodium sulfate, sodium carbonate, sodium chloride, or a combination thereof; the second base The metal group metal salt is a potassium metal salt, a barium metal salt, or a barium metal salt such as potassium sulfate, potassium carbonate, potassium chloride, barium sulfate, barium carbonate, barium chloride, barium sulfate, barium carbonate, barium chloride, or The combination above. It is noted that, in order to obtain the above infrared absorbing material having a specific chemical structure and a specific crystal phase ratio, the weight ratio of the cerium-containing precursor to the first and second alkali metal group metal salts is about 2 and 6 And wherein the weight ratio of the first alkali metal group metal salt to the second alkali metal group metal salt is between about 0.5 and 2. Furthermore, the heating process performed on the mixture comprises a first heating phase and a second heating phase, and the difference in heating temperatures of the first heating phase and the second heating phase is greater than or equal to 20 ° C (eg, greater than approximately greater than Or equal to 30 °C :). For example, the heating temperature in the first heating stage is about 90-150 ° C, and the heating time is about 10-24 hours; and the heating temperature in the second heating stage is about 151-200 ° C, heating time. It is about 10~24 hours. It is worth noting that when the reaction time in the first heating stage or the second heating stage is less than 10 hours or more than 24 hours, the M ¹ metal element (such as sodium) and the M ² metal element (such as potassium) of the tungsten bronze may be seriously affected. The amount of doping, and the conversion of the crystal form. For example, when the M ¹ metal element is sodium (Na), when the reaction time of the first heating stage or the second heating stage is insufficient (less than ten hours), the sodium doped tungsten bronze is easily retained in the tetragonal crystal. Phase, but not easy to convert to cubic phase; for example, when the M ² metal element is potassium (K), when the reaction time of the first heating stage or the second heating stage is insufficient (less than ten hours), it is easy to make Potassium-doped tungsten bronze is unstable in the hexagonal phase and progresses toward the tetragonal phase. Further, the heating process may be, for example, a hydrothermal process.

According to an embodiment of the present invention, the first alkali metal group metal salt and the second alkali metal group metal salt may be mixed with the cerium-containing precursor by a hydrothermal method to form a mixture, and the mixture is disposed as an aqueous solution and encapsulated in water. In the hot kettle, the first heating stage and the second heating stage are sequentially performed. The reaction mixture forms a reactant supersaturated solution and forms a crystal nucleus by reaction, followed by crystallization.

According to other embodiments of the present invention, the present invention also provides a heat insulating structure. Referring to FIG. 2 , the thermal insulation structure 10 can include a first functional layer 12 , wherein the first functional layer 12 can be disposed on the first substrate 14 . The first functional layer 12 can comprise the infrared absorbing material 11 of the present invention. The first functional layer 12 may further include an adhesive 13 in which the infrared absorbing material 11 is dispersed. The method of forming the first functional layer 12 may include the following steps: First, the infrared absorbing material 11 and the binder 13 are dissolved in a solvent to form a dispersion. The adhesive 13 can be an organic binder (for example, an acrylic resin, an epoxy resin, a quartz resin, a phenoxy resin, a polystyrene resin). Urethane resin) _3⁄4 urea resin, ABS resin, PVB resin, polyacid resin, fluorine resin, polycarbonate, polystyrene, polyamide , starch, cellulose, the aforementioned copolymer or a mixture of the foregoing, etc.), an inorganic binder (for example, tetraethoxysilane (TEOS), triisopropoxy 4 (aluminum triisopropoxide), tetrabutyl (zirconium) Tetrabutoxide) or tetraisopropoxy drink (titanium tetraisopropoxide), etc., or pressure sensitive adhesive. The solvent may, for example, be water, decyl alcohol, ethanol, n-butanol, isopropanol, cyclohexanone, mercaptoethyl ketone, decyl t-butyl ketone, etc., diethyl ether, ethylene glycol dioxime ether, ethylene glycol. Ether, ethylene glycol ether, tetrahydrofuran (THF), etc., propylene glycol propylene glycol (PGMEA), ethyl-2-ethoxyethanol acetate, ethyl 3-ethoxypropionate, isoamyl acetate, etc. Chloroform, n-hexane, heptane, pentane, etc., benzene, toluene, diphenylbenzene, etc., or cyclohexane. The dispersion may further contain a dispersing agent to disperse the outer absorbent material 11 in a solvent. The dispersing agent may be a polymeric dispersing agent such as a polyester, a polyamide, a polyamic acid ester, a polyester, or a combination thereof.

