KR101602486B1 - Fabricating method of light shielding structure - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light shielding material, a light shielding structure, and a method of manufacturing the same. The light-shielding structure includes a transparent substrate and a thin film. The thin film is coated on the transparent substrate and has a plurality of carbon-doped tungsten oxides represented by the following formula (I).
M _x WC _y O _z (I)
Wherein x is 1, y is 0, y is 0, x is 0, y is 0, y is 0, y is 0, z < / = 3.

Description

TECHNICAL FIELD [0001] The present invention relates to a fabrication method of a light shielding structure,

The present invention relates to a light shielding material, a light shielding structure, and a manufacturing method thereof. More specifically, the present invention relates to a light shielding material for shielding infrared rays, a light shielding structure, and a method of manufacturing the same.

Due to the recent overuse of fossil fuels, the greenhouse effect is becoming increasingly serious. One major cause is the heat generated by visible and near-infrared rays on the Earth, which is causing the Earth's temperature to increase rapidly. Therefore, energy conservation and reduction of carbon emissions are two important issues.

The wavelength of sunlight is in the range of 300 to 2500 nm. These sunlight wavelength ranges include 14% ultraviolet, 40% visible, and 44% infrared. Conventional glass has a high light transmittance but is poor in heat insulation. Scientists and engineers have attempted to coat the metal film on glass, which is commonly used in automobiles or buildings, in order to shield the infrared rays by reflecting the sun's rays. For example, a metal thin film containing aluminum or silver is used. However, this type of metal foil can also block electromagnetic waves, negatively affecting electronic products such as GPS, ETC or portable communication devices. Moreover, most metal films are generally produced by physical vapor deposition (PVD) or chemical vapor deposition (CVD) methods, and their manufacturing costs are high.

Another solution is to add pigments or dyes to the glass to block sunlight. However, such a product is disadvantageous in that the light transmittance of the visible light is poor and the infrared light shielding effect is poor.

Currently, some commercially available products are made of infrared blocking films using LaB ₆ , antimony doped tin oxide (ATO), indium doped tin oxide (ITO), or other ceramic compounds. However, LaB ₆ absorbs visible light. ATO and ITO exhibit excellent light transmittance in the visible light region, but light shielding in the infrared region is poor.

Further, another commercially available product is a film obtained by using an alkali metal-doped tungsten oxide powder and is used as an infrared ray shielding material. However, this product has a problem of balance between the light transmittance of the visible light and the infrared light shielding.

The present invention provides a light shielding material, a light shielding structure, and a manufacturing method thereof for blocking infrared rays.

According to one aspect of the present invention, a light shielding material is provided. The shading material is a complex of carbon-doped tungsten oxide represented by the following formula.

M _x W c _y O _z

Wherein x is 1, y is 0, y is 0, x is 0, y is 0, y is 0, y is 0, z < / = 3. The carbon-doped tungsten oxide is formed from co-doping of a carbon allotrope having a dopant and a tungsten-containing compound.

According to another aspect of the present invention, a method of manufacturing a light shielding material is provided. The method comprises the steps of preparing a powder containing a tungsten-containing compound, a dopant and an isotropic carbon, adding abrasive particles to the powder to form a mixed powder, pulverizing the mixed powder to form an initial material, Treating the initial material with a mixed gas to form carbon-doped tungsten oxide represented by the following chemical formula.

M _x W c _y O _z

Wherein x is 1, y is 0, y is 0, x is 0, y is 0, y is 0, y is 0, z < / = 3.

According to another aspect of the present invention, a light shielding structure is provided. The structure includes a transparent substrate and a thin film. The thin film is coated on the transparent substrate and has a plurality of carbon-doped tungsten oxides represented by the following formula.

M _x W c _y O _z

Wherein x is 1, y is 0, y is 0, x is 0, y is 0, y is 0, y is 0, z < / = 3.

According to a further aspect of the present invention, a method of manufacturing a light shielding structure is provided. The method comprises: preparing a plurality of carbon-doped tungsten oxides represented by the following formula: Adding the carbon-doped tungsten oxide to the solvent and uniformly dispersing the carbon-doped tungsten oxide in the solvent; Adding a medium into the solvent to obtain a dispersion solution; Coating the dispersion solution on a transparent substrate; And solidifying the medium in the dispersion solution to form a thin film.

