KR102385854B1 - Eco-Friendly Light-to-Heat Conversion Particulate, Dispersion Thereof and Manufacturing Method Thereof - Google Patents

Abstract

The present invention relates to an eco-friendly light-to-heat conversion particulate, a dispersion thereof, and a manufacturing method of the same dispersion and, more specifically, to an eco-friendly light-to-heat conversion particulate, a dispersion thereof, and a manufacturing method of the same dispersion, in which, when light is irradiated for a certain period of time, the eco-friendly light-to-heat conversion particulate absorbs the light in place of a medium to generate energy, and when the medium receives the energy, the dispersion which amplifies vibration energy due to a resonance effect to emit radiant heat is provided, such that the exothermic property after light absorption is represented by the equation, T_1 - T_0 = ΔT_1', T_0 < T_1 where T_0 is initial temperature, T_1 is later temperature and ΔT_1' is later temperature minus initial temperature, and efficiency of heat conversion becomes more than 1.1 times as compared with that of light absorption.

Description

Eco-Friendly Light-to-Heat Conversion Particulate, Dispersion Thereof and Manufacturing Method Thereof

The present invention relates to environmentally friendly light-to-heat conversion microparticles, a dispersion thereof, and a method for manufacturing the dispersion, and more particularly, when irradiated with light for a certain period of time, eco-friendly light-to-heat conversion microparticles replace light with light By absorbing energy to generate energy, and providing a dispersion in which the vibrational energy is amplified by the resonance effect and radiant heat is emitted when the medium receives this energy, the exothermic characteristics after light absorption are T _l - T ₀ = ΔT _l' , T ₀ < T _l (T ₀ : initial temperature, T _l : later temperature, ΔT _l' : later temperature - initial temperature) and eco-friendly light-to-heat conversion microparticles that have a heat conversion efficiency of 1.1 times or more compared to light absorption, and their dispersion It relates to a sieve and a method for producing a dispersion thereof.

Organic Light-Emitting Diode (OLED) refers to a thin-film light-emitting diode made of a film of an organic compound in which a light-emitting layer responds to an electric current and emits light. In the display manufacturing process using this, LITI (Laer Induced Thermal Imaging) places a donor film, a film coated with an RGB color organic light emitting compound on a glass substrate, on the backplane, and then irradiates a laser to the panel. As a method of forming a light emitting diode, it has a principle of converting absorbed laser light into high heat and depositing an organic light emitting compound on a substrate by sublimation.

An article to which this principle can be applied is a thermal insulation fiber. When a light-to-heat conversion metal oxide is applied or contained in the thermal insulation fiber, sunlight is converted to heat and the body temperature rises, and it reduces the heat loss of the human body by blocking the radiant heat emitted from the skin. Double Effect can maximize the performance of thermal insulation fibers.

Existing light-to-heat conversion materials include carbon black, various complexes, copper compounds, oxychloro compounds, oxynitride compounds, TCO (Transparent Conductive Oxide), etc., but carbon black (Carbon Black) is limited in its use due to its dark color, metal complexes have limitations in absorption of a narrow range of wavelengths and heat resistance and durability, and copper compounds such as copper sulfide (Cu _2-x S) have limitations in absorption of a wide range of wavelengths. There is a problem that the durability gradually decreases with the

Korean Patent Application Laid-Open No. 10-2017-0022429 (2017.03.02.) relates to a heating element 90 manufactured including carbon nanotubes and a polymer material. The heating efficiency of the heating element is improved by making it In addition, an object of the present invention is to provide a heating element that adjusts the amount of heat generated according to the purpose of use by controlling the amount of carbon nanotubes included in the heating element, and exhibits high electrical conductivity even with a small amount compared to the existing heating element.

To this end, the heating element 90 includes 4 to 45% by weight of the dispersed carbon nanotubes, 54 to 94% by weight of the polymer material in which the carbon nanotubes are dispersed, and to more uniformly blend the carbon nanotubes and the polymer material. It is characterized in that it is prepared by molding a mixture containing 1 to 2% by weight of carbon black to be added.

In this case, the carbon black is a black fine carbon powder obtained by incomplete combustion or thermal decomposition of natural gas or liquid hydrocarbons, and the size of carbon particles is 1 to 500 nm and is similar to graphite. The prior art describes that such carbon black can be added to more uniformly mix the carbon nanotubes and the polymer material.

However, as mentioned above, since the conventional heating element 90 uses carbon black similar to graphite, if the heating element 90 is to be used for clothes, etc., it is difficult to apply due to the dark color of the heating element 90 . limitations are bound to follow.

In addition, in recent years, consumers are extremely reluctant to expose their body to harmful substances such as radiation emission due to an increased level of consciousness. There was a problem.

Accordingly, the related industry is demanding the development of a new type of eco-friendly light-to-heat conversion material that exhibits high light-to-heat conversion efficiency and heat retention, and does not have any harmful effects due to radiation.

Korean Patent Publication No. 10-2017-0022429 (2017.03.02.)

The present invention has been devised to solve the above problems,

It is an object of the present invention, when natural light or artificial light is irradiated to a dispersion in which eco-friendly light-to-heat conversion fine particles are distributed in a medium for a certain period of time, the eco-friendly light-to-heat conversion fine particle absorbs light instead of the medium to generate energy and the generated energy causes the medium to vibrate, causing the medium to accumulate heat or radiate heat to the surroundings.

Another object of the present invention is to form a surface plasmon by first absorbing the locally polarized energy (Polarons) by the environmentally friendly light-to-heat conversion particles when the dispersion is irradiated with light, and the medium surrounding the particles When the energy emitted by the particles is received as vibration energy, the vibration energy is amplified by the resonance effect, so that radiant heat is emitted based on the thermodynamic theory.

Another object of the present invention is to position a polymer medium around the particles of environmentally friendly light-to-heat conversion particles to receive energy from the particles to cause molecular vibrations, so that high light-to-heat conversion efficiency and high heat retention can be achieved even with low thermal conductivity. to make it work.

Another object of the present invention is to provide an environmentally friendly light-to-heat conversion particle dispersion to eliminate the possibility of damage to the body caused by radiation, as well as to improve the efficiency of electronic products caused by soft errors that temporarily cause errors in semiconductors. This is to prevent malfunction and to enable eco-friendly light-to-heat conversion microparticles formed of non-anisotropic stable isotope complex tungsten oxide to be used in insulating fibers, master batches, and multi-layer films.

Another object of the present invention is that the exothermic characteristics after light absorption are T _l - T ₀ = ΔT _l' , T ₀ < T _l (T ₀ : initial temperature, T ₁ : later temperature, ΔT _l' : later temperature - first temperature) to provide an environmentally friendly light-to-heat conversion particle dispersion.

Another object of the present invention is to provide an environmentally friendly light-to-heat conversion particulate dispersion having a heat conversion efficiency of 1.1 times or more compared to light absorption.

Another object of the present invention is to provide an environmentally friendly light-to-heat conversion particle dispersion that does not prevent soft errors and harm to radiation.

Another object of the present invention is to provide an eco-friendly light-to-heat conversion particulate dispersion that has a radiation intensity of 148 Bq/m ³ or less, which is a standard value of living radiation.

Another object of the present invention is that high energy unsensitized composite tungsten oxide is doped with ^(y) A _x ^(z) WO _(3-n) ( ^(y) A: stable isotope, x: ^(y) A ( Doping) number of elements, y: mass number of A, z: mass number of W, (3-n): number of oxygen, 0.01 ≤ x < 2, 0 ≤ n ≤ 1.5) form of cubic type, At least one of hexagonal, tetragonal, orthorhombic, and monoclinic crystal structures are formed so that the problem of increasing the particle size does not occur during compound preparation. In the formation of a light-to-heat conversion layer in which transmittance is important, it is to prevent the occurrence of a problem of clouding due to scattering of light by particles.

Another object of the present invention is to form ^(z) WO _(3-n) crystals having fine lattice defects in high-energy unsensitized complex tungsten oxide to form a polaron, a type of polarization field, inside the crystal, and , the resulting ^(y) A _x ^(z) WO _(3-n) compound lowers the band gap, resulting in stronger absorption of infrared wavelengths or wider wavelength ranges.

Another object of the present invention is to lower the energy band value according to the Fermi Level to 0.01 or more in the high energy unsensitized composite tungsten oxide ^(y) A _x ^(z) WO _(3-n) The excitation (excited state) of electrons by the hybrid orbital formation is advantageous, so that the conductivity is improved, and the x value becomes less than 2 to have stable crystallinity.

Another object of the present invention is to increase the near-infrared blocking properties by configuring the n value to be 0 or more in the high energy unsensitized composite tungsten oxide ^(y) A _x ^(z) WO _(3-n) , and the n value to 1.5 or less to maintain a stable crystal structure.

Another object of the present invention, in the form ^(y) A _x ^(z) WO _(3-n) ^(y) at the A site, alkali metal stable isotope, alkaline earth metal stable isotope, rare earth stable isotope, ^(24,25,26) Mg, ^{(90,91,92,94)} Zr, ^(50,52,53 ) ^,54) Cr, ⁽⁵⁵⁾ Mn, ^{(54,56,57,58)} Fe, ^{(96,98,99,100,101,102,104)} Ru, ⁽⁵⁹⁾ Co, ⁽¹⁰³⁾ Rh, ^(191,193) Ir, ^{(58,60, 61,62,64)} Ni, ^{(102,104,105,106,108,110)} Pd, (190,192,194,195,196,198 ⁾ Pt, ^(63,65) Cu, ^(107,109) Ag, ⁽¹⁹⁷⁾ Au, ^{(64,66,67,68,70)} Zn, ⁽ 106,108,110,111,112,114) ⁾ Cd, ⁽²⁷⁾ Al, ^{(69,71 )} Ga, (203,205) Tl, ^(28,29,30) Si, ^{(70,72,73,74,76)} Ge, (112,114,115,116,117,118,119,120,122,124 ⁾ Sn, ^{(204,206,207,208)} Pb, ^(121,123) Sb, ^(10,11) B, ⁽¹⁹⁾ F, ⁽³¹⁾ P, (32,33,34,36 ⁾ S, ^{(74,76,77,78,80)} Se, ^{(79 ,81)} Br, (120,122,123,124,125,126 ⁾ Te, ^{(46,47,48,49,50)} Ti, ⁽⁹³⁾ Nb, ⁽⁵¹⁾ V, ^{(92,94,95,96,97,98)} Mo, ⁽¹⁸¹ ) ⁾ Ta, ⁽¹⁸⁵⁾ Re, ⁽⁹⁾ Be, ^{(176,177,178,179,180)} Hf, ^{(184,187,188,189,190,192)} Os, and ⁽¹²⁷⁾ I are densely replaced by any one or more to express excellent light-to-heat conversion properties.

Another object of the present invention is to configure the content of environmentally friendly light-to-heat conversion microparticles in the polymer medium to be 0.01 to 80% by weight, so that sufficient light-to-heat conversion properties are expressed according to the use, and the medium caused by a rapid temperature rise to prevent deformation of

Another object of the present invention is to produce high-energy unsensitized composite tungsten hydrate by a liquid phase co-precipitation method with simple synthesis conditions, thereby making it easy to generate particles and control the particle size. To provide a particulate dispersion for conversion.

Another object of the present invention is to select and use light absorbing elements constituting the eco-friendly light-to-heat conversion particulate dispersion as stable isotopes, and precursors made of the selected and used stable isotopes are radioactive through a separate purification process. It minimizes materials and blocks the generation of radioactive materials (radon ( ²²⁰ Ra), uranium ( ²³⁴ U), thorium ( ²³⁰ Th), etc.)

Another object of the present invention is to include various additives such as a dispersant, a UV blocker, a thickener, a fluidizer, a mold release agent, an antioxidant, and a curing agent in the environmentally friendly light-to-heat conversion particulate dispersion to suit the type and content of additives. This is to be selected, the content of the additive is made to be 1 to 30% by weight to obtain sufficient dispersion and distribution, and to prevent product defects due to the additive not being dried in the article to which the composition is applied.