Next, the dispersion is coated on the first substrate 14 to form a coating. The method of covering (for example, coating) the dispersion on the first substrate 14 may be spin coating, bar coating, blade coating, or roller coating. ), wire bar coating, or dip coating. The first substrate 14 may comprise a glass substrate, a transparent plastic substrate, or a combination of the foregoing. Next, the coated first substrate 14 is dried in an oven at a temperature of about 25 to 200 ° C for about 0.5 to 60 minutes to obtain the first functional layer 12 . The thickness of the first functional layer 12 may be between Ιμπι and 50μπι, for example, 3⁄4. Between 4μπι and 6μπι.

According to an embodiment of the invention, the thermal insulation structure 10 of the present invention may further comprise a second substrate

16, disposed on the first functional layer 12, please refer to FIG. In other words, the first functional layer 12 is located between the first substrate 14 and the second substrate 16. The material and thickness of the second substrate 16 may be the same as or different from the first substrate 14.

According to another embodiment of the present invention, the heat insulating structure 10 of the present invention may further include a third substrate 22 disposed on the second substrate 16, please refer to FIG. The second substrate 16 and the third substrate 22 are separated by a cavity 20, and the support structure 18 surrounds the cavity 20. The cavity 20 can be vacuum or filled with air (or other gas). The material and thickness of the third substrate 22 may be the same as or different from the first substrate 14. The support structure 18 may be made of glass or resin.

According to some embodiments of the present invention, the thermal insulation structure 10 of the present invention may further include a second functional layer 24 disposed on the third substrate 22 and a fourth substrate 26 disposed on the second function. Above layer 24, please refer to Figure 5. The material and thickness of the second functional layer 24 may be the same as or different from the first functional layer 12; and the material and thickness of the fourth substrate 26 may be the same as or different from the first substrate 14.

The above and other objects, features, and advantages of the present invention will become more apparent and understood.

Preparation of infrared absorbing materials Example 1

Add 30g ammonium metatungstate (manufactured and sold by SHOWA) with 4.388 g sodium carbonate (manufactured and sold by Alfa Aesar) and 2.488 g potassium carbonate (manufactured and sold by Alfa Aesar) in 95 ml of deionized water and mix well. The above solution was poured into a stainless steel closed reaction kettle, and the reaction was hydrothermally reacted at 120 ° C for 12 hours, and then heated to 180 ° C for 12 hours. The precipitated product was washed and dried in a vacuum oven at 50 ° C for 4 hours. , a powder product is obtained, and the average particle diameter is about 80 nm.

The obtained product was analyzed by X-ray photoelectron spectrometer (XPS), and the ratio of Na, K and W was found to be 0.69:0.3:1 (the predicted product conformed to the chemical formula Nao.69Ko.3WO3) » Analyze the product by X-ray Diffractometer (XRD), see Figure 6. As can be seen from Figure 6, the product consists of hexagonal tungsten bronzes (HTB) and cubic tungsten bronzes (CTB). The above products were quantitatively analyzed by Inductively Coupled Plasma (Atomic Emission Spectrometer, ICP-AES) to find cubic tungsten bronzes (CTB) and hexagonal phase tungsten bronze ( hexagonal tungsten bronzes, the ratio of HTB) is (1 persons O.OO ⁵⁾ mole ^{_{0/0: (99 ± 0.005}} ) mol ^_0/0.

Next, the light transmission pattern of the product for a wavelength of 400 nm to 2500 nm was measured, and the results are shown in Fig. 7; and, the light absorption pattern of the product for a wavelength of 400 nm to 2500 nm was measured, and the results are shown in Fig. 8. The absorption area of the light absorption spectrum at a wavelength of 780 nm to 2500 nm was integrated, and the results are shown in Table 1.