M _x W c _y O _z

Wherein x is 1, y is 0, y is 0, x is 0, y is 0, y is 0, y is 0, z < / = 3.

The carbon is provided as a difference slag according to the invention the doped tungsten oxide (M _y O _{z x} WC) exhibits excellent barrier property shows a high transmittance in the infrared region in the visible light region. Further, a high energy ball milling method is applied to the mixed powder to cause an alloy phenomenon to form an initial material. Compared with the conventional manufacturing method using a wet process, in the present invention, it is possible to prevent the generation of a highly corrosive and highly contaminated by-product using a dry process.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention will become more fully understood from the detailed description given hereinafter, with reference to the accompanying drawings.
1 is a flow chart showing a manufacturing process of a light shielding material according to one embodiment of the present invention.
2 is a flow chart showing a manufacturing process of a light-shielding structure according to one embodiment of the present invention.
3A is a side view showing a light-shielding structure according to one embodiment of the present invention.
3B is a side view showing a light-shielding structure according to another embodiment of the present invention.
4 is a graph showing the particle size-frequency of the light-shielding structure according to one embodiment of the present invention.
5 is a graph showing the wavelength-transmittance of the light-shielding structure according to FIG.

Since tungsten trioxide (WO ₃ ) lacks effective free electrons, it has poor absorption and reflection properties in the visible light and near infrared region, and can not be an effective light shielding material. When the atomic ratio of tungsten to oxygen is less than 3, a hypoxic state or an oxygen deficiency site is formed, and free electrons are generated in tungsten oxide. When the atomic ratio of tungsten to oxygen is less than 2.2, the crystalline phase of tungsten dioxide (WO ₂ ) disappears. Therefore, in the present invention, the dopant and carbon are chemically stabilized by adding into the lattice of tungsten trioxide, and the atomic ratio of tungsten and oxygen is controlled to less than 3. By this process, tungsten oxide can have sufficient free electrons and become an effective shielding material.

1 is a flow chart showing a manufacturing process of a light shielding material according to one embodiment of the present invention. The process includes the steps of preparing a powder including a tungsten-containing compound, a dopant, and an isotropic carbon; adding abrasive particles to the powder to form a mixed powder (110); grinding the mixed powder to form an initial substance A step 120 of forming a carbon-doped tungsten oxide layer 120, and a step 130 of forming a carbon-doped tungsten oxide by heat-treating the initial material with a mixed gas. The carbon-doped tungsten oxide is represented by the following formula (I)

M _x WC _y O _z (I)

Wherein x is 1, y is 0, y is 0, x is 0, y is 0, y is 0, y is 0, z < / = 3.

The tungsten-containing compound described above may be tungsten trioxide powder and / or tungsten dioxide powder. The dopant (M) may be an oxide, hydroxide, carbonate, tungstate, chloride, nitrate, sulfate, oxalate, or nitrogene oxide containing M.

The dopant M may be an alkali metal, an alkaline earth metal, a rare earth metal, B, C, F, Al, Si, P, S, Cl, Ti, V, Cr, Mn, Fe, Co, Ni, , Ge, As, Se, Br, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Hf, Ta, Re, Os, , Hg, Tl, Pb, Bi, Po, or At. When a large amount of dopant is added, more free electrons will be generated and the light shielding effect will be increased. When the value of x gradually approaches 1, the shading effect becomes gradually better.

Additionally, to adequately control the amount of free electrons, chemical stability, and shade effectiveness, a suitable amount of carbon isotope is added to replace the partially substituted oxygen content. The carbon isotope may be carbon black, graphite, carbon nanotubes, or graphene. By this method, the carbon-doped tungsten oxide of the present invention has excellent light-shielding properties and excellent heat insulation against sunlight.

In step 110, the abrasive particles comprise high purity SiC (silicon carbide) of 5 mm and 10 mm. The weight ratio of abrasive grains to powder in the mixed powder is 8: 1.

In step 120, the mixed powder is pulverized in a high energy ball milling for 30 minutes to 6 hours.

In step 130, the mixed gas comprises an inert gas and / or a reducing gas. As the inert gas and / or the reducing gas, nitrogen (N ₂ ), hydrogen (H ₂ ), methane (CH ₄ ), or argon (Ar) may be mixed at a random ratio. An advantageous condition for the mixed gas is that hydrogen (5 vol%), methane (5 vol%), and argon (90 vol%) are used. The heat treatment temperature is 100 to 1000 占 폚, and the heat treatment time is 1 to 12 hours.