Another object of the present invention is to use an eco-friendly light-heat conversion particulate dispersion for thermal insulation fibers, so that it can have a double effect of thermal insulation by the light-heat conversion effect, and the existing color in dyeing of fibers It is to be able to freely express without significantly lowering the color, so that toning, coloring, dyeing, etc. are excellent.

Another object of the present invention is to increase the compatibility with other masterbatch chips by configuring the length of the masterbatch chip formed by the environmentally friendly light-to-heat conversion particle dispersion to be 1 mm to 5 mm, and the length during the manufacturing process. This is to avoid cutting problems.

Another object of the present invention is to increase the light-to-heat conversion effect to facilitate the deposition of organic devices by increasing the light-to-heat conversion effect by configuring the multilayer film to have a thickness of 0.1 μm to 50 μm when constructing a multilayer film using environmentally friendly light-to-heat conversion particles. while increasing production efficiency.

Another object of the present invention is to configure the multilayer film used in the display manufacturing process to have a visible light transmittance of 10% or more based on 550 nm when an eco-friendly light-to-heat conversion particle dispersion is used. to facilitate the detection of defects.

The present invention is implemented by an embodiment having the following configuration in order to achieve the above object.

According to one embodiment of the present invention, the present invention contains high-energy unsensitized composite tungsten oxide, there is no harm caused by radiation, and absorbs light on behalf of the medium, and then converts the absorbed light into thermal energy. It is characterized in that it is delivered to the medium.

According to another embodiment of the present invention, the high-energy unsensitized composite tungsten oxide is ^(y) A _x ^(z) WO _(3-n) in the form of, ^(y) A and ^(z) W is a stable isotope, wherein x is the number of elements doped in ^(y) A according to the reductive property, y is the mass number of A, and z is the mass number of W, and (3- n) is characterized in that it means the number of oxygen.

According to another embodiment of the present invention, in the present invention, ^(y) A includes any one or more of a non-radioactive alkali metal stable isotope, a non-radioactive alkaline earth metal stable isotope, and a non-radioactive rare earth stable isotope characterized.

According to another embodiment of the present invention, in the present invention, ^(y) A is any one of ³³ Cs, ³⁹ K, ²³ Na, ⁹⁸ Mo, ¹²⁰ Sn, ²⁷ Al, ⁸⁵ Rb, ⁶³ Cu, and ⁶⁴ Zn It is characterized by including the above.

According to another embodiment of the present invention, the high energy unsensitized composite tungsten oxide is a cubic type, a hexagonal type, a tetragonal type, an orthorhombic type. ) type, it is characterized in that it contains any one or more of a monoclinic type.

According to another embodiment of the present invention, in the ^(y) A _x ^(z) WO _(3-n) , x is 0.01 or more and less than 2.

According to another embodiment of the present invention, in ^(y) A _x ^(z) WO _(3-n) , n is 0 or more and 1.5 or less.

According to another embodiment of the present invention, the ^(z) W, it is characterized in that it includes any one or more of ¹⁸² W, ¹⁸³ W, ¹⁸⁴ W, ¹⁸⁶ W.

According to another embodiment of the present invention, the present invention is characterized in that it includes an environmentally friendly light-to-heat conversion particle and a medium for accumulating or radiating thermal energy converted from the eco-friendly light-to-heat conversion particle.

According to another embodiment of the present invention, in the present invention, the environmentally friendly light-to-heat conversion microparticle dispersion, the exothermic characteristics after light absorption, T _l - T ₀ = ΔT _{1 '} , T ₀ < T ₁ (T ₀ : initial temperature, T _l : later temperature, ΔT _l' : later temperature - initial temperature).

According to another embodiment of the present invention, the eco-friendly light-to-heat conversion particulate dispersion is characterized in that the heat conversion efficiency compared to light absorption is 1.1 times or more.

According to another embodiment of the present invention, the environmentally friendly light-to-heat conversion particulate dispersion, the radiation intensity is 148 Bq/m ³ or less, characterized in that.

According to another embodiment of the present invention, the present invention provides a medium providing step of providing a medium containing particles for environmentally friendly light-to-heat conversion, and a high-energy non-sensitized complex tungsten oxide, so that harmfulness caused by radiation is reduced. There is no, and after absorbing light on behalf of the medium, and converting the absorbed light into thermal energy and transferring the absorbed light to the medium, a particle providing step of providing particles for eco-friendly light-to-heat conversion, and the medium and the eco-friendly light-to-thermal conversion It characterized in that it comprises a dispersion forming step of forming an eco-friendly light-heat conversion particulate dispersion containing particulates.

According to another embodiment of the present invention, in the present invention, the step of providing fine particles forms a high-energy unsensitized composite tungsten oxide in the form of oxygen-deficient ^(y) A _x ^(z) WO _(3-n) and ^(y) A and ^(z) W are stable isotopes, and x is the number of elements doped to ^(y) A according to reductive plasticity, and y is is the mass number of A, z is the mass number of W, and (3-n) is the number of oxygen.

According to another embodiment of the present invention, the oxide forming step is characterized in that it comprises a hydrate synthesis step of synthesizing a high-energy unsensitized complex tungsten hydrate.

According to another embodiment of the present invention, in the hydrate synthesis step, the precursor providing step of providing a precursor as a stable isotope, and after the precursor providing step, the precursor is dissolved in a solvent 10 times or more, and It is characterized in that it comprises a dissolution purification step of refining, and a precipitation step that causes precipitation by inputting an opposite acid value (pH) after the dissolution and purification step.

According to another embodiment of the present invention, the hydrate synthesis step is characterized in that it is made by a liquid phase co-precipitation method.

According to another embodiment of the present invention, in the present invention, in the oxide forming step, after the hydrate synthesis step, in order to remove hydroxyl groups (-OH) and water molecules from the synthesized high-energy unsensitized complex tungsten hydrate The first calcination step of calcining, and after the first calcination step, the second reduction calcination step of reducing calcination under the input of an inert gas to form oxygen deficiency and crystallinity of the high-energy unsensitized complex tungsten oxide characterized by including.

According to another embodiment of the present invention, the inert gas, N ₂ , Ar, Ne and CO ₂ It is characterized in that it contains any one or more.

According to another embodiment of the present invention, in the present invention, in the step of providing fine particles, after the step of forming the oxide, a dispersion to form a dispersion sol comprising a high energy unsensitized complex tungsten oxide, a dispersant, and a solvent It is characterized in that it comprises a sol-forming step.

According to another embodiment of the present invention, a dispersed sol, a binder for a fiber fixing agent, short fibers, long fibers, spun yarns, filament yarns, PF (Polyester Filament Yarn), POY (Pre Oriented Yarn or Partial Orinted) Yarn), FDY (Fully Draw Yarn), DTY (Draw Textured Yarn), and ITY (Interlaced Yarn or Irregular Twisted Yarn) characterized in that it contains any one or more base fibers.

According to another embodiment of the present invention, the thermal insulation fiber is formed by spraying a mixture of the dispersion sol and the binder for the fiber fixing agent on the surface of the base fiber and drying it.

According to another embodiment of the present invention, the present invention is characterized in that the environmentally friendly light-heat conversion microparticles and at least one medium of a synthetic polymer and a natural polymer are melt-kneaded by an extruder and then injected.

According to another embodiment of the present invention, the present invention is characterized in that 1 wt% to 30 wt% of the masterbatch is included in 100 wt% of the base thermoplastic polymer masterbatch and spun.

According to another embodiment of the present invention, the present invention includes environmentally friendly light-to-heat conversion fine particles and a thermoplastic polymer, but having a thickness of 0.1 μm to 50 μm, and having a transmittance of 10% or more at a visible light wavelength of 550 nm characterized.

According to another embodiment of the present invention, the present invention includes environmentally friendly light-to-heat conversion microparticles and a thermoplastic polymer, but has a thickness of 0.1 μm to 50 μm, and the surface temperature difference after irradiation with light is T _l - T ₀ = ΔT _l' , T ₀ < T _l (T ₀ : initial temperature, T _l : later temperature, ΔT _l' : later temperature - initial temperature).

The present invention can obtain the following effects by the configuration, combination, and use relationship described below with the present embodiment.

In the present invention, when natural light or artificial light is irradiated to a dispersion in which eco-friendly light-to-heat conversion particles are distributed in a medium for a certain period of time, eco-friendly light-heat conversion microparticles absorb light instead of the medium to generate energy, The generated energy causes the medium to vibrate, which has the effect of causing the medium to accumulate heat or dissipate heat to the surroundings.

According to the present invention, when light is irradiated to the dispersion, environmentally friendly light-to-heat conversion particles first absorb the locally polarized energy (Polarons) to form a surface plasmon, and the medium surrounding the particles is When the emitted energy is received as vibration energy, the vibration energy is amplified by the resonance effect, thereby deriving the effect of allowing radiant heat to be emitted based on the thermodynamic theory.

The present invention provides an effect of providing high light-to-heat conversion efficiency and high thermal insulation even with low thermal conductivity by locating a polymer medium around the particles of environmentally friendly light-to-heat conversion particles to receive energy from the particles and cause molecular vibrations there is

The present invention provides an eco-friendly light-to-heat conversion particle dispersion to eliminate the possibility of body damage caused by radiation, as well as prevent malfunction of electronic products due to soft errors that temporarily cause errors in semiconductors And, it has the effect of enabling eco-friendly light-to-heat conversion microparticles formed of anisotropic stable isotope complex tungsten oxide to be used in thermal insulation fibers, master batches, and multi-layer films.

The present invention is an eco-friendly product in which the exothermic characteristics after light absorption are T _l - T ₀ = ΔT _l' , T ₀ < T _l (T ₀ : initial temperature, T _l : later temperature, ΔT _l’ : later temperature - initial temperature) An effect of providing a particulate dispersion for light-to-heat conversion is obtained.

The present invention has an effect of providing an environmentally friendly light-to-heat conversion particle dispersion having a heat conversion efficiency of 1.1 times or more compared to light absorption.

The present invention has the effect of providing an eco-friendly light-to-heat conversion particle dispersion that is free from soft errors and harmful to radiation.

The present invention derives the effect of providing an eco-friendly light-to-heat conversion particle dispersion that has a radiation intensity of 148 Bq/m ³ or less, which is a standard value of living radiation.

The present invention provides a high-energy unsensitized composite tungsten oxide ^(y) A _x ^(z) WO _(3-n) ( ^(y) A: a stable isotope, x: an element doped with ^(y) A number of, y: mass number of A, z: mass number of W, (3-n): number of oxygen, 0.01 ≤ x < 2, 0 ≤ n ≤ 1.5) of cubic, hexagonal ) type, tetragonal type, orthorhombic type, and at least one of monoclinic type crystal structures are formed to prevent the problem of increasing the particle size during compound preparation, and permeability is important In the formation of the light-to-heat conversion layer, there is an effect of preventing the occurrence of a problem of clouding due to scattering of light by particles.

The present invention forms ^(z) WO _(3-n) crystals having fine lattice defects in high-energy unsensitized composite tungsten oxide to form a polaron, a type of polarization field, inside the crystal, and finally ^{( y)} The A _x ^(z) WO _(3-n) compound has the effect of lowering the band gap and consequently absorbing the infrared wavelength more strongly or a wider wavelength range.

In the present invention, the high energy unsensitized composite tungsten oxide ^(y) A _x ^(z) WO _(3-n) has an x value of 0.01 or more to lower the energy band value according to the Fermi level to form a hybrid orbit. The excitation (excited state) of the electrons is advantageous, so that the conductivity is improved, and the x value becomes less than 2 to obtain the effect of having stable crystallinity.

The present invention is a high-energy unsensitized composite tungsten oxide ^(y) A _x ^(z) WO _(3-n) by configuring the n value to be 0 or more to increase the near-infrared blocking properties, and to configure the n value to be 1.5 or less to determine It has the effect of allowing the structure to be stably maintained.