Comparative Example 1

Add 30 g of ammonium metatungstate (manufactured and sold by Sigma-Aldrich) and 4.388 g of sodium carbonate (manufactured and sold by Alfa Aesar) to 71 ml of deionized water and mix well. Pour the prepared solution into a stainless steel closed reactor. After 12 hours of constant temperature hydrothermal reaction at 120 ° C, the reaction was continued to be heated to 180 ° C for 12 hours, and the precipitated product was washed and dried in a vacuum oven at 50 ° C for 4 hours to obtain a powder product having an average particle diameter of about 80 years old.

The obtained product was analyzed by X-ray photoelectron spectrometer (XPS) to find that the ratio of Na to W was 0.69:1. The product was analyzed by X-ray Diffractometer (XRD) and it was found that the product consisted of cubic tungsten bronze (CTB). Next, the light transmission pattern of the product for a wavelength of 400 nm to 2500 nm was measured, and the results are shown in Fig. 7; and, the light absorption pattern of the product for a wavelength of 400 nm to 2500 nm was measured, and the results are shown in Fig. 8. The absorption area of the absorption pattern was integrated at a wavelength of 780 nm to 2500 nm, and the results are shown in Table 1. Comparative Example 2

30 g of ammonium metatungstate (manufactured and sold by Sigma-Aldrich) and 2.488 g of potassium carbonate (manufactured and sold by Alfa Aesar) were added to 66.3 ml of deionized water and mixed well. The prepared solution was poured into a stainless steel closed reaction kettle. After 12 hours of constant temperature hydrothermal reaction at 120 ° C, the mixture was continuously heated to 180 ° C for 12 hours, and the precipitated product was washed and dried in a vacuum oven at 50 ° C for 4 hours to obtain a powder product having an average particle diameter of about At 80 nm, the obtained powder samples were subjected to correlation analysis.

The obtained product was analyzed by X-ray photoelectron spectrometer (XPS), and the ratio of K to W was found to be 0.3:1. The product was analyzed by X-ray Diffractometer (XRD) and found to be composed of hexagonal tungsten bronze (HTB). Next, the light transmission pattern of the product for a wavelength of 400 nm to 2500 nm was measured, and the results are shown in Fig. 7; and, the light absorption pattern of the product for a wavelength of 400 nm to 2500 nm was measured, and the results are shown in Fig. 8. The absorption area of the absorption spectrum at a wavelength of 780 nm to 2500 nm was integrated, and the results are shown in Table 1.

Table 1

7 and 8, and Table 1, the infrared absorbing material (Example 1) of the present invention has an average transmittance of about 60% or more in the visible (400 nm to 780 nm) wavelength band. Further, the infrared absorbing material (Example 1) of the present invention has a higher absorption capacity in the infrared (780 nm - 2500 nm) wavelength band than Comparative Examples 1 and 2.

Example 2

30 g of ammonium metatungstate (manufactured and sold by Sigma-Aldrich) was mixed with 4.388 g of sodium carbonate (manufactured and sold by Alfa Aesar) and 2.488 g of potassium carbonate (manufactured and sold by Alfa Aesar) in 95 ml of deionized water. The prepared solution was poured into a stainless steel closed reaction kettle, and hydrothermally reacted at 120 ° C for 15 hours, and then heated to 180 ° C for 12 hours. The precipitated product was washed and dried in a vacuum oven at 50 ° C. After 4 hours, a powder product was obtained with an average particle size of about 80 nm.

The obtained product was subjected to X-ray photoelectron spectrometer (XPS). Analysis, it is known that the ratio of Na, K and W is 0.69:0.3: 1 (the predicted product conforms to the chemical formula Nao.69 o.3WO3)» The product is analyzed by X-ray Diffractometer (XRD), please refer to the figure. 3. As can be seen from Figure 3, the product consists of hexagonal tungsten bronzes (HTB) and cubic tungsten bronzes (CTB). The above products were quantitatively analyzed by Inductively Coupled Plasma (Atomic Emission Spectrometer, ICP-AES), and cubic tungsten bronzes (CTB) and hexagonal phase tungsten bronze (hexagonal) were obtained. The ratio of tungsten bronzes, HTB) is (1 ± 0.00 ⁵ ) moles ⁰ / ₀ : (99 ± 0.005) mole %.