FIG. 2 is a flow chart illustrating a fabrication process of a light-shielding structure according to one embodiment of the present invention, comprising the steps of preparing (200) a plurality of carbon-doped tungsten oxides; Adding the carbon-doped tungsten oxide to the solvent and uniformly dispersing the carbon-doped tungsten oxide in the solvent (210); Adding a medium into the solvent to obtain a dispersion solution (220); Coating (230) the dispersion solution on a transparent substrate; And solidifying the medium in the dispersion solution to form a thin film (240).

In step 200, the carbon-doped tungsten oxide is produced by the manufacturing method of FIG.

In step 210, the solvent is obtained by mixing toluene and a dispersion medium in a weight ratio of 6: 1.

In step 220, the medium is selected from the group consisting of a polyester resin, a PI resin, a polycarbonate resin, a polyethylene resin, a polyvinyl chloride resin, a polyvinylidene chloride resin, a polyvinyl alcohol resin, a polystyrene resin, a polyvinyl butyral resin, Vinyl acetate copolymer material, polypropylene resin, acrylic resin, fluororesin, silicone resin, ketone resin, phenoxy resin, polyethylene terephthalate resin, polyamino resin, urea resin, acrylonitrile-butadiene- Resin), polyether resin, polyamide, acrylic resin, epoxy resin, or UV resin.

In step 230, the dispersion solution may be coated onto a substrate using a wire bar coating, a gravure coating, a spray coating, a dip coating, a slit coating, a spin coating, Coated on a transparent substrate by a spin coating, a rod coating, a roll coating or a doctor blade coating method.

The transparent substrate may be selected from PET, acrylic resin, polyurethane, polycarbonate, polyethylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, fluororesin, or glass, depending on the purpose.

3A is a side view showing a light-shielding structure according to one embodiment of the present invention. 3A, the light shielding structure 300 includes a transparent substrate 310 and a thin film 320. The thin film 320 is coated on the transparent substrate 310. The thickness of the thin film 320 is 0.5 to 200 탆. The thin film 320 includes a plurality of dispersing bodies 321. The dispersion 321 is a carbon-doped tungsten oxide represented by the following formula (I).

M _x WC _y O _z (I)

Wherein x is 1, y is 0, y is 0, x is 0, y is 0, y is 0, y is 0, z < / = 3.

3B is a side view showing a light-shielding structure according to another embodiment of the present invention. 3B, the light shielding structure 300 includes two transparent substrates 310 and a thin film 320, which is disposed between two transparent substrates 310 and has a plurality of dispersing bodies 321, Respectively. In this embodiment, triethylene glycol, diethylhexanoate, or polyvinyl butyral is further added into the dispersion solution. In this case, the two transparent substrates 310 can be bonded together due to the dispersion solution to which the material of the group having the viscous characteristic is added. First, a thin film 320 is formed after applying the dispersion solution. Next, the thin film 320 is disposed between the two transparent substrates 310. Thereafter, a light-shielding structure 300 as shown in FIG. 3B is formed using a thermal bonding method. This embodiment can be applied to explosion-proof glass.

In another embodiment of the present invention, the transparent substrate may have a plurality of dispersion bodies (not shown) therein. First, the transparent substrate 310 is immersed in the dispersion solution. Next, the transparent substrate 310 is heated to a molten state. The dispersion is uniformly mixed into a transparent substrate in a molten state. For example, the transparent substrate may be PET. The PET is immersed in the dispersion solution, and a plurality of dispersions are present on the surface of the PET. After the heating and cooling steps, a plurality of dispersion bodies are contained in the PET.

When the lattice structure of the dispersion liquid 321 is hexagonal, both the light transmittance in the visible light region and the light shielding property in the infrared region are excellent. When the lattice structure of the dispersion liquid 321 is amorphous, cubic, or tetragonal, the light transmittance in the visible light region is still excellent, but the light shielding property in the infrared region is poor.

The thin film 320 of the present invention not only absorbs a large amount of near-infrared rays and far-infrared rays, but also absorbs some visible light rays, and the thin film appears blue or green.