The present invention, in the form ^(y) A _x ^(z) WO _(3-n) ^(y) at the A site, alkali metal stable isotope, alkaline earth metal stable isotope, rare earth stable isotope, ^(24,25,26) Mg, ^{(90,91,92,94)} Zr, ^(50,52,53 ) ^,54) Cr, ⁽⁵⁵⁾ Mn, ^{(54,56,57,58)} Fe, ^{(96,98,99,100,101,102,104)} Ru, ⁽⁵⁹⁾ Co, ⁽¹⁰³⁾ Rh, ^(191,193) Ir, ^{(58,60, 61,62,64)} Ni, ^{(102,104,105,106,108,110)} Pd, (190,192,194,195,196,198 ⁾ Pt, ^(63,65) Cu, ^(107,109) Ag, ⁽¹⁹⁷⁾ Au, ^{(64,66,67,68,70)} Zn, ⁽ 106,108,110,111,112,114) ⁾ Cd, ⁽²⁷⁾ Al, ^{(69,71 )} Ga, (203,205) Tl, ^(28,29,30) Si, ^{(70,72,73,74,76)} Ge, (112,114,115,116,117,118,119,120,122,124 ⁾ Sn, ^{(204,206,207,208)} Pb, ^(121,123) Sb, ^(10,11) B, ⁽¹⁹⁾ F, ⁽³¹⁾ P, (32,33,34,36 ⁾ S, ^{(74,76,77,78,80)} Se, ^{(79 ,81)} Br, (120,122,123,124,125,126 ⁾ Te, ^{(46,47,48,49,50)} Ti, ⁽⁹³⁾ Nb, ⁽⁵¹⁾ V, ^{(92,94,95,96,97,98)} Mo, ⁽¹⁸¹ ) ⁾ Ta, ⁽¹⁸⁵⁾ Re, ⁽⁹⁾ Be, ^{(176,177,178,179,180)} Hf, ^{(184,187,188,189,190,192)} Os, and ⁽¹²⁷⁾ I have an effect of densely replacing any one or more of I to express excellent light-to-heat conversion properties.

The present invention is configured so that the content of environmentally friendly light-to-heat conversion microparticles in the polymer medium is 0.01 to 80% by weight, so that sufficient light-to-heat conversion properties are expressed according to the use, and deformation of the medium due to rapid temperature rise is prevented to derive the effect

The present invention produces high-energy unsensitized complex tungsten hydrate by a liquid-phase co-precipitation method with simple synthesis conditions to facilitate particle generation and control of particle size, thereby dispersing environmentally friendly light-to-heat conversion particles having uniform size particles. It has the effect of providing a body.

The present invention selects and uses light absorbing elements constituting an eco-friendly light-to-heat conversion particulate dispersion as stable isotopes, and the precursors made of the selected and used stable isotopes undergo a separate purification process to minimize radioactive materials, , it has the effect of blocking the production of radioactive materials ((radon ( ²²⁰ Ra), uranium ( ²³⁴ U), thorium ( ²³⁰ Th), etc.)

The present invention includes various additives such as a dispersant, a sunscreen agent, a thickener, a fluidizer, a mold release agent, an antioxidant, and a curing agent in the eco-friendly light-heat conversion particulate dispersion, so that the type and content of the additive can be selected according to the use. In order to ensure that the content of the additive is 1 to 30% by weight, sufficient dispersion and distribution are obtained, and the effect of preventing product defects due to the additive that is not dried in the article to which the composition is applied is derived.

The present invention uses an eco-friendly light-heat conversion particulate dispersion for thermal insulation fibers, which can have a double effect of thermal insulation by the light-heat conversion effect, and greatly reduces the existing color even in dyeing of fibers. It has the effect of making it excellent in toning, coloring, dyeing, etc. because it can be freely expressed without anything.

The present invention is a problem in which the length of the masterbatch chip formed by the eco-friendly light-to-heat conversion particle dispersion is 1 mm to 5 mm, thereby increasing the compatibility with other masterbatch chips, and length cutting during the manufacturing process has the effect of preventing

In the present invention, when constructing a multilayer film using environmentally friendly light-to-heat conversion particles, the thickness of the multilayer film is configured to be 0.1 μm to 50 μm, thereby increasing the light-to-heat conversion effect to facilitate the deposition of organic devices while increasing the production efficiency. heightening effect.

In the present invention, when the multilayer film used in the display manufacturing process is constructed using an eco-friendly light-to-heat conversion particulate dispersion, the visible light transmittance is configured to be 10% or more based on 550 nm, so that the detection of defects in the organic light emitting device is easy. It has the effect of making it easier.

1 is a view showing a method for manufacturing an environmentally friendly light-to-heat conversion composite tungsten oxide fine particle dispersion according to an embodiment of the present invention.
2 is a view showing an oxide forming step.
Figure 3 is a view showing the hydrate synthesis step.

Hereinafter, preferred embodiments of the eco-friendly light-to-heat conversion particles according to the present invention, a dispersion thereof, and a method for manufacturing the dispersion will be described in detail with reference to the accompanying drawings. In the following description of the present invention, if it is determined that a detailed description of a well-known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted. Unless otherwise specified, all terms in this specification have the same general meaning as understood by those of ordinary skill in the art to which the present invention belongs, and in case of conflict with the meaning of the terms used in this specification, the According to the definition used in the specification.

Molecular motion is largely divided into vibrational motion, rotational motion, and translational motion. At molecular kinetic energy of 10 to 1,000 J/mol, a change in rotational motion occurs, at molecular kinetic energy of 1 to 1,000 kJ/mol, a change in vibrational motion occurs, and at molecular kinetic energy above that, nuclear fission may occur. there is.

Elements include stable isotopes and radioactive isotopes. When a material is composed of radioactive isotopes and has a flux of 0.05 cts/cm ² /hr or more, Soft Error, Soft Error Upset, and Single Event Upset (Single Event Upset, SEU) may cause problems. When a radioactive material is placed inside a vehicle, etc., a malfunction of the electronic device is induced by radiation emitted from the radioactive material, which may cause serious accidents. In addition, since products such as fibers are in direct contact with the human body, various diseases may occur in the body continuously exposed to radiation. Therefore, the type of isotope constituting the substance needs to be carefully considered.

The non-radioactive isotope described in the present specification refers to an isotope whose nucleus is stable and does not emit radiation or is detected above the error range of nuclide analysis among isotopes of an element. It is a concept that includes a half-life that is so long that it cannot be observed.

Methods for composing radioactive isotopes into stable isotopes through purification and separation include the use of an ion exchange resin, a method of adhering an absorbent such as silica gel to an electroplating bath to adjust the pH, and 10-fold dissolution and pH adjustment and a method using a zeolite filter, an electromagnetic separation method, a plasma separation method, a centrifugal separation method, a laser method, a laser molecular method, a stable isotope production method using optical pumping (Isotope Selective Optical Pumping: ISOP), a chelate resin, an anion exchange resin, a cation Various methods such as an exchange resin or a method using a titania-based water absorbent resin may be applied.

On the other hand, a supramolecular cage based on a Crystal System Prismatic that can obtain only C ₆₀ among the mixed fullerenes by encapsulating 1:1 fullerene C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₄ made of carbon only. (Cristina Garcia-simon, Marc Garcia-Borras, Laura Gomez, Teodor Parella, Silvia Osuna, Jordi Juanhuix, Inhar Imaz, Daniel Maspoch, Miquel Costas & Xavi Ribas. Sponge-like molecular cage for purification of fullerences. See Nature Communications. 26, 5557 (2014)), an apparatus capable of economically manufacturing water having a specific stable isotope composition using isotope fractionation by evaporation (Korean Patent Application Laid-Open No. 10-2013-0009016 ( 2013.01.23.)) can also be used. Preferably, a 10-fold dissolution - pH adjustment - zeolite filter method that is easy to mass-produce may be used.

The present invention eco-friendly light-to-heat conversion particulate dispersion (1), the exothermic characteristics after light absorption, T _l - T ₀ = ΔT _l' , T ₀ < T _l (T ₀ : initial temperature, T _l : later temperature , ΔT _l' : later temperature - initial temperature), and it is characterized in that the heat conversion efficiency compared to light absorption is 1.1 times or more. In addition, the eco-friendly light-to-heat conversion particle dispersion (1) has a radiation intensity of 148 Bq/m ³ or less, which is a standard value of living radiation.

The eco-friendly light-to-heat conversion particle dispersion 1 includes a medium 10 and eco-friendly light-to-heat conversion microparticles 30 .

The medium 10 refers to a configuration formed of any one or more of a synthetic polymer and a natural polymer. The medium 10 is configured to contain the environmentally friendly light-to-heat conversion microparticles 30, which will be described later, and may be formed of a polymer or copolymer made of a polymer, a low molecular weight, or a monomer type organic compound. The medium 10 is acrylic (Acryl)-based, urethane-based, ester-based, epoxy-based, carbonate-based, PVB (Poly Vinyl Butyral), EVA (Ethylene-Vinyl Acetate) , polyimide-based, isocyanate-based, PET (PolyEthylene Terephtalate)-based or all things recognized as polymers, oligomers for photocuring, monomers for photocuring, etc.; Inorganic polymer, that is, it may be composed of any one or more of an organic/inorganic hybrid copolymer or a polymer compound consisting of elements other than carbon (C) in the polymer chain skeleton structure. More preferably, it may be a transparent polymer. In addition, secondary processing or particulates are included in the medium 10 so that various properties such as heat retention of fibers, heat retention of other members, quick-drying of members, pattern formation of members, conductivity, antistatic properties, and infrared reflectivity are expressed. can do.

The medium 10 does not have light absorption characteristics, but environmentally friendly light-to-heat conversion particles 30 to be described later absorb light instead of the medium 10 to generate thermal energy, and to reduce vibration due to the generated thermal energy. The medium 10 receives and accumulates heat, and the accumulated heat is re-radiated to the surroundings.

The eco-friendly light-to-heat conversion microparticles 30 have no harm caused by radiation, absorb light on behalf of the medium 10, convert the absorbed light into thermal energy, and deliver it to the medium 10 say composition. In terms of the mechanism that absorbs light and converts it into heat, it is generally recognized that the infrared absorbing material itself absorbs light and then emits heat. Its performance can vary greatly. That is, the stable isotope composition ratio of eco-friendly photo-thermal conversion composite tungsten oxide, lattice constant range (a-axis: 7.3000 Å to 7.4200 Å, c-axis: 7.5700 Å to 7.6300 Å), crystallinity (cubic type, hexagonal) Hexgonal, Tetragonal, Orthorhombic, Monoclinic), concentration of oxygen (Lorentzian and Gaussian) %), particle size, particle volume, particle shape, and other factors determine the infrared absorption characteristics primarily.

When the energy absorbed by the eco-friendly light-to-heat conversion particles 30 is emitted and reflected again, assuming that the continuity of the particles is limited, the particles are locally polarized energy (Polaron) rather than a medium located in the middle of the continuous phase. ) are absorbed first to form a surface plasmon. If the surrounding medium was in the form of a polymer, the polymer that could not absorb near-infrared rays well received the energy re-emitted by the particles as vibration energy, and the vibration energy of the polymer was amplified as a resonance frequency (resonance) and radiated heat based on thermodynamic theory. A resonance effect of re-radiation occurs.

For example, when a polymer film colored with a dye is attached to low-E glass for construction, windows may be damaged by high heat due to strong sunlight in summer, and an infrared laser capable of irradiating 1,064 nm wavelength In the case of irradiating the transparent PET film with an output of 2 W (watt) or more, infrared rays are transmitted without any change. there is.

Therefore, it can be seen that the resonance effect in which the energy transferred to the medium 10 is amplified after the light absorption of the eco-friendly light-to-heat conversion particles 30 is emitted as heat.