Next, the penetration pattern of the product for the wavelength of 400 nm to 2500 nm is measured. The result is shown in Fig. 9; and, the absorption pattern of the product for the wavelength of 400 nm to 2500 nm is measured, and the absorption wavelength of the absorption pattern is 780 nm to 2500 nm. The area is integrated and the results are shown in Table 2.

Example 3

Add 30 g of ammonium metatungstate (manufactured and sold by Sigma-Aldrich) with 4.388 g of sodium carbonate (manufactured and sold by Alfa Aesar) and 5.865 g of cesium carbonate (manufactured and sold by Alfa Aesar) in 95 ml of deionized water and mix well. The prepared solution was poured into a stainless steel closed reaction kettle, and hydrothermally reacted at 120 ° C for 12 hours, and then heated to 180 ° C for 12 hours. The precipitated product was washed and dried in a vacuum oven at 50 ° C. After 4 hours, a powder product was obtained with an average particle size of about 80 nm.

The obtained product was analyzed by X-ray photoelectron spectrometer (XPS), and the ratio of Na, Cs and W was found to be 0.69:0.3:1 (the predicted product was in accordance with the chemical formula Nao. ₆₉ Cs. ₃ W0 ₃ ). Quantitative analysis of the above products by Inductively Coupled Plasma - Atomic Emission Spectrometer (ICP-AES) revealed cubic copper bronzes (CTB) and hexagonal phase 4 black bronze The ratio of (hexagonal tungsten bronzes, HTB) is (1 ± 0.005) moles ⁰ / ₀ : (99 ± 0.005) moles ⁰ / ₀ .

Next, the penetration pattern of the product for a wavelength of 400 nm to 2500 nm is measured, and the result is shown in FIG. 10; and, the absorption pattern of the product for a wavelength of 400 nm to 2500 nm is measured, and the absorption wavelength of the absorption pattern is 780 nm to 2500 nm. The area is integrated and the results are shown in Table 2.

Comparative Example 3

30 g of ammonium metatungstate (manufactured and sold by Sigma-Aldrich) was mixed with 4.388 g of sodium carbonate (manufactured and sold by Alfa Aesar) and 2.488 g of potassium carbonate (manufactured and sold by Alfa Aesar) in 95 ml of deionized water. Pour the above prepared solution into a stainless steel closed reaction kettle, and heat the water at 120 ° C. After 12 hours, the mixture was continuously heated to 180 ° C for 6 hours, and the precipitated product was washed and dried under constant temperature in a vacuum oven at 50 ° C for 4 hours to obtain a powder product having an average particle diameter of about 80 nm.

The obtained product was analyzed by X-ray photoelectron spectrometer (XPS), and the ratio of Na, K and W was found to be 0.46:0.3:1 (the predicted product conformed to the chemical formula Nao. ₄₆ KQ. ₃ W0 ₃ ). The product was analyzed by X-ray Diffractometer (XRD) and it was found that the product consisted of hexagonal tungsten bronzes and tetragonal tungsten bronzes (TTB).

Next, the penetration pattern of the product for a wavelength of 400 nm to 2500 nm is measured, and the result is shown in FIG. 9; and, the absorption spectrum of the product for a wavelength of 400 nm to 2500 nm is measured, and the absorption area of the wavelength of the light absorption spectrum is 780 nm to 2500 nm. The integration is performed and the results are shown in Table 2.

Comparative Example 4

30 g of ammonium metatungstate (manufactured and sold by Sigma-Aldrich) was mixed with 4.388 g of sodium carbonate (manufactured and sold by Alfa Aesar) and 2.488 g of potassium carbonate (manufactured and sold by Alfa Aesar) in 95 ml of deionized water. The prepared solution was poured into a stainless steel closed reaction kettle, and the mixture was heated at 150 ° C for 6 hours under constant temperature, and then heated to 180 ° C for 12 hours. The precipitated product was washed and dried in a vacuum oven at 50 ° C. After 4 hours, a powder product was obtained with an average particle size of about 80 nm.