If the diameter of the dispersion 321 in the thin film 320 is too large, the thin film 320 exhibits poor transparency as a frosted glass due to geometrical scattering or Mie scattering in the visible light region . Therefore, in the present invention, the diameter of the dispersion body 321 is adjusted to 1 to 1000 nm to obtain an excellent transmittance for optical use.

4 is a graph showing the particle size-frequency of the light-shielding structure according to one embodiment of the present invention. In the present invention, the particle size of the light shielding material (dispersion) is measured with a particle size analyzer (Mastersizer, Malvern, UK). The particle size analyzer measures the particle size using a laser diffraction scattering technique (ISO 13320 manual) Scattered light of different angles and densities is generated as the laser beam passes through the particle sample. [0040] The particle size analyzer measures and records the scattered light spectrum and then analyzes the scattered light spectrum to calculate the particle size distribution. 4, the horizontal axis represents the particle size in nanometers (nm), and the vertical axis represents the frequency in percent (%). The shading material with an atomic ratio of Cs: W: C = 0.32: (D90) with a cumulative distribution of 50%, the maximum average diameter being 54 nm, and the cumulative distribution being 90% of particles (D90). Sir is 110nm.

5 is a graph showing the wavelength-transmittance of the light-shielding structure according to FIG. The transparent substrate 310 is PET, and the atomic ratio of the dispersion body 321 is Cs: W: C = 0.32: 1: 0.4. The horizontal axis represents the wavelength in nanometers (nm), and the vertical axis represents the transmittance in percentage (%). In Fig. 5, it can be seen that light transmission takes place at 380 to 780 nm. The transmittance at 500 nm is 69%, the transmittance at 1000 nm is 3%, and the transmittance at 1500 nm is 1%. As shown in Fig. 5, the light-shielding structure of the present invention exhibits excellent light transmittance in the visible light region and excellent light transmittance in the infrared region.

The following specific embodiments are provided for further explanation.

<Comparative Example>

In the comparative example, PET having a thickness of 23 占 퐉 was used as a transparent substrate. The transmittance of the total solar spectrum (300 to 2500 nm) was 89.2% or more. The transmittance in the visible light region was 90% and the transmittance in the infrared region was 85%. Therefore, the shading effect of PET is poor.

&Lt; Example 1 >

Powder containing 231.84 g of tungsten trioxide, 45.09 g of cesium oxide, and 12 g of carbon black was placed in a high energy ball milling containing 5 mm and 10 mm high purity SiC abrasive grains. The weight ratio of abrasive grains to powder was 8: 1. After milling for 1 hour, an initial material of the shading material was obtained. The initial material was then placed in an oven and heat treated at 500 占 폚 for 1 hour in the presence of a mixed gas comprising hydrogen (5 vol%), methane (5 vol%) and argon (90 vol%). At this time, the pressure was 1 atm. The specific surface area of the obtained light-shielding material was 50 m ² / g.

The chemical composition of the obtained light shielding material was analyzed using EDS, and as a result, the atomic ratio was Cs: W: C = 0.32: 1: 0.4. This shows that Cs and C are doped into tungsten oxide to form a new compound.

Then, the light-shielding material was mixed with toluene and a dispersion medium. The weight ratio of the light-shielding material, toluene, and dispersion medium was 3: 6: 1. The slurry containing particles having an average particle size of 60 nm was then vibrated using ultrasonic waves. Thereafter, the slurry was mixed with acrylic resin at a weight ratio of 1: 9 to obtain a dispersion solution.

The dispersion solution was coated on the PET by a doctor blade coating method. The dispersion solution was dried for 10 minutes using hot air at 100 占 폚. Then, a translucent and blue-colored thin film was obtained with a thickness of 10 mu m. The results are shown in FIG. 5, and the optical characteristics thereof are shown in Table 1 below. The average transmittance in the visible light region was 65% and the shading coefficient (SC) was 0.42.

&Lt; Example 2 >

231.84 g of tungsten trioxide, 31 g of sodium oxide, and 12 g of carbon black was placed in a high energy ball mill containing 5 mm and 10 mm high purity SiC abrasive grains. The weight ratio of abrasive grains to powder was 8: 1. After milling for 1 hour, an initial material of the shading material was obtained. The initial material was then placed in an oven and heat treated at 500 占 폚 for 1 hour in the presence of a mixed gas comprising hydrogen (5 vol%), methane (5 vol%) and argon (90 vol%). At this time, the pressure was 1 atm. The specific surface area of the obtained light-shielding material was 53 m ² / g.