In addition, heat transfer in non-metals is mainly caused by vibrations caused by phonons, which are quasi-particles generated by quantizing the lattice vibrations of atoms in a solid. Thermal conduction by phonons causes thermal resistance by phonon scattering, which includes phonon-phonon scattering, boundary scattering, and defect scattering. ), impurity scattering, etc. may affect heat conduction. If this scattering is suppressed, the average moving distance of the maximum phonon is increased, and as a result, the highest thermal conductivity can be obtained.

In the boundary scattering (Boundary Scattering), the presence of a thermal barrier is related to the acoustic mismatch defect between the medium and the particles, thereby lowering the movement of phonons by various scattering, thereby lowering the thermal conductivity, This causes the temperature inside the dispersion to rise, and as a result, the energy absorbed by light causes the temperature to rise.

According to this mechanism, the eco-friendly light-to-heat conversion particles 30 have a distance between the particles, and the intermediate medium 10 allows for smooth molecular vibration like a polymer, so that when the thermal conductivity is low, high light-to-heat conversion efficiency and high heat retention.

The eco-friendly light-to-heat conversion microparticles 30 are melt-kneaded through an extruder together with a medium composed of at least one of a synthetic polymer and a natural polymer to form a masterbatch. In general, in order to inject the eco-friendly light-to-heat conversion microparticles 30 into a thermoplastic resin-type masterbatch, the dispersed sol in the solution cannot be added, and it cannot be put into the screw-type masterbatch injection machine. In addition, when the eco-friendly light-to-heat conversion microparticles 30 themselves are introduced, there are problems in particle aggregation and miscibility with the thermoplastic masterbatch. - When the microparticles for heat conversion 30 are granulated in a form wrapped with a dispersant, dry mixed with a thermoplastic resin masterbatch, and put into an injection machine, the eco-friendly light-heat conversion microparticles 30 are well distributed inside the thermoplastic resin. A masterbatch of the form can be prepared. In order to remove the solvent from the prepared dispersion sol, spray drying, a reduced pressure dryer, etc. may be used, and drying may be carried out for 24 hours in an oven having a temperature of preferably 130 ° C. or higher.

Masterbatch polymers include polyethylene, polyvinylchloride, polypropylene, polystyrene, polyacrylonitrile, styrene-acrylonitrile, Acrylonitrile-Butadiene-Styrene, Polymethylmethacrylate, Polytetrafluoroethylene, Polychlorotrifluoroethylene, Polyamide, Poly Resin containing phthalamide, polycarbonate, polyethyleneoxide, acetal, polyethylene terephthalate (PET), polybutylene terephthalate, PBT ), thermoplastic polymers such as Polyester, Polysulfone, Polyphenylene Sulfide, Polyetherimide, Polymer Alloy, Recycle Polymer, and other thermoplastic polymers extracted from cotton It may be selected from natural polymers such as staple fiber polymers and cellulose.

Provide at least one kind of the polymer, mix 0.01% to 20% by weight of the solidified dispersed sol in the total content, put it in a twin-screw extruder, and melt-knead at a temperature of 200 ℃ at this time to form a final masterbatch chip there is. If the content of the solidified dispersed sol is less than 0.01% by weight, sufficient light-to-heat conversion effect cannot be obtained, and when it exceeds 20% by weight, there may be a problem in economic efficiency along with a decrease in strength of spinning, yarn, filament, etc. Because.

The length of the masterbatch chip may be preferably comprised of 1 mm to 5 mm. If the length of the masterbatch chip is less than 1 mm, the compatibility with other masterbatch chips is poor, and if the length of the masterbatch chip exceeds 5 mm, the length may be cut during the manufacturing process. Although the shape of the masterbatch chip is not limited to any specific shape, it may preferably be manufactured in a cylindrical shape. The masterbatch is included in 100% by weight of the base thermoplastic polymer masterbatch in an amount of 1% to 30% by weight, and the filament yarn is prepared in a direct spinning machine under the conditions of a general spinning temperature of 250°C and a spinning speed of 500 to 5,000 m/min. can form. According to the shape of the spinning nozzle, the cross-sectional shape of the spinning filament may be selected from one or more of C-shaped, O-shaped, star-shaped, triangular, polygonal, Y-shaped, cross-shaped, oval, square, #-shaped, and *-shaped. By securing an air layer by this cross-sectional shape and further increasing the warming effect, a double effect can be obtained. When manufacturing synthetic fibers, the initial crystallinity is small and the unoriented or low-orientation state undrawn yarn made by extruding the melt is 1 denier to 250 denier using a stretching machine having a draw ratio of 1.3 to 2.0 times. It may be formed of a drawn yarn. If it is less than 1 denier, the drawing speed is slow, so the production time is long, economical efficiency is lowered, and the problem of lowering fiber strength occurs. In addition, 250 denier or more may cause a problem of poor weaving because the diameter is too large.

The eco-friendly light-to-heat conversion microparticles 30 may be mixed with a thermoplastic polymer to form a multilayer film that is an eco-friendly light-to-heat conversion layer. At this time, the thermoplastic polymer is not limited as long as it is a polymer that can have transparency and processability, and it may be preferable that the eco-friendly light-heat conversion microparticles 30 be contained in an amount of 0.001 wt% to 80 wt% in 100 wt% of the binder. there is. If the content of the eco-friendly light-to-heat conversion particles 30 is less than 0.001 wt%, the light-to-heat conversion effect is insignificant, and when it exceeds 80 wt%, the temperature is rapidly increased due to too high light-to-heat conversion efficiency. This is because rising can cause deformation of the distribution. Preferably, the multilayer film may have a thickness of 0.1 μm to 50 μm. When the thickness of the multilayer film is less than 0.1 μm, the light-to-heat conversion effect is lowered, so organic device deposition is not smooth. can In addition, the multilayer film may be configured to have a transmittance of 10% or more at 550 nm among the wavelengths of visible light. Accordingly, it is possible to more easily detect a defect during a display manufacturing process using the light-to-thermal conversion characteristic. The multilayer film is formed such that the surface temperature difference after irradiation with light is T _l - T ₀ = ΔT _l' , T ₀ < T _l (T ₀ : initial temperature, T _l : later temperature, ΔT _l’ : later temperature - initial temperature) do. For application as a transparent light-to-thermal conversion material in the display manufacturing process, it is preferable in terms of visibility that the size of the eco-friendly light-to-heat conversion fine particles 30 is λ/4 or less of the visible light wavelength (λ).

The environmentally friendly light-to-heat conversion particles 30 include high-energy unsensitized composite tungsten oxide 31 . The high-energy unsensitized composite tungsten oxide 31 is in the form of ^(y) A _x ^(z) WO _(3-n) , wherein ^(y) A and ^(z) W are stable isotopes, and x is ^(y) is the number of elements doped to A according to the reduction plasticity, y is the mass number of A, z is the mass number of W, and (3-n) is the number of oxygen, preferably oxygen may indicate a lack of The high-energy non-sensitized composite tungsten oxide 31 may better absorb an infrared portion of natural light or artificial light. ^(z) WO _(3-n) constituting the smallest unit in the molecular structure of the high-energy unsensitized composite tungsten oxide 31 is tungsten ( ^(z) W ⁺⁶ ) having a proton number of +6 and tungsten having a valence of +5 ( ^(z) W ⁺⁵ ) is a mixed state, and the negative charge (0 ^-2 ) bond state of oxygen (O) is not in equilibrium and oxygen is partially absent, so the valence band formed by the entire molecule in the oxygen-deficient space The work function value is expressed as an energy level corresponding to the band gap between the (Valence Band) and the conduction band, and ^(z) WO _(3-n) is higher than WO ₃ without infrared absorption characteristics. It absorbs infrared wavelengths much more strongly.

Preferably, x of ^(y) A _x ^(z) WO _(3-n) is 0.01 ≤ x < 2, and n of ^(y) A _x ^(z) WO _(3-n) is 0 ≤ n ≤ 1.5.

When the x value is 0.01 or higher, the energy band value according to the Fermi level is lowered, so that the excitation (excited state) of electrons due to the formation of hybrid orbits is advantageous, and the conductivity is improved, and the hexagonal system in the cubic crystal phase (Hexagonal) When formed into a crystalline phase, the maximum possible insertion x value must be less than 2 to have stable crystallinity. When the x value is 2 or more, crystallinity ^distortion may occur and ^cause an ^unstable state of the particles. However, for example, when the x value is 2 and tungsten is +6, a white powder is obtained as Cs ₂ WO ₄ with no properties in the chemical quantitative molecular formula, and the positive valence number is +8 and the negative valence number is -8. When non-stoichiometric composite tungsten, heat shielding, conductivity, and electromagnetic wave absorption can be expected. In order to induce lattice defects with positive elements or to induce energy resonance due to oxygen deficiency, the x value should be less than 2. .

When n is less than 0, there is a problem that the oxygen content is sufficient and the plasma absorption is lowered in the range of 1.0 eV ~ 1.8 eV, which is the electron excitation energy band value due to the equilibrium of the polarized electrons, so that the near-infrared blocking properties are lowered, and when n is 1.5 If it is higher than that, the oxygen content is too low, which causes distortion of the crystal structure (Jahn-Teller distortion), which causes a problem that the crystal structure cannot be maintained.

In the high-energy unsensitized composite tungsten oxide 31, another stable isotope ^(y) A _x may be added and combined in ^(z) WO _(3-n) crystallinity constituting the minimum unit. . At this time, it is preferable that the positive element is not added to the depleted oxygen site, but that the positive stable isotope is doped and added to tungsten. When the stable isotope ^(y) A _x is positive, it behaves like a P-type semiconductor. After the stable isotope is doped ^(z) , the crystal of WO _(3-n) has fine lattice defects and a polaron, a type of polarization field, is formed inside the crystal, and finally ^(y) A _x ^(z ) ⁾ WO _(3-n) compounds lower the band gap and consequently absorb the infrared wavelength more strongly or a wider wavelength range.

The ^(y) A may be composed of at least one of a non-radioactive alkali metal stable isotope, a non-radioactive alkaline earth metal stable isotope, and a non-radioactive rare earth stable isotope. Preferably, ^(y) A is ^(24,25,26) Mg, ^{(90,91,92,94)} Zr, ^{(50,52,53,54)} Cr, ⁽⁵⁵⁾ Mn, ⁽ 54,56 ^,57,58) Fe, ^{(96,98,99,100,101,102,104)} Ru, ⁽⁵⁹⁾ Co, ⁽¹⁰³⁾ Rh, ^(191,193) Ir, ^{(58,60,61,62,64)} Ni, (102,104,105,106,108,110 ⁾ Pd, ⁽ 190,192,194,195,196,198 ⁾ Pt, ^(63,65) Cu, ^(107,109) Ag, ⁽¹⁹⁷⁾ Au, ^{(64,66,67,68,70)} Zn, (106,108,110,111,112,114 ⁾ Cd, ⁽²⁷⁾ Al, ^(69,71) Ga , ^(203,205) Tl, ^(28,29,30) Si, ^{(70,72,73,74,76)} Ge, (112,114,115,116,117,118,119,120,122,124 ⁾ Sn, ^{(204,206,207,208)} Pb, (121,123 ⁾ Sb, ^(10,11) B, ⁽¹⁹⁾ F, ⁽³¹⁾ P, (32,33,34,36 ⁾ S, ^{(74,76,77,78,80)} Se, ^(79,81) Br, (120,122,123,124,125,126 ⁾ Te, ^{(46,47 ,48,49,50)} Ti, ⁽⁹³⁾ Nb, ⁽⁵¹⁾ V, ^{(92,94,95,96,97,98)} Mo, ⁽¹⁸¹⁾ Ta, ⁽¹⁸⁵⁾ Re, ⁽⁹⁾ Be, ^{( 176,177,178,179,180)} Hf, ^{(184,187,188,189,190,192)} Os, and ⁽¹²⁷⁾ I may be any one or more. More preferably, ^(y) A may be composed of at least one of ¹³³ Cs, ³⁹ K, ²³ Na, ⁹⁸ Mo, ¹²⁰ Sn, ²⁷ Al, ⁸⁵ Rb, ⁶³ Cu, and ⁶⁴ Zn.