The obtained product was analyzed by X-ray photoelectron spectrometer (XPS), and the ratio of Na, K and W was found to be 0.46:0.3:1 (the predicted product conformed to the chemical formula Nao. ₄₆ KQ. ₃ W0 ₃ ). The product was analyzed by X-ray Diffractometer (XRD) and found to be composed of hexagonal tungsten bronzes (HTB) and tetragonal tungsten bronzes (TTB).

Comparative Example 5

30 g of ammonium metatungstate (manufactured and sold by Sigma-Aldrich) was mixed with 4.388 g of sodium carbonate (manufactured and sold by Alfa Aesar) and 4.147 g of potassium carbonate (manufactured and sold by Alfa Aesar) in 99.2 ml of deionized water. The prepared solution was poured into a stainless steel closed reaction vessel, and then hydrothermally reacted at 120 ° C for 6 hours, and then heated to 150 ° C for 24 hours. The precipitated product was washed and dried in a vacuum oven at 50 ° C. After 4 hours, a powder product was obtained with an average particle size of about 80 nm.

The obtained product was analyzed by X-ray photoelectron spectrometer (XPS), and the ratio of Na, K and W was found to be 0.46:0.5:1 (the predicted product was in accordance with the chemical formula Nao. ₄₆ KQ. ₅ W0 ₃ ). The product was analyzed by X-ray Diffractometer (XRD) and was found to be The product consists of tetragonal tungsten bronzes (TTB).

Next, the penetration pattern of the product for the wavelength of 400 nm to 2500 nm is measured. The result is shown in FIG. 9; and, the light absorption pattern of the product for the wavelength of 400 nm to 2500 nm is measured, and the wavelength of the light absorption spectrum is 780 nm to 2500 nm. The absorption area was integrated and the results are shown in Table 2.

Table 2

It can be seen from Examples 1 to 3 and Comparative Examples 3 to 5 that since the reaction time of Comparative Examples 3 to 5 in the first heating stage or the second heating stage is less than 10 hours, the sodium potassium element of tungsten bronze is affected. Doping amount, and conversion of crystal form. For example, in the case of sodium (Na) doping, when the reaction time in the first heating stage or the second heating stage is insufficient (less than ten hours), the doping amount is insufficient to convert its crystal form into cubic crystal. The phase stays in the tetragonal phase; in the case of potassium (K) doping, when the reaction time in the first heating stage or the second heating stage is insufficient (less than ten hours), it is easy to make potassium-doped tungsten bronze in the hexagonal The crystal phase is unstable and develops toward the tetragonal phase. In addition, as can be seen from FIG. 6 and Table 2, when the tungsten bronze composite is composed of a specific proportion of hexagonal tungsten bronze (HTB) and hexagonal tungsten bronze (HTB), the tungsten bronze is composed of tungsten bronze. The average light transmittance of the composite in the visible light band is about 60% or more, and has a high absorption capacity in the infrared light (780 nm - 2500 nm) band.

Thermal insulation structure

Example 4

The tungsten bronze composite described in Example 1 was used. The infrared absorbing material of _69. ₃ ¹ \^0 ₃ ) is pulverized and dispersed to form a dispersion liquid with a polymer dispersant (DISPERBYK-2000) and a solvent (propylene glycol mono-methyl ether acetate). Next, the dispersion is mixed with an acrylic resin and applied to blue glass (TAIWANGLASS, TGI Tinted Glass Ocean Blue). On 5 mm), after curing, a film layer having an infrared absorbing material is formed to obtain a heat insulating structure (1) (having a structure as shown in Fig. 2).