The chemical composition of the obtained light-shielding material was analyzed using EDS, and as a result, the atomic ratio was Na: W: C = 0.9: 1: 0.2. This shows that Na and C are doped into tungsten oxide to form a new compound.

Then, the light-shielding material was mixed with toluene and a dispersion medium. The weight ratio of the light-shielding material, toluene, and dispersion medium was 3: 6: 1. The slurry containing particles having an average particle size of 60 nm was then vibrated using ultrasonic waves. Thereafter, the slurry was mixed with acrylic resin at a weight ratio of 1: 9 to obtain a dispersion solution.

The dispersion solution was coated on the PET by a doctor blade coating method. The dispersion solution was dried for 10 minutes using hot air at 100 占 폚. Then, a translucent and blue-colored thin film was obtained with a thickness of 10 mu m. The optical characteristics are shown in Table 1, and the average transmittance in the visible light region was 70% and the SC was 0.45.

&Lt; Example 3 >

A powder containing 231.84 g of tungsten trioxide, 13.9 g of indium oxide and 12 g of carbon black was placed in a high energy ball mill containing 5 mm and 10 mm high purity SiC abrasive grains. The weight ratio of abrasive grains to powder was 8: 1. After milling for 1 hour, an initial material of the shading material was obtained. The initial material was then placed in an oven and heat treated at 500 占 폚 for 1 hour in the presence of a mixed gas comprising hydrogen (5 vol%), methane (5 vol%) and argon (90 vol%). At this time, the pressure was 1 atm. The specific surface area of the obtained light-shielding material was 51 m ² / g.

The chemical composition of the obtained light-shielding material was analyzed by using EDS. As a result, the atomic ratio was In: W: C = 0.1: 1: 0.4. This shows that In and C are doped into tungsten oxide to form a new compound.

Then, the light-shielding material was mixed with toluene and a dispersion medium. The weight ratio of the light-shielding material, toluene, and dispersion medium was 3: 6: 1. The slurry containing particles having an average particle size of 60 nm was then vibrated using ultrasonic waves. Thereafter, the slurry was mixed with acrylic resin at a weight ratio of 1: 9 to obtain a dispersion solution.

The dispersion solution was coated on the PET by a doctor blade coating method. The dispersion solution was dried for 10 minutes using hot air at 100 占 폚. Then, a translucent and blue-colored thin film was obtained with a thickness of 10 mu m. The optical characteristics are shown in Table 1, and the average transmittance in the visible light region was 55% and the SC was 0.50.

<Example 4>

A powder comprising 231.84 g of tungsten trioxide, 8.4 g of calcium oxide, and 12 g of carbon black was placed in a high energy ball mill containing 5 mm and 10 mm high purity SiC abrasive grains. The weight ratio of abrasive grains to powder was 8: 1. After milling for 1 hour, an initial material of the shading material was obtained. The initial material was then placed in an oven and heat treated at 500 占 폚 for 1 hour in the presence of a mixed gas comprising hydrogen (5 vol%), methane (5 vol%) and argon (90 vol%). At this time, the pressure was 1 atm. The specific surface area of the obtained light-shielding material was 54 m ² / g.

The chemical composition of the obtained light-shielding material was analyzed using EDS, and as a result, the atomic ratio was Ca: W: C = 0.15: 1: 0.2. This shows that Ca and C are doped into tungsten oxide to form a new compound.

Then, the light-shielding material was mixed with toluene and a dispersion medium. The weight ratio of the light-shielding material, toluene, and dispersion medium was 3: 6: 1. The slurry containing particles having an average particle size of 60 nm was then vibrated using ultrasonic waves. Thereafter, the slurry was mixed with acrylic resin at a weight ratio of 1: 9 to obtain a dispersion solution.

The dispersion solution was coated on the PET by a doctor blade coating method. The dispersion solution was dried for 10 minutes using hot air at 100 占 폚. Then, a translucent and blue-colored thin film was obtained with a thickness of 10 mu m. The optical characteristics are shown in Table 1, and the average transmittance in the visible light region was 62% and the SC was 0.45.