For example, among alkali metals, cesium (Cs) has a total of 40 isotopes with an atomic weight of 112 to 151, and cesium ( ¹³³ Cs) with a mass number of 133 is a non-radioactive stable isotope that does not emit radiation. There is this. Therefore, ^(y) A can be viewed as ⁽¹³³⁾ Cs.

In addition, tungsten (W) is a non-radioactive stable isotope that does not emit radiation, and ¹⁸² W, ¹⁸³ W, ¹⁸⁴ W, and ¹⁸⁶ W exist, and the high energy unsensitized composite tungsten oxide 31 can use them. Therefore, ^(y) A _x ^(z) WO _(3-n) in ^(z) W can be ⁽¹⁸²⁾ W, ⁽¹⁸³⁾ W, ⁽¹⁸⁴⁾ W, ⁽¹⁸⁶⁾ W.

The ^(y) A _x ^(z) WO _(3-n) compound is a complex tungsten oxide composed of stable isotopes, and various methods may be used for the manufacturing process. A method prepared by a liquid phase co-precipitation method after a blue-treated filter, and in the case of a metal among stable isotope precursors, it is also possible to synthesize a peroxide type precursor using hydrogen peroxide (H ₂ O ₂ ), or In the case of a metal oxide among the stable isotope precursors, inorganic carbonate salts using ammonium carbonate ((NH ₄ ) ₂ CO ₃ ), ammonium bicarbonate ((NH ₄ )HCO ₃ , NH ₅ CO ₃ ), etc. And it is most preferably synthesized as an ammonium metal acid precursor. The stable isotope complex tungsten oxide manufacturing method is not particularly limited. Stable isotope precursors can be prepared by various methods, for example, electromagnetic separation method, plasma separation method, centrifugal separation method, laser method, laser molecular method, stable isotope production method using optical pumping (Isotope Selective Optical Pumping: ISOP) It is also produced by ElectroKhimPribor (EKP), Kurchatov Institute, Ureco, etc. For example, the types of precursors containing stable isotopes produced by the electromagnetic method of ORNL include ¹⁰⁷ Ag ( ¹⁰⁷ Ag, Assay: 99.09%), ¹⁰⁹ Ag ( ¹⁰⁹ Ag, Assay: 99.42%), ¹³⁰ Ba ( ¹³⁰ Ba(NO ₃ ) ₂ , Assay:37.61%), ¹³⁵ Ba ( ¹³⁵ BaCO ₃ , Assay:93.38%), ¹³⁸ Ba ( ¹³⁸ BaCO ₃ , Assay:99.67%), ⁴⁰ Ca ( ⁴⁰ CaCO ₃ , Assay:99.99%), ⁴² Ca ( ⁴² CaCO ₃ , Assay: 94.49%), ⁴³ Ca ( ⁴³ CaCO ₃ , Assay: 83.93%), ⁴⁴ Ca ( ⁴⁴ CaCO ₃ , Assay: 98.89%), ⁴⁰ Ca ( ⁴⁰ CaF ₂ , Assay: 99.97%), ¹¹⁴ Cd ( ¹¹⁴ CdO, Assay:99.27%), ¹¹² Cd ( ¹¹² CdO, Assay:98.23%), ¹⁴⁰ Ce ( ¹⁴⁰ CeO ₂ , Assay:99.84%), ¹⁴² Ce ( ¹⁴² CeO ₂ , Assay:92.85%), ⁵² Cr ( ⁵² Cr ₂ O ₃ , Assay:99.9%), ⁵⁰ Cr ( ⁵⁰ Cr ₂ O ₃ , Assay:97.65%), ⁵³ Cr ( ⁵³ Cr ₂ O ₃ , Assay:98.23%), ⁵² Cr ( ⁵² Cr ₂ ) O ₃ , Assay:99.9%), ⁵⁴ Cr ( ⁵⁴ Cr ₂ O ₃ , Assay: 96.78%), ⁶³ Cu ( ⁶³ CuO, Assay: 99.89%), ⁶⁵ Cu ( ⁶⁵ CuO, Assay:99.7%), ¹⁶⁴ Dy ( ¹⁶⁴ Dy ₂ O ₃ , Assay: 98.47%), ¹⁶³ Dy ( ¹⁶³ Dy ₂ O ₃ , Assay: 96.86%), ¹⁶² Dy ( ¹⁶² Dy ₂ O ₃ , Assay: 96.28%), ¹⁶¹ Dy ( ¹⁶¹ Dy ₂ O ₃ , Assay: 95.75%), ⁵⁶ Fe ( ⁵⁶ Fe ₂ O ₃ , Assay: 99.98), ⁷¹ Ga ( ⁷¹ Ga ₂ O ₃ , Assay:99.8%), ¹⁸⁰ Hf ( ¹⁸⁰ HfO ₂ , Ass ay:98.29%), ¹⁷⁸ Hf ( ¹⁷⁸ HfO ₂ , Assay:94.75%), ¹⁷⁷ Hf ( ¹⁷⁷ HfO ₂ , Assay:91.38%), ³⁹ K ( ³⁹ KCl, Assay:99.99), ⁴¹ K ( ⁴¹ KCl, Assay) :99.17), ¹³⁹ La ( ¹³⁹ La ₂ O ₃ , Assay:99.99%), ²⁴ Mg ( ²⁴ MgO, Assay:99.92%), ²⁵ Mg ( ²⁵ MgO, Assay: 98.81%), ⁹⁸ Mo ( ⁹⁸ MoO ₃ , Assay: 97.52%), ⁹² Mo ( ⁹² MoO ₃ , Assay: 98.27%), ¹⁴⁴ Nd ( ¹⁴⁴ Nd ₂ O ₃ , Assay: 97.51%), ¹⁴³ Nd ( ¹⁴³ Nd ₂ O ₃ , Assay: 91.63%), ¹⁴⁵ Nd ( ¹⁴⁵ Nd ₂ O ₃ , Assay:91.73%), ¹⁹² Os ( ¹⁹² Os, Assay:99.4%), ¹⁹⁰ Os ( ¹⁹⁰ Os, Assay:97.31%) ¹⁸⁸ Os ( ¹⁸⁸ Os, Assay:94.98%),, ²⁰⁸ Pb ( ²⁰⁸ PbCO ₃ , Assay: 99.86%), ⁸⁵ Rb ( ⁸⁵ RbCl, Assay: 99.85%), ⁸⁷ Rb ( ⁸⁷ RbCl, Assay: 99.85%), ¹⁸⁷ Re ( ¹⁸⁷ Re, Assay: 99.39%), ³² S ( ³² S, Assay: 99.89%), ²⁸ Si ( ²⁸ SiO ₂ , Assay: 99.94%), ²⁹ Si ( ²⁹ SiO ₂ , Assay: 95.65%), ¹¹⁶ Sn ( ¹¹⁶ SnO ₂ , Assay: 96.68%), ¹²⁰ Sn ( ¹²⁰ SnO ₂ , Assay: 98.57%), ⁸⁶ Sr ( ⁸⁶ SrCO ₃ , Assay: 97.02%), ⁸⁶ Sr ( ⁸⁶ Sr(NO ₃ ) ₂ , Assay: 95.73%), ⁸⁸ Sr ( ⁸⁸ SrCO ₃ , Assay:99.84%), ¹²⁴ Te ( ¹²⁴ TeO ₂ , Assay:96.7%), ⁴⁸ Ti ( ⁴⁸ TiO ₂ , Assay:99.25%), ²⁰⁵ Tl ( ²⁰⁵ Tl ₂ O ₃ , Ass ay:99.45%), ¹⁸⁴ W ( ¹⁸⁴ WO ₃ , Assay: 95.09%), ¹⁸⁶ W ( ¹⁸⁶ WO ₃ , Assay:97.5%), ¹⁸³ W ( ¹⁸³ WO ₃ , Assay: 87.53%), ¹⁷⁴ Yb ( ¹⁷⁴ Yb ) ₂ O ₃ , Assay: 98.97%), ¹⁷⁶ Yb ( ¹⁷⁶ Yb ₂ O ₃ , Assay: 97.79%), ⁶⁸ Zn ( ⁶⁸ ZnO, Assay: 99.71%), ⁶⁴ Zn (ZnO, Assay: 99.68%), ⁹⁰ Zr ( ⁹⁰ ZrO ₂ , Assay: 99.36%), ⁹¹ Zr ( ⁹¹ ZrO ₂ , Assay: 94.59%), and the like, and numerous other precursors may be used. The precursors have already been used in many fields, such as information technology, biotechnology, nanotechnology, aerospace technology, and environmental energy technology.

More preferably, the high-energy unsensitized composite tungsten oxide 31 may be synthesized by a liquid phase co-precipitation method. According to the liquid phase co-precipitation method, the non-radioactive stable isotope is first selected, and the precursor of the desired element is dissolved in a solvent 10 times or more in the form of peroxide and inorganic carbonate or ammonium metal, and the opposite acid value of the purified reaction mixture When a certain amount of (pH) is added, precipitation and precipitation occur, and during this process, the desired inorganic compound can be synthesized by adjusting the temperature, solvent, dropping material, reaction time, etc. In general, the composition ratio of the compound also tends to increase or decrease according to the increase or decrease of the precursor input amount, but the compound composition ratio according to the precursor input amount is not limited or limited, and it is natural and known that it is determined according to the type and method of analysis of the final product. In addition, the reactor is not particularly limited, and there is no restriction on the equipment of the heat source, so there is an advantage that the existing equipment can be fully utilized.

For example, high energy unsensitized composite tungsten hydrate (Composite Tungsten Hydroxide) is tungsten chloride (WCl ₂ ) in which tungsten (W) is included and composed of stable isotopes ( ¹⁸² W, ¹⁸³ W, ¹⁸⁴ W, ¹⁸⁶ W). , tungstic acid (H ₂ WO ₄ ), tungsten (W), tungsten trioxide (WO ₃ ), sodium tungstate dihydrate (Na ₂ WO ₄ .2H ₂ O), tungsten hexapropanolate (C ₁₈ H ₄₂ O ₆ ) W), ammonium metatungstate hydrate ((NH ₄ ) ₆ H ₂ W ₁₂ O ₄₀ ·H ₂ O), tungsten selenide (H ₂ Se ₂ W), tungsten telluride (WTe ₂ ), tungsten boride (BH) ₂ W) and the like, and when the precursor is in the form of a metal or oxide, hydrogen peroxide and ammonium carbonate or ammonium bicarbonate may be used to further use the precursor in the form of a peroxide liquid, inorganic carbonate, or ammonium metal, and the precursor are not limited to Among the precursors, 30 wt% of ammonium metatungstate hydrate ((NH ₄ ) ₆ H ₂ W ₁₂ O ₄₀ ·H ₂ O) as a white powder; ^(y) A _x ( ^(y) A: non-radioactive stable isotope, x: number of elements doped to ^(y) A according to reductive plasticity, y: mass number of A, 0.01≤x<2) Applicable protons, non-radioactive alkali metal stable isotope, non-radioactive alkaline earth metal stable isotope, non-radioactive rare earth stable isotope, ^(24,25,26) Mg, ^{(90,91,92,94)} Zr, ^{( 50,52,53,54)} Cr, ⁽⁵⁵⁾ Mn, ^{(54,56,57,58)} Fe, ^{(96,98,99,100,101,102,104)} Ru, ⁽⁵⁹⁾ Co, ⁽¹⁰³⁾ Rh, ^(191,193) Ir, ^{(58,60,61,62,64)} Ni, (102,104,105,106,108,110 ⁾ Pd, (190,192,194,195,196,198 ⁾ Pt, ^(63,65) Cu, ^(107,109) Ag, ⁽¹⁹⁷⁾ Au, ^{(64,66,67,68,70} ) ⁾ Zn, ^{(106,108,110,111,112,114)} Cd, ⁽²⁷⁾ Al, ^{(69,71 )} Ga, (203,205) Tl, ^(28,29,30) Si, ^{(70,72,73,74,76)} Ge, (112,114,115,116,117,118,119,120,122,124 ⁾ Sn, ^{(204,206,207,208)} Pb, (121,123 ⁾ Sb, ^(10,11) B, ⁽¹⁹⁾ F, ⁽³¹⁾ P, (32,33,34,36 ⁾ S, ^{(74,76,77,78,80 )} Se, ^(79,81) Br, (120,122,123,124,125,126 ⁾ Te, ^{(46,47,48,49,50)} Ti, ⁽⁹³⁾ Nb, ⁽⁵¹⁾ V, ^{(92,94,95,96,97,98} ) Potassium hydroxide comprising and consisting of potassium stable isotopes ( ³⁹ K, ⁴¹ K ⁾ in Mo, ⁽¹⁸¹⁾ Ta, ⁽¹⁸⁵⁾ Re, ⁽⁹⁾ Be, ^{(176,177,178,179,180)} Hf, ^{(184,187,188,189,190,192)} Os, ⁽¹²⁷⁾ I 15% by weight of potassium carbonate (K ₂ CO ₃ ) among (KOH), potassium chloride (KCl) and potassium carbonate (K ₂ CO ₃ ); 450% by weight of distilled water, which is a multiple of 10 by weight, was put into a container and dissolved, filtered with a filter paper treated with zeolite having adsorption to radioactive substances on one side, and put into a four-neck flask reactor, and a heating mantle Maintain 80 ℃ and stir slowly for 3 hours, dissociate 50% by weight of organic acid in distilled water, and use a dropping funnel in the flask reactor in which the precursor is previously dissolved, at a constant speed for 20 minutes If the dropwise proceeds during the time, the colorless and transparent solution is gradually formed into a yellow viscous liquid, and after aging for a certain period of time, the reaction is terminated, and the filter and by-products are washed to obtain 45 wt% of a beige reactant.