Example 5

The infrared absorbing material of the tungsten bronze composite (Nao. ₆₉ Cs.. ₃ W0 ₃ ) described in Example 3 was mixed with a polymer dispersant (DISPERBYK-116), a solvent (propylene glycol oxime ether acetate, ropylene glycol mono-). Methyl ether acetate) is pulverized and dispersed to form a dispersion. Next, the dispersion was mixed with a polyvinyl butyral resin (polyvinyl butyral), and applied to the first clear glass (TAIWANGLASS, TGI Clear Float Glass 5 mm) and the second clear glass (TAIWANGLASS, TGI). Between Clear Float Glass 5mm), a film layer having an infrared absorbing material is formed after curing to obtain a heat insulating structure (2) (having a structure as shown in FIG. 3).

Example 6

The infrared absorbing material of the tungsten bronze composite (Nao. ₆₉ Cs.. ₃ W0 ₃ ) described in Example 3 was pulverized with a polymer dispersant (DISPERBYK-116), a solvent (ethyl acetate, ethyl acetate), Disperse to form a dispersion. Next, the dispersion is mixed with an epoxy resin, and applied between green glass (TAIWANGLASS, TGI Tinted Glass French Green 5 mm) and clear glass (TAIWANGLASS, TGI Clear Float Glass 5 mm) to form an infrared absorbing material after curing. The film layer is obtained with a heat insulating structure (3) (having a structure as shown in Fig. 3).

Example 7

The infrared absorbing material of the tungsten bronze composite (Nao. ₆₉ Cs.. ₃ W0 ₃ ) described in Example 1 was pulverized and dispersed with a polymer dispersant (Efka PX4300) and a solvent (butanone, methyl ethyl ketone). A dispersion is formed. Next, the dispersion was mixed with an acrylic pressure sensitive adhesive, and applied between green glass (TAIWANGLASS, TGI Tinted Glass French Green 5 mm) and first clear glass (TAIWANGLASS, TGI Clear Float Glass 5 mm), and formed to have infrared rays after curing. A layer of absorbent material. Next, a second clear glass (TAIWANGLASS, TGI Clear Float Glass 5mm) is disposed on the first clear glass, wherein the second clear glass and the first clear glass are supported by a structure (material is foamed) The elastic warm edge spacers are spaced apart to form a cavity. Wherein the cavity is filled with air. A heat insulating structure (4) is obtained (having a structure as shown in Fig. 4).

Example 8

The tungsten bronze composite described in Example 1 was used. _69. ₃ ¹ \^0 ₃ ) The infrared absorbing material is pulverized and dispersed with a polymer dispersant (DISPERBYK-116) and a solvent (ethyl acetate, ethyl acetate) to form a dispersion. Next, the dispersion is mixed with an epoxy resin and applied to a fluorine-doped tin oxide (FTO) glass. Between (Pilkington, Low-E Glass) and clear glass (TAIWANGLASS, TGI Clear Float Glass 5mm), after curing, a film layer having an infrared absorbing material is formed. Next, green glass (TAIWANGLASS, TGI Tinted Glass French Green 5mm) is disposed on the clear glass, wherein the green glass and the clear glass are separated by a support structure (the elastic warm edge spacer of the foam material) To form a cavity. Wherein the cavity is filled with air. A heat insulating structure (5) is obtained (having a structure as shown in Fig. 4).

Example 9

The infrared light absorbing material of the tungsten bronze composite (Nao. ₆₉ Cs.. ₃ W0 ₃ ) described in Example 3 and the polymer dispersant (DISPERBYK-2000), solvent (propylene glycol oxime ether acetate, propylene glycol mono -methyl ether acetate) is pulverized and dispersed to form a dispersion. Next, the dispersion is mixed with an acrylic resin, and applied between green glass (TAIWANGLASS, TGI Tinted Glass French Green 5 mm) and clear glass (TAIWANGLASS, TGI Clear Float Glass 5 mm) to form an infrared light absorbing material after curing. Membrane layer. The structure obtained in the above steps is defined as the first composite structure.

Then, the above steps are repeated to obtain a second composite structure.

Finally, the second composite structure is disposed on the first composite structure, wherein the clear glass of the first composite structure and the green glass of the second composite structure are separated by a support structure (material is aluminum strip) to form Cavity. A heat insulating structure (6) is obtained (having the structure shown in Fig. 5).