&Lt; Example 5 >

A powder comprising 231.84 g of tungsten trioxide, 45.09 g of cesium oxide, and 12 g of carbon black was placed in a high energy ball mill containing 5 mm and 10 mm high purity SiC abrasive grains. The weight ratio of abrasive grains to powder was 8: 1. After milling for 1 hour, an initial material of the shading material was obtained. The initial material was then placed in an oven and heat treated at 750 占 폚 for 1 hour in the presence of a mixed gas comprising hydrogen (5 vol%), methane (5 vol%) and argon (90 vol%). At this time, the pressure was 1 atm. The specific surface area of the obtained light-shielding material was 46 m ² / g.

The chemical composition of the obtained light shielding material was analyzed using EDS, and as a result, the atomic ratio was Cs: W: C = 0.32: 1: 0.4. This shows that Cs and C are doped into tungsten oxide to form a new compound.

Then, the light-shielding material was mixed with toluene and a dispersion medium. The weight ratio of the light-shielding material, toluene, and dispersion medium was 3: 6: 1. The slurry containing particles having an average particle size of 60 nm was then vibrated using ultrasonic waves. Thereafter, the slurry was mixed with acrylic resin at a weight ratio of 1: 9 to obtain a dispersion solution.

The dispersion solution was coated on the PET by a doctor blade coating method. The dispersion solution was dried for 10 minutes using hot air at 100 占 폚. Then, a translucent and blue-colored thin film was obtained with a thickness of 10 mu m. The optical characteristics are shown in Table 1, and the average transmittance in the visible light region was 68% and the SC was 0.40.

&Lt; Example 6 >

A powder comprising 231.84 g of tungsten trioxide, 45.09 g of cesium oxide, and 12 g of carbon black was placed in a high energy ball mill containing 5 mm and 10 mm high purity SiC abrasive grains. The weight ratio of abrasive grains to powder was 8: 1. After milling for 1 hour, an initial material of the shading material was obtained. The initial material was then placed in an oven and heat treated at 1000 占 폚 for 1 hour in the presence of a mixed gas comprising hydrogen (5 vol%), methane (5 vol%) and argon (90 vol%). At this time, the pressure was 1 atm. The specific surface area of the obtained light-shielding material was 42 m ² / g.

The chemical composition of the obtained light shielding material was analyzed using EDS, and as a result, the atomic ratio was Cs: W: C = 0.32: 1: 0.4. This shows that Cs and C are doped into tungsten oxide to form a new compound.

Then, the light-shielding material was mixed with toluene and a dispersion medium. The weight ratio of the light-shielding material, toluene, and dispersion medium was 3: 6: 1. The slurry containing particles having an average particle size of 60 nm was then vibrated using ultrasonic waves. Thereafter, the slurry was mixed with acrylic resin at a weight ratio of 1: 9 to obtain a dispersion solution.

The dispersion solution was coated on the PET by a doctor blade coating method. The dispersion solution was dried for 10 minutes using hot air at 100 占 폚. Then, a translucent and blue-colored thin film was obtained with a thickness of 10 mu m. The optical characteristics are shown in Table 1, and the average transmittance in the visible light region was 62% and the SC was 0.42.

&Lt; Example 7 >

A powder comprising 231.84 g of tungsten trioxide, 45.09 g of cesium oxide, and 12 g of carbon black was placed in a high energy ball mill containing 5 mm and 10 mm high purity SiC abrasive grains. The weight ratio of abrasive grains to powder was 8: 1. After milling for 1 hour, an initial material of the shading material was obtained. The initial material was then placed in an oven and heat treated at 750 占 폚 for 5 hours in the presence of a mixed gas comprising hydrogen (5 vol%), methane (5 vol%) and argon (90 vol%). At this time, the pressure was 1 atm. The specific surface area of the obtained light-shielding material was 41 m ² / g.

The chemical composition of the obtained light shielding material was analyzed using EDS, and as a result, the atomic ratio was Cs: W: C = 0.32: 1: 0.4. This shows that Cs and C are doped into tungsten oxide to form a new compound.

Then, the light-shielding material was mixed with toluene and a dispersion medium. The weight ratio of the light-shielding material, toluene, and dispersion medium was 3: 6: 1. The slurry containing particles having an average particle size of 60 nm was then vibrated using ultrasonic waves. Thereafter, the slurry was mixed with acrylic resin at a weight ratio of 1: 9 to obtain a dispersion solution.