The high-energy unsensitized composite tungsten hydrate synthesized by the liquid phase co-precipitation method exists in the presence of a hydroxyl group (-0H), and thus primary calcination is performed to completely remove the hydroxyl group and water molecules. need to be rough Calcination refers to an operation in which a certain substance is heated to a high temperature to remove some or all of its volatile components.

The temperature of the primary calcination is preferably maintained in the range of 200 ~ 400 ℃. When the calcination temperature is less than 200 ° C, the hydroxyl group (-OH) and water molecules cannot be completely removed, so hydroxyl groups and water molecules may remain. do. In addition, when the calcination temperature exceeds 400 °C, the growth of the particles proceeds, so that it is impossible to obtain nano-sized particles, and haze may occur in the final product. More preferably, the temperature of the primary calcination may be maintained in the range of 200 ~ 300 ℃.

The crystal defects of the high-energy unattenuated composite tungsten oxide 31 may be induced by secondary reduction firing. Reductive calcination refers to a calcination method in which incomplete combustion occurs when air is insufficiently supplied during combustion, and hydrogen in carbon dioxide or fuel decomposition products causes a reducing action on the object to be heated.

The secondary reduction calcination does not use hydrogen gas with a risk of explosion, but reduces oxygen deficiency in metal oxides by introducing an inert gas (including any one or more of N ₂ , Ar, Ne, and CO ₂ ) without the risk of explosion. It is preferable to give If hydrogen gas is used, not only expensive special equipment to inject gas is required, but also if the injection conditions of hydrogen gas are not suitable, a large explosion may occur with just a little oxygen, which increases the risk of operation. This is to reduce the cost and make it easier to use the existing firing equipment. The powder formed by the secondary reduction calcination may have a dark blue color. That is, by simply mixing independently existing oxides such as tungsten trioxide (WO ₃ ) and cesium oxide (Cs ₂ O), there is absolutely no infrared shielding effect. If the above oxides are sintered together at a constant temperature in a nitrogen atmosphere and then the powder has a blue color, it should be expressed as a Cs _x W _y O _z compound in which WO ₃ and Cs ₂ O are combined with oxygen deficiency due to incomplete combustion, and only by XRD analysis It has been sufficiently confirmed and has already been announced. Therefore, WO ₃ is yellow and Cs ₂ O is white precursors are electron/charge symmetric, and there is no reason to use them as a thermal insulation fiber material because their simple mixing and alone have absolutely no effect on infrared shielding.

The high-energy unsensitized composite tungsten oxide 31 may be any one of a cubic type, a hexagonal type, a tetragonal type, an orthorhombic type, and a monoclinic type. It may be composed of one or more, and preferably may be prepared in the form of a dispersed sol to minimize the size of the secondary agglomerated fine particles 30 and to facilitate spraying or liquid dyeing when applied to fibers.

Hereinafter, an environmentally friendly light-to-heat conversion method (S1) of the particulate dispersion for conversion will be described. In order to avoid duplicate description, the description of the above-described content has been simplified or omitted.

The eco-friendly light-to-heat conversion method (S1) of the particulate dispersion manufacturing method includes a medium providing step (S10), a particulate providing step (S30), and a dispersion forming step (S50).

The medium providing step (S10) refers to a step of providing the medium 10 containing the eco-friendly light-to-thermal conversion particles 30 . The medium 10 does not have light absorption characteristics, but the eco-friendly light-to-thermal conversion particles 30 absorb light on behalf of the medium 10 to generate thermal energy, and vibration due to the generated thermal energy. The medium 10 receives and accumulates heat, and has a characteristic of re-radiating the accumulated heat to the surroundings. This medium 10 may be composed of a synthetic polymer or a natural polymer. Specifically, the medium 10 is acryl-based, urethane-based, ester-based, epoxy-based, carbonate-based, PVB (Poly Vinyl Butyral), EVA (Ethylene-Vinyl)-based Acetate), polyimide, isocyanate, PET (PolyEthylene Terephtalate), or anything recognized as a polymer, including oligomers for light curing, monomers for light curing, etc. Or, it may be composed of at least one of an inorganic polymer, that is, a polymer compound formed of elements other than carbon (C) in the polymer chain skeleton structure, or an organic/inorganic hybrid copolymer. It may be preferable that the medium 10 is made of a transparent polymer so that a heat shielding film made through the composition can exhibit excellent optical properties.

The particulate providing step (S30) includes the high-energy unsensitized composite tungsten oxide 31, there is no harm caused by radiation, and absorbs light instead of the medium, and then converts the absorbed light into thermal energy. It refers to the step of providing the environmentally friendly light-to-heat conversion particles 30 to the medium. The particulate providing step (S30) includes an oxide forming step (S31) and a dispersed sol forming step (S33).

The oxide forming step (S31) is a step of forming an oxygen-deficient ^(y) A _x ^(z) WO _(3-n) type high-energy unsensitized composite tungsten oxide, wherein ^(y) A and ^{( z)} W is a non-radioactive stable isotope, wherein x is the number of elements doped in ^(y) A according to reductive plasticity, y is the mass number of A, and z is the mass number of W, The above (3-n) means the number of oxygen, preferably lack of oxygen. Preferably, x may have a value of 0.01 or more and less than 2, and n may have a value of 0 or more and 1.5 or less. When the x value is 0.01 or higher, the energy band value according to the Fermi level is lowered, so that the excitation (excited state) of the electrons by the hybrid orbital formation is advantageous, and the conductivity is improved, and the hexagonal (cubic) crystal phase When it is formed into a hexagonal) crystal phase, the maximum x value that can be inserted should be less than 2 to have stable crystallinity. When the x value is 2 or more, crystallinity ^distortion may occur and ^cause an ^unstable state of the particles. However, for example, when the x value is 2 and tungsten is +6, a white powder is obtained as Cs ₂ WO ₄ with no properties in the chemical quantitative molecular formula, and the positive valence number is +8 and the negative valence number is -8. When non-stoichiometric composite tungsten, heat shielding, conductivity, and electromagnetic wave absorption can be expected. In order to induce lattice defects with positive elements or to induce energy resonance due to oxygen deficiency, the x value should be less than 2. . When n is less than 0, there is a problem that the oxygen content is sufficient and the plasma absorption is lowered in the range of 1.0 eV ~ 1.8 eV, which is the electron excitation energy band value due to the equilibrium of the polarized electrons, so that the near-infrared blocking properties are lowered, and when n is 1.5 If it is higher than that, the oxygen content is too low, which causes distortion of the crystal structure (Jahn-Teller distortion), which causes a problem that the crystal structure cannot be maintained.

The oxide forming step (S31) includes a hydrate synthesis step (S311), a primary calcination step (S313), and a secondary reduction calcination step (S315).

The hydrate synthesis step (S311) refers to a step of synthesizing a high-energy unsensitized complex tungsten hydrate. Preferably, the hydrate synthesis step (S311) may be performed by a liquid phase co-precipitation method. In the case of oxides prepared by melting and oxidizing at high temperatures to obtain oxides, elements such as uranium ( ²³⁴ U) and thorium ( ²³⁰ Th) present in trace amounts in the raw material cannot be completely removed, and microwave or thermal plasma ( Although high-temperature synthesis such as high-temperature part temperature 10,000K to 15,000K) can shorten the synthesis time, an unexpectedly high energy is used during the synthesis process, and unwanted radioactive materials harmful to the human body may be generated. Therefore, in the hydrate synthesis step (S311), the synthesis proceeds at a low temperature and low energy state by a liquid phase co-precipitation method, and radioactive materials (radon ( ²²⁰ Ra), uranium ( ²³⁴ U), thorium ( ²³⁰ Th), etc.) are generated. It is preferable to block the light, thereby providing an environmentally friendly light-to-heat conversion particulate dispersion 1 having a becquerel strength of 148 Bq/m ³ or less. In addition, by preparing a high-energy unsensitized complex tungsten hydrate by a liquid phase co-precipitation method with simple synthesis conditions, particle generation and particle size control are easy to obtain uniform nano-sized particles.

The hydrate synthesis step (S311) includes a precursor providing step (S3111), a dissolution purification step (S3113), and a precipitation step (S3115).

The precursor providing step (S3111) refers to a step of providing a precursor as a stable isotope, and the dissolution and purification step (S3113) is, after the precursor providing step (S3111), the precursor is dissolved in a solvent of 10 times or more, It refers to the step of refining, and the precipitation step (S3115) refers to a step of causing precipitation by inputting an opposite acid value (pH) after the dissolution and purification step (S3113). Through this, it is possible to block the generation of radioactive materials by performing synthesis at a relatively low temperature and low energy state. During this process, a desired inorganic compound can be synthesized by adjusting the temperature, solvent, dropping material, reaction time, etc. In this case, the reactor is not particularly limited, and the existing equipment can be fully utilized because there is no restriction on the equipment of the heat source.

The primary calcination step (S313) refers to a step of calcining to remove hydroxyl groups (-OH) and water molecules from the synthesized high-energy unsensitized complex tungsten hydrate after the hydrate synthesis step (S311). Through the first calcination step (S313), it is possible to obtain nano-sized particles by minimizing the growth of particles while completely removing hydroxyl groups and water molecules from the high-energy unsensitized composite tungsten hydrate.

The secondary reduction and calcination step (S315) refers to a step of reducing calcination under the input of an inert gas for crystallinity and oxygen deprivation of the high-energy unsensitized composite tungsten oxide after the first calcination step (S313). . The inert gas may include any one or more of N ₂ , Ar, Ne, and CO ₂ . The crystal defects of the high-energy unsensitized composite tungsten oxide 31 may be induced by the secondary reduction and firing step (S315). Reductive calcination refers to a calcination method in which incomplete combustion occurs when air is insufficiently supplied during combustion, and hydrogen in carbon dioxide or fuel decomposition products causes a reducing action on the object to be heated. In the secondary reduction and firing step (S315), metal oxide is reduced by introducing an inert gas (including any one or more of N ₂ , Ar, Ne, and CO ₂ ) without the risk of explosion without using hydrogen gas having a risk of explosion. crystallinity and oxygen starvation. If hydrogen gas is used, not only expensive special equipment to inject gas is required, but also if the injection conditions of hydrogen gas are not suitable, a large explosion may occur with just a little oxygen, which increases the risk of operation. This is to reduce the cost and make it easier to use the existing firing equipment. The powder formed by the secondary reduction calcination may have a dark blue color.