Example 10

The infrared absorbing material of the tungsten bronze composite (Nao. ₆₉ Cs.. ₃ W0 ₃ ) described in Example 3 was pulverized with a polymer dispersant (DISPERBYK-116), a solvent (butanone, methyl ethyl ketone), Disperse to form a dispersion. Next, the dispersion is mixed with an acrylic resin, and applied between green glass (TAIWANGLASS, TGI Tinted Glass French Green 5 mm) and first clear glass (TAIWANGLASS, TGI Clear Float Glass 5 mm) to form an infrared absorbing material after curing. The film layer. The structure obtained in the above steps is defined as the first composite structure.

Next, the infrared absorbing material of the tungsten bronze composite (Nao. ₆₉ Cs.. ₃ W0 ₃ ) described in Example 3 was pulverized with a polymer dispersant (Efka PX4300) and a solvent (ethyl acetate, ethyl acetate). Disperse to form a dispersion. Next, the dispersion is mixed with an acrylic resin, and applied between a second clear glass (TAIWANGLASS, TGI Clear Float Glass 5 mm) and a third clear glass (TAIWANGLASS, TGI Clear Float Glass 5 mm) to form an infrared absorption after curing. The film layer of the material. The structure obtained in the above step is defined as the second composite structure.

Finally, a second composite structure is disposed on the first composite structure, wherein the first composite structure The first clear glass and the second clear glass of the second composite structure are separated by a support structure (material is an aluminum strip) to form a cavity. A heat insulating structure (7) is obtained (having a structure as shown in Fig. 5).

The visible light transmittance (%) and the solar transmittance (%) of the thermal insulation structures (1) to (7) described in Examples 4-10 are shown in Table 3, and the results are shown in Table 3:

table 3

From the above results, it is understood that the infrared absorbing material according to the present invention can be further applied to a heat insulating structure, and the heat insulating structure has both the effects of calendering and heat insulation.

The present invention has been disclosed in connection with the preferred embodiments thereof, and is not intended to limit the invention, and any modifications and refinements may be made without departing from the spirit and scope of the invention. The scope of protection shall be as defined in the appended claims.

Claims

claims

1. An infrared absorbing material, containing:

Tungsten bronze composite has a chemical formula expressed as follows:

, where 0.6≤x≤0.8,

0.2≤y≤0.33, 0.8≤x+y<l, and 2<z≤3, and M ¹ is lithium (Li) or sodium (Na), M ² is potassium (K), rubidium (Rb), or Cesium (Cs), wherein the swan bronze composite is composed of cubic crystal phase tungsten bronze and hexagonal crystal phase tungsten bronze.

2. The infrared absorbing material according to claim 1, wherein the ratio of the cubic crystal phase tungsten bronze to the hexagonal crystal phase tungsten bronze is between 0.995 mol%: 99.005 mol% and 5.005 mol%: 94.995 mol%. .

3. The infrared absorbing material according to claim 1, wherein the swan bronze composite has a chemical formula expressed as follows: Na _x K _y WO _z , where 0.6≤x≤0.8, 0.2≤y≤0.33, 0.8≤x+y <l, and 2<z≤3.

4. The infrared absorbing material of claim 1, wherein the swan bronze composite has a chemical formula expressed as follows: Na _x Cs _y WO _z , where 0.6≤x≤0.8, 0.2≤y≤0.33, 0.8≤x+y <l, and 2<z≤3.

5. The infrared absorbing material as claimed in claim 1, wherein the swan bronze composite has an average particle size between 20nm and 200nm.

6 methods for manufacturing infrared absorbing materials, including:

Provide swan-containing precursors;

Provide a first alkali metal group metal salt and a second alkali metal group metal salt;

Mixing the first alkali metal group metal salt, the second alkali metal group metal salt, and the wan-containing precursor to form a mixture; and

The mixture is subjected to a heating process to obtain the infrared absorbing material according to claim 1, wherein the heating process includes a first heating stage and a second heating stage.

7. The method for manufacturing an infrared absorbing material as claimed in claim 6, wherein the weight ratio of the ion-containing precursor to the first and second alkali metal group metal salts is between 2 and 6.