The dispersion solution was coated on the PET by a doctor blade coating method. The dispersion solution was dried for 10 minutes using hot air at 100 占 폚. Then, a translucent and blue-colored thin film was obtained with a thickness of 10 mu m. The optical characteristics are shown in Table 1, and the average transmittance in the visible light region was 67% and the SC was 0.412.

&Lt; Example 8 >

A powder comprising 231.84 g of tungsten trioxide, 45.09 g of cesium oxide, and 12 g of carbon black was placed in a high energy ball mill containing 5 mm and 10 mm high purity SiC abrasive grains. The weight ratio of abrasive grains to powder was 8: 1. After milling for 1 hour, an initial material of the shading material was obtained. The initial material was then placed in an oven and heat treated at 750 占 폚 for 10 hours in the presence of a mixed gas comprising hydrogen (5 vol%), methane (5 vol%) and argon (90 vol%). At this time, the pressure was 1 atm. The specific surface area of the obtained light-shielding material was 38 m ² / g.

The chemical composition of the obtained light shielding material was analyzed using EDS, and as a result, the atomic ratio was Cs: W: C = 0.32: 1: 0.4. This shows that Cs and C are doped into tungsten oxide to form a new compound.

Then, the light-shielding material was mixed with toluene and a dispersion medium. The weight ratio of the light-shielding material, toluene, and dispersion medium was 3: 6: 1. The slurry containing particles having an average particle size of 60 nm was then vibrated using ultrasonic waves. Thereafter, the slurry was mixed with acrylic resin at a weight ratio of 1: 9 to obtain a dispersion solution.

The dispersion solution was coated on the PET by a doctor blade coating method. The dispersion solution was dried for 10 minutes using hot air at 100 占 폚. Then, a translucent and blue-colored thin film was obtained with a thickness of 10 mu m. The optical characteristics are shown in Table 1, and the average transmittance in the visible light region was 64% and the SC was 0.42.

&Lt; Example 9 >

A powder comprising 231.84 g of tungsten trioxide, 45.09 g of cesium oxide, and 12 g of carbon black was placed in a high energy ball mill containing 5 mm and 10 mm high purity SiC abrasive grains. The weight ratio of abrasive grains to powder was 8: 1. After milling for 1 hour, an initial material of the shading material was obtained. The initial material was then placed in an oven and heat treated at 750 占 폚 for 5 hours in the presence of a mixed gas comprising hydrogen (5 vol%), methane (5 vol%) and argon (90 vol%). At this time, the pressure was 1 atm. The specific surface area of the obtained light-shielding material was 41 m ² / g.

The chemical composition of the obtained light shielding material was analyzed using EDS, and as a result, the atomic ratio was Cs: W: C = 0.32: 1: 0.4. This shows that Cs and C are doped into tungsten oxide to form a new compound.

Then, the light-shielding material was mixed with toluene and a dispersion medium. The weight ratio of the light-shielding material, toluene, and dispersion medium was 3: 6: 1. The slurry containing particles having an average particle size of 60 nm was then vibrated using ultrasonic waves. Thereafter, the slurry was mixed with a UV resin at a weight ratio of 1: 9 to obtain a dispersion solution.

The dispersion solution was coated on the PET by a doctor blade coating method. The dispersion solution was dried for 10 minutes using hot air at 100 占 폚. Then, a translucent and blue-colored thin film was obtained with a thickness of 10 mu m. The optical characteristics are shown in Table 1, and the average transmittance in the visible light region was 70% and the SC was 0.40.

C.C. T.T. S.S.A. Suzy T (%) SC C.E. 89.2 One Cs, W, C, O 500 ° C / 1 hr 50 Acrylic resin 65 0.42 2 Na, W, C, O 500 ° C / 1 hr 53 Acrylic resin 70 0.45 3 In, W, C, O 500 ° C / 1 hr 51 Acrylic resin 55 0.5 4 Ca, W, C, O 500 ° C / 1 hr 54 Acrylic resin 62 0.45 5 Cs, W, C, O 750 ° C / 1hr 46 Acrylic resin 68 0.4 6 Cs, W, C, O 1000 ° C / 1hr 42 Acrylic resin 62 0.42 7 Cs, W, C, O 750 ° C / 5hrs 41 Acrylic resin 67 0.41 8 Cs, W, C, O 750 ° C / 10hrs 38 Acrylic resin 64 0.42 9 Cs, W, C, O 750 ° C / 5hrs 41 UV resin 70 0.4 CE: Comparative Example
CC: chemical composition
TT: Heat treatment temperature / time
SSA: specific surface area (m ² / g)
T: transmittance in visible light region

SC are ratios between the Examples (1-9) and the Comparative Examples (PET having a thickness of 23 mu m) under the same light irradiation conditions. The smaller the value of SC, the better the shading effect.