The dispersed sol forming step (S33) refers to a step of forming a dispersed sol including the high energy unsensitized composite tungsten oxide 31, a dispersing agent, and a solvent after the oxide forming step (S31). The dispersed sol is mixed with a binder for a fiber fixing agent to form short fibers, long fibers, spun yarns, filament yarns, PF (Polyester Filament Yarn), POY (Pre Oriented Yarn or Partial Orinted Yarn), FDY (Fully Draw Yarn), DTY (Draw) Textured Yarn) and ITY (Interlaced Yarn or Irregular Twisted Yarn) may be sprayed on the surface of any one or more of the base fibers, and may be dried to form insulating fibers. Preferably, when spraying the mixture including the dispersion sol and the binder for the fiber fixing agent to the base fiber, it may be preferable to spray at a nozzle pressure of 0.5 MPa.

The dispersion forming step ( S50 ) refers to a step of forming the eco-friendly light-to-heat conversion particulate dispersion 1 including the medium 10 and the eco-friendly light-to-heat conversion particulate 30 . The formed dispersion has a form in which the eco-friendly light-to-heat conversion fine particles 30 are dispersed between the medium 10, and when light is irradiated, the eco-friendly light-to-heat conversion fine particle 30 is formed in the medium Instead of (10), light, preferably near-infrared wavelength, is absorbed, and the absorbed energy generates heat. It can accumulate and dissipate the accumulated heat to the surroundings.

When the eco-friendly light-to-heat conversion fine particles are, for example, ⁽¹³³⁾ Cs _0.3 ⁽¹⁸⁴⁾ WO ₃ , and when the fine particles are distributed in the medium, elemental analysis of the dispersion (1) results in a molar ratio of ¹³³ Cs / ¹⁸⁴ W is measured within the range of the above molecular formula, but oxygen always appears as a value exceeding 3. For elemental analysis of the dispersion (1), it is preferable to measure only the molar ratios of metal elements (eg, cesium, tungsten) except oxygen, and if necessary, the dispersion is pre-treated (solvent, strong acid, strong acid, mixed acid). Acid), etc., can be used to properly extract only the fine particles and measure the oxygen ratio with a non-metal element analysis equipment (eg: ONH836). Therefore, for the dispersion containing the fine particles, the molar ratio of the tungsten element and the positive element (eg, ¹³³ Cs/ ¹⁸⁴ W = 0.27, 0.29, 0.3, 0.32, 0.33) is taken as a measurement value by elemental analysis, and the becquerel strength (eg, nuclide analysis) :≤0.05 Bq), and contrasting the representative peaks of the reference crystallinity corresponding to the microparticles by crystallization analysis (Example: (JCPDS card No. 83-1334, Cs _0.32 WO ₃ , Hexagonal), (ICDD card No. 81) -2144, Cs _0.3 WO ₃ , Hexagonal)) It is most preferable to determine the specific radioactivity, crystallinity and composition of the final compound (eg, final compound ⁽¹³³⁾ Cs _0.3 ⁽¹⁸⁴⁾ WO ₃ , Hexagonal). In addition, it is also possible to further confirm the particles distributed in the dispersion by mass spectrometry, bioradioactivity measurement, SEM, TEM, and the like.

Hereinafter, the excellent light-to-heat conversion properties, heat retention, and eco-friendliness of the eco-friendly light-to-heat conversion particulate dispersion will be described through specific experiments.

(1) Preparation of specimens

1) Example 1

Ammonium metatungstate hydrate ((NH ₄ ) ₆ H ₂ as a precursor containing one or more of tungsten stable isotopes ( ⁽¹⁸²⁾ W, ⁽¹⁸³⁾ W, ⁽¹⁸⁴⁾ W, ⁽¹⁸⁶⁾ W) ⁽¹⁸⁴⁾ W ₁₂ O ₄₀ H ₂ O) 30% by weight and cesium carbonate ( ⁽¹³³⁾ Cs ₂ CO ₃ ) containing cesium stable isotope ( ⁽¹³³⁾ Cs) 15% by weight with distilled water 450% by weight After putting them together in a container and dissolving them, they were filtered under reduced pressure with a filter paper treated with Prussian Blue and Zeolite on one side, and then put into a four-neck flask reactor.

Maintaining 80 ℃ using a heating mantle (Heating Mantle) and slowly stirred for 3 hours to dissociate into a liquid, and an inorganic acid or an organic acid was used as the dropping material (if it is possible to adjust the pH to 4 or less, it is irrelevant).

Among them, 50% by weight of fumaric acid was dissociated in distilled water and dropped into the flask reactor in which the precursor was dissolved using a dropping funnel at a constant speed for 20 minutes, and the translucent solution was A precipitate was gradually formed.

After aging for a certain period of time, the reaction was terminated and the filter and by-products were washed to obtain a gray-white reaction product. Sievert, a SI unit system indicating dose equivalent, was measured with a radioactivity measuring instrument QSF104m. As a result, the safety standard 0.4 0.15 μSv/h, which is lower than μSv/h, was measured, confirming the safety of the radioactivity level.

After obtaining cesium tungsten oxide in a hydrated state by the above process, it is calcined for about 2 hours at 200 ° C in air, transferred to the inside of an electric furnace, filled with nitrogen (N ₂ ) gas, maintained at 600 ° C for 3 hours, and then cooled. By terminating the reduction calcination, a dark blue high-energy unsensitized cesium tungsten oxide powder was obtained, and as a result of elemental analysis, nuclide analysis, mass spectrometry, and crystal analysis, Hexagonal ⁽¹³³⁾ Cs _0.3 ⁽¹⁸⁴⁾ WO ₃ turned out to be

High energy unsensitized cesium tungsten oxide ( ⁽¹³³⁾ Cs _0.3 ⁽¹⁸⁴⁾ WO ₃ ) powder 20% by weight, dispersant 0.5% by weight, alcohol-based solvent 79.5% by weight, 0.5mm zirconium beads 60% to the total volume A ball mill was performed for 72 hours to obtain a dispersed sol.

For solidification of the obtained dispersed sol, it was dried at 100° C. in a hot air dryer with smooth exhaust for 24 hours to obtain a dispersed solid. 6% by weight of the dispersed solid and 94% by weight of the PET thermoplastic polymer were mixed, put into a twin-screw extruder, and melt-kneaded at a temperature of 220° C. to obtain a dark blue masterbatch chip in the form of a column with an average length of 2.5 mm.

After that, high energy unsensitized cesium tungsten oxide ( ⁽¹³³⁾ Cs _0.3 ⁽¹⁸⁴⁾ WO ₃ ) 2 wt% of masterbatch chips and 98 wt% of PET masterbatch are mixed with a spinning nozzle of type O After being put into a spinning machine, spinning at 150 denier under the conditions of a spinning temperature of 250°C and a spinning speed of 1,000 m/min. Fibers containing cesium tungsten oxide ( ⁽¹³³⁾ Cs _0.3 ⁽¹⁸⁴⁾ WO ₃ ) were obtained.

2) Example 2

In Example ₁ , in the process of synthesizing high _- energy ^unsensitized complex tungsten oxide powder, the starting raw material was potassium carbonate ( ^{(39 ) )} K ₂ CO ₃ ) Example 2 was prepared under the same conditions as in Example 1 except that 15 wt% was added. That is, the positive element of the high-energy unsensitized cesium tungsten oxide ( ⁽¹³³⁾ Cs _0.3 ⁽¹⁸⁴⁾ WO ₃ ) of Example 1 is replaced with potassium ( ³⁹ K) from the existing cesium ( ¹³³ Cs), Fibers containing sensitized potassium tungsten oxide ( ⁽³⁹⁾ K _0.26 ⁽¹⁸⁴⁾ WO ₃ ) were obtained.

3) Example 3

In Example 1, in the process of synthesizing high-energy unsensitized complex tungsten oxide powder, the starting raw material was cesium carbonate ( ⁽¹³³⁾ Cs ₂ CO ₃ ) instead of ammonium-molybdate containing a stable molybdenum isotope ( ⁹⁸ Mo) ((NH ₄ ) ₆ ⁽⁹⁸⁾ Mo ₇ O ₂₄ ) Example 2 was prepared under the same conditions as in Example 1 except that 19.63 wt% was added. That is, the positive element of the high-energy unsensitized cesium tungsten oxide ( ⁽¹³³⁾ Cs _0.3 ⁽¹⁸⁴⁾ WO ₃ ) of Example 1 is replaced with molybdenum ( ⁹⁸ Mo) from the existing cesium ( ¹³³ Cs), Fibers containing sensitized molybdenum tungsten oxide ( ⁽⁹⁸⁾ Mo _0.3 ⁽¹⁸⁴⁾ WO _2.75 ) were obtained.

4) Example 4

In Example 1, in the process of synthesizing the high-energy unsensitized complex tungsten oxide powder, the starting raw material was cesium carbonate ( ⁽¹³³⁾ Cs ₂ CO ₃ ) instead of tin carbonate containing a stable tin isotope ( ¹²⁰ Sn) ( ^{(120 )} Sn(CO ₃ ) ₂ ) Example 2 was prepared under the same conditions as in Example 1 except that 17.28 wt% was added. That is, the positive element of the high-energy non-sensitized cesium tungsten oxide ( ⁽¹³³⁾ Cs _0.3 ⁽¹⁸⁴⁾ WO ₃ ) of Example 1 is replaced with tin ( ¹²⁰ Sn) from the existing cesium ( ¹³³ Cs), and high energy micro Fibers containing sensitized tin tungsten oxide ( ⁽¹²⁰⁾ Sn _0.26 ⁽¹⁸⁴⁾ WO ₃ ) were obtained.

5) Example 5

In Example 1, in the process of synthesizing the high-energy unsensitized complex tungsten oxide powder, the starting raw material was cesium carbonate ( ⁽¹³³⁾ Cs ₂ CO ₃ ), instead of aluminum carbonate containing an aluminum stable isotope ( ²⁷ Al) ( ^{(27 )} Al ₂ (CO ₃ ) ₃ ) Example 2 was prepared under the same conditions as in Example 1 except that 15 wt% was added. That is, the positive element of the high-energy unsensitized cesium tungsten oxide ( ⁽¹³³⁾ Cs _0.3 ⁽¹⁸⁴⁾ WO ₃ ) of Example 1 is replaced with aluminum ( ²⁷ Al) from the conventional cesium ( ¹³³ Cs), so that the high energy Fibers containing sensitized aluminum tungsten oxide ( ⁽²⁷⁾ Al _0.25 ⁽¹⁸⁴⁾ WO ₃ ) were obtained.

6) Example 6

In Example ₁ , in the process of synthesizing high _- energy unsensitized complex tungsten oxide powder, the starting raw material was rubidium carbonate ^{(( 85 ) )} Rb ₂ CO ₃ ) Example 2 was prepared under the same conditions as in Example 1 except that 20 wt% was added. That is, the positive element of the high-energy unsensitized cesium tungsten oxide ( ⁽¹³³⁾ Cs _0.3 ⁽¹⁸⁴⁾ WO ₃ ) of Example 1 is replaced with rubidium ( ⁸⁵ Rb) from the conventional cesium ( ¹³³ Cs), and high energy is not sensitized rubidium tungsten oxide ( ⁽⁸⁵⁾ Rb _0.3 ⁽¹⁸⁴⁾ WO _2.95 ), and the medium was changed from polyethylene terephthalate (PET) to nylon (Nylon).

7) Example 7

In Example 1, in the process of synthesizing high-energy unsensitized complex tungsten oxide powder, the starting raw material was replaced with cesium carbonate ( ⁽¹³³⁾ Cs ₂ CO ₃ ), but kappa carbonate containing copper stable isotope ( ⁶³ Cu) ( ⁽⁶³ ) ⁾ CuCO ₃ ) Example 2 was prepared under the same conditions as in Example 1 except that 20 wt% was added. That is, the positive element of the high-energy unsensitized cesium tungsten oxide ( ⁽¹³³⁾ Cs _0.3 ⁽¹⁸⁴⁾ WO ₃ ) of Example 1 was replaced with copper ( ⁶³ Cu) from the existing cesium ( ¹³³ Cs), and the high-energy micro Fibers containing sensitized copper tungsten oxide ( ⁽⁶³⁾ Cu _0.3 ⁽¹⁸⁴⁾ WO ₃ ) were obtained.

8) Example 8

In Example 1, in the process of synthesizing high-energy unsensitized complex tungsten oxide powder, the starting raw material was zinc carbonate ( ⁽⁶⁴ ) containing zinc stable isotope ( ⁶⁴ Zn) instead of cesium carbonate ( ⁽¹³³⁾ Cs ₂ CO ₃ ). ⁾ ZnCO ₃ ) Example 2 was prepared under the same conditions as in Example 1 except that 19.35 wt% was added. That is, the positive element of the high-energy unsensitized cesium tungsten oxide ( ⁽¹³³⁾ Cs _0.3 ⁽¹⁸⁴⁾ WO ₃ ) of Example 1 is replaced with zinc ( ⁶⁴ Zn) from the conventional cesium ( ¹³³ Cs), and high energy Fibers containing sensitized zinc tungsten oxide ( ⁽⁶⁴⁾ Zn _0.3 ⁽¹⁸⁴⁾ WO ₃ ) were obtained.

9) Example 9

In Example 1, the medium was changed from polyethylene terephthalate (PET) to acrylic (Acryl), and a dispersion sol of high energy unsensitized cesium tungsten oxide ( ⁽¹³³⁾ Cs _0.3 ⁽¹⁸⁴⁾ WO ₃ ) was prepared. After preparation, 5% by weight of the binder for the fiber fixing agent is additionally added compared to the sol, sprayed with a 0.5 MPa nozzle pressure on the general polyester fiber, dried in a hot air dryer at 120 ° C for 40 minutes, and then high energy unsensitized cesium tungsten oxide ( ^{( 133)} Cs _0.3 ⁽¹⁸⁴⁾ WO ₃ ) to obtain a fiber coated on the surface. That is, in applying the high-energy unsensitized cesium tungsten oxide ( ⁽¹³³⁾ Cs _0.3 ⁽¹⁸⁴⁾ WO ₃ ), it was applied in the form of coating on the surface of a general fiber instead of injecting it into a yarn.

10) Example 10

In Example 9, in the process of synthesizing the high-energy unsensitized complex tungsten oxide powder of Example 9, the starting raw material was sodium carbonate containing a stable sodium isotope ( ²³ Na) instead of cesium carbonate ( ⁽¹³³⁾ Cs ₂ CO ₃ ). ( ⁽²³⁾ NaCO ₃ ) Example 2 was prepared under the same conditions as in Example 1 except for adding 19.35 wt%. That is, the positive element of the high-energy unsensitized cesium tungsten oxide ( ⁽¹³³⁾ Cs _0.3 ⁽¹⁸⁴⁾ WO ₃ ) of Example 1 is replaced with sodium ( ²³ Na) from the existing cesium ( ¹³³ Cs), Fibers containing sensitized sodium tungsten oxide ( ⁽²³⁾ Na _0.3 ⁽¹⁸⁴⁾ WO ₃ ) were obtained.

11) Comparative Example 1

In Example 1, a polyester fiber without inorganic particles was prepared without preparing high energy unsensitized cesium tungsten oxide ( ⁽¹³³⁾ Cs _0.3 ⁽¹⁸⁴⁾ WO ₃ ). That is, the light-to-heat conversion efficiency of fibers excluding materials such as high-energy unsensitized cesium tungsten oxide ( ⁽¹³³⁾ Cs _0.3 ⁽¹⁸⁴⁾ WO ₃ ) was prepared as a comparison group.

12) Comparative Example 2

In Example 10, a comparison group in which the medium was changed from acrylic to silicone was prepared.

(2) Experimental method

1) Mass spectrometry (MS) of particulates is a device including RF generator, Torch, Nebulizer, Spray Chamber, Skimmer cone, Focusing systen, Quadrupole, ESA and magnet, and mixed acid (HNO ₃ : HF: HClO ₄ =4:4:1) through the sample pretreatment process, and measurements were made according to the above conditions.

2) nuclide analysis of particulates In the HASL-300 method, nuclide analysis was performed under the conditions of 0 to 16,384 channels, 5 to 3,000 keV, Detect Efficiency (by Nal(Tl)) 30%, and 0 to 4.5 kV High Voltage. Isotopes with radioactivity are called radionuclides.

3) The microparticles were measured by X-ray diffraction analysis (X-ray diffraction, XRD), and the crystal structure was confirmed by comparison with an X-ray diffraction data card.

4) The size of the particles was confirmed under the conditions of HITACHI (JAPAN) S-2400 SEM (Scanning Electron Microscope), 15 kw.

5) In the light-heating test of the fiber coated with fine particles, a 220 V, 500 W, 3200 K infrared lamp was placed at a distance of 30 cm from the fiber, and the temperature when irradiated with light for 10 minutes and light for 10 minutes After irradiation, the fiber temperature 20 minutes after the light irradiation was stopped was measured using a non-contact thermometer.

6) The living becquerel strength (Bq/m ³ ) of the dispersion containing fine particles was measured using an RD-200 radioactivity meter.

(3) Experiment result

1) Result of mass spectrometry of particulates

The results of measuring the particles by mass spectrometry (MS) are shown in Tables 1 to 3 below.

division Example 1 Example 2 Example 3 Example 4 Example 5 ^(y) A ⁽¹³³⁾ Cs ⁽³⁹⁾ K ⁽⁹⁸⁾ Mo ⁽¹²⁰⁾ Sn ⁽²⁷⁾ Al ^(z) W ⁽¹⁸⁴⁾ W ⁽¹⁸⁴⁾ W ⁽¹⁸⁴⁾ W ⁽¹⁸⁴⁾ W ⁽¹⁸⁴⁾ W

division Example 6 Example 7 Example 8 Example 9 Example 10 ^(y) A ⁽⁸⁵⁾ Rb ⁽⁶³⁾ Cu ⁽⁶⁴⁾ Zn ⁽¹³³⁾ Cs ⁽²³⁾ Na ^(z) W ⁽¹⁸⁴⁾ W ⁽¹⁸⁴⁾ W ⁽¹⁸⁴⁾ W ⁽¹⁸⁴⁾ W ⁽¹⁸⁴⁾ W

division Comparative Example 1 Comparative Example 2 ^(y) A - ⁽²³⁾ Na ^(z) W - ⁽¹⁸⁴⁾ W

2) Result of nuclide analysis of particulates

Tables 4 to 6 show the results of measuring the fine particles by the nuclide analysis (HASL-300) method. In Tables 4 to 6, E(Bq) indicates the presence or absence of a radionuclide corresponding to a positive element, and T(Bq) indicates the presence or absence of a radionuclide corresponding to a tungsten element. The threshold value for determining the presence or absence of radionuclides of the positive element is 0.02, and the threshold value for determining the presence or absence of radionuclides of the tungsten element is 0.05, confirming that there is no radionuclide in Examples and Comparative Examples except Comparative Example 1.

division Example 1 Example 2 Example 3 Example 4 Example 5 E(Bq) ≤0.02 ≤0.02 ≤0.02 ≤0.02 ≤0.02 T(Bq) ≤0.05 ≤0.05 ≤0.05 ≤0.05 ≤0.05

division Example 6 Example 7 Example 8 Example 9 Example 10 E(Bq) ≤0.02 ≤0.02 ≤0.02 ≤0.02 ≤0.02 T(Bq) ≤0.05 ≤0.05 ≤0.05 ≤0.05 ≤0.05

Comparative Example 1 Comparative Example 2 E(Bq) - ≤0.02 T(Bq) - ≤0.05

3) Result of X-ray diffraction analysis of fine particles

The results of measuring the crystal form of the fine particles by X-ray diffraction analysis (X-ray Dirrfaction, XRD) are shown in Tables 7 to 9 below. Examples 1, 2, 5, 6, 8, 9 are hexagonal type, Examples 3 and 7 are orthorhombic type, Examples 4, 10 and Comparative Example 2 are tetragonal type appeared as

division Example 1 Example 2 Example 3 Example 4 Example 5 XRD Determination hexagonal system hexagonal system orthorhombic tetragonal system hexagonal system

division Example 6 Example 7 Example 8 Example 9 Example 10 XRD Determination hexagonal system orthorhombic hexagonal system hexagonal system tetragonal system

division Comparative Example 1 Comparative Example 2 XRD Determination - tetragonal system

4) Result of particle size measurement

As a result of SEM measurement, in Example 1, the particle size was about 30 nm, and the powder was blue (when the fine particles were calcined in air, they appeared grayish white), and it was found that the particles were reduced due to lack of oxygen, not a complete oxide. In the remaining Examples and Comparative Examples, the particle size and powder color are shown in Tables 10 to 12 below.

division Example 1 Example 2 Example 3 Example 4 Example 5 particle size 30nm 30nm 40nm 50nm 30nm powder color blue blue dark blue dark brown blue

division Example 6 Example 7 Example 8 Example 9 Example 10 particle size 30nm 40nm 30nm 30nm 40nm powder color light blue greenish blue greenish blue blue dark blue

division Comparative Example 1 Comparative Example 2 particle size - 40nm powder color - dark blue

5) Light-heating test result

T ₀ is the initial temperature, T ₁ is the temperature after 10 minutes of light irradiation, T ₂ is the temperature after 20 minutes after stopping the light irradiation, and the values are shown in Tables 13 to 15 below. When Examples 1 to 10 and Comparative Example 1 were compared, higher light-to-heat conversion efficiency and heat retention were confirmed in the fiber containing the microparticles of the present invention. And when comparing Examples 1 to 10 and Comparative Example 2, when the medium is made of polyethylene terephthalate (PET) or acrylic (Acryl), it is superior to light-heat compared to that of silicon (Silicon). It has been shown to exhibit conversion efficiency and heat retention.

division Example 1 Example 2 Example 3 Example 4 Example 5 T ₀ 17.44℃ 17.32℃ 17.42℃ 17.41℃ 17.36℃ T ₁ 28.72℃ 28.62℃ 28.70℃ 28.79℃ 28.63℃ T ₂ 24.48℃ 24.17℃ 24.23℃ 24.27℃ 24.18℃

division Example 6 Example 7 Example 8 Example 9 Example 10 T ₀ 17.43℃ 17.39℃ 17.38℃ 17.44℃ 17.25℃ T ₁ 28.71℃ 28.67℃ 28.68℃ 28.98℃ 28.63℃ T ₂ 24.24℃ 24.21℃ 24.21℃ 24.24℃ 24.18℃

division Comparative Example 1 Comparative Example 2 T ₀ 17.42℃ 17.25℃ T ₁ 24.71℃ 26.72℃ T ₂ 22.32℃ 23.15℃

6) Measurement result of becquerel strength

As a result of measuring the fibers containing fine particles for living radioactivity with the RD-200 radioactivity meter, as shown in Tables 16 to 18 below, all were confirmed to have a reference value of 148 Bq/m ³ or less.

division Example 1 Example 2 Example 3 Example 4 Example 5 becquerel strength 18.66 Bq/m ³ 19.78 Bq/m ³ 24.12 Bq/m ³ 23.22 Bq/m ³ 24.86 Bq/m ³

division Example 6 Example 7 Example 8 Example 9 Example 10 becquerel strength 18.32 Bq