8. The method for manufacturing an infrared absorbing material as claimed in claim 6, wherein the weight ratio of the first alkali metal group metal salt to the second alkali metal group metal salt is between 0.5 and 2.

9. The method for manufacturing an infrared absorbing material as claimed in claim 6, wherein before the phosphorus-containing precursor is mixed with the first and second alkali metal group metal salts, the phosphorus-containing precursor is further dissolved in water. An aqueous solution with a phosphorus-containing precursor is formed.

10. The method for manufacturing an infrared absorbing material according to claim 6, wherein before the 鹐-containing precursor is mixed with the first and second alkali metal group metal salts, the first and second alkali metal group metal salts The metal salt is further dissolved in water to form an aqueous solution having the first and second alkali metal group metal salts.

11. The method for manufacturing an infrared absorbing material according to claim 6, wherein the heating temperature of the first heating stage is between 90°C and 150°C.

12. The method of manufacturing an infrared absorbing material according to claim 6, wherein the heating time of the first heating stage is between 10 hours and 24 hours.

13. The method for manufacturing an infrared absorbing material according to claim 6, wherein the heating temperature of the second heating stage is between 151°C and 200°C.

14. The method of manufacturing an infrared absorbing material according to claim 6, wherein the heating time of the second heating stage is between 10 hours and 24 hours.

15. The method for manufacturing an infrared absorbing material according to claim 6, wherein the difference in heating temperature between the first heating stage and the second heating stage is greater than or equal to 20°C.

16. The method for manufacturing an infrared absorbing material according to claim 6, wherein the tungsten-containing precursor includes ammonium metatungstate, ammonium orthotungstate, ammonium paratungstate, alkali metal tungstate, tungstic acid, tungsten silicide, sulfide Tungsten, tungsten oxychloride, tungsten alkoxide, tungsten hexachloride, tungsten tetrachloride, tungsten bromide, tungsten fluoride, tungsten carbide, tungsten oxycarbide, or a combination of the above.

17. The method for manufacturing an infrared absorbing material according to claim 6, wherein the first alkali metal group metal salt is a lithium metal salt, a sodium metal salt, or a combination of the above.

18. The method for manufacturing an infrared absorbing material according to claim 6, wherein the first alkali metal group metal salt is lithium sulfate, lithium carbonate, lithium chloride, sodium sulfate, sodium carbonate, sodium chloride, or the above combination.

19. The method for manufacturing an infrared absorbing material according to claim 6, wherein the second alkali metal group metal salt is a potassium metal salt, a rubidium metal salt, a cesium metal salt, or a combination of the above.

20. An insulating structure comprising:

the first base material; and

The first functional layer is configured on the first substrate, wherein the first functional layer includes an infrared absorbing material, wherein the infrared absorbing material includes a tungsten bronze composite, with a chemical formula expressed as follows:

Among them, 0.6≤x≤0.8, 0.2≤y≤0.33, 0.8≤x+y<l, and 2<z≤3, and M ¹ is lithium (Li) or sodium (Na), and M ² is potassium (K) , rubidium (Rb), or cesium (Cs), wherein the tungsten bronze composite is composed of cubic crystal phase tungsten bronze and hexagonal crystal phase tungsten bronze.

21. The thermal insulation structure of claim 20, wherein the first substrate is a glass substrate or a plastic substrate.

22. The thermal insulation structure of claim 20, wherein the first functional layer further includes a binder, and the infrared absorbing material is dispersed in the binder.

23. The thermal insulation structure of claim 20, further comprising:

The second base material is arranged on the first functional layer.

24. The thermal insulation structure of claim 23, further comprising:

third substrate; and

A support structure is arranged between the second base material and the third base material, wherein the second base material, the third base material, and the support structure form a cavity.

25. The thermal insulation structure of claim 24, further comprising:

The second functional layer is arranged on the third substrate; and

The fourth base material is arranged on the second functional layer.

26. The thermal insulation structure of claim 24, wherein the second functional layer is made of the same material as the first functional layer.