The carbon is provided as a difference slag according to the invention the doped tungsten oxide (M _y O _{z x} WC) exhibits excellent barrier property shows a high transmittance in the infrared region in the visible light region. Further, a high energy ball milling method is applied to the mixed powder to cause an alloy phenomenon to form an initial material. Compared with the conventional manufacturing method using a wet process, in the present invention, it is possible to prevent the generation of a highly corrosive and highly contaminated by-product using a dry process.

Although the present invention has been described by some specific examples, other embodiments are possible. Therefore, the spirit and scope of the appended claims are not to be limited by the embodiments described herein.

It will be apparent to those skilled in the art that various modifications and variations can be made in the structure of the present invention without departing from the scope and spirit of the present invention. As described above, the present invention includes modifications and variations of the present invention which come within the scope of the following claims.

Claims (24)

delete delete delete delete delete (a) preparing a powder comprising a tungsten-containing compound, a dopant, and a carbon isotope;
(b) adding abrasive particles to the powder to form a mixed powder;
(c) pulverizing the mixed powder to form an initial material;
(d) heat treating the initial material with a mixed gas to form a carbon-doped tungsten oxide light-blocking material represented by the following formula (I)
Manufacturing Method of Shading Structure ::
M _x WC _y O _z (I)
Wherein x is 1, y is 0, y is 0, x is 0, y is 0, y is 0, y is 0, z < / = 3.
7. The method of claim 6, wherein the tungsten-containing compound is tungsten trioxide or tungsten dioxide.
The method of claim 6, wherein the dopant is selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, B, C, F, Al, Si, P, S, Cl, Ti, V, Cr, Mn, Fe, Co, Zn, Ga, Ge, As, Se, Br, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Hf, Pt, Au, Hg, Tl, Pb, Bi, Po, At, and combinations thereof.
The method according to claim 6, wherein the carbon isotope is selected from the group consisting of carbon black, graphite, carbon nanotubes, graphenes, and combinations thereof.
The method according to claim 6, wherein the abrasive grains are made of SiC.
The method according to claim 6, wherein the mixed powder is formed by mixing the abrasive grains and the powder at a weight ratio of 8: 1.
7. The process according to claim 6, wherein, in step (c), the grinding of the mixed powder is carried out by high energy ball milling for 30 minutes to 6 hours.
7. The method of claim 6, wherein the mixed gas comprises hydrogen, methane, and argon.
The method according to claim 6, wherein the heat treatment temperature is 100 to 1000 ° C, and the heat treatment time is 1 to 12 hours.
delete delete delete delete The method according to claim 6, wherein the light shielding material is particles having a diameter of 1 to 1000 nm.
The method according to claim 19, wherein the light shielding material has a diameter of 1 to 150 nm.
The method according to claim 6,
Forming a thin film having a plurality of the carbon-doped tungsten oxides; And
Further comprising the step of coating said thin film on a transparent substrate.
22. The method according to claim 21, wherein the thin film has a thickness of 0.5 to 200 mu m.
The method according to claim 6,
Adding a solvent and uniformly dispersing the carbon-doped tungsten oxide in the solvent;
Adding a medium into the solvent to obtain a dispersion solution;
Coating the dispersion solution on a transparent substrate; And
And solidifying the medium in the dispersion solution to form a thin film.
24. The method of claim 23, wherein the medium is selected from the group consisting of a polyester resin, a PI resin, a polycarbonate resin, a polyethylene resin, a polyvinyl chloride resin, a polyvinylidene chloride resin, a polyvinyl alcohol resin, a polystyrene resin, a polyvinyl butyral resin, Vinyl acetate copolymer material, polypropylene resin, acrylic resin, fluororesin, silicone resin, ketone resin, phenoxy resin, polyethylene terephthalate resin, polyamino resin, urea resin, acrylonitrile-butadiene- Resin), polyether resin, polyamide, acrylic resin, epoxy resin, UV resin, and combinations thereof.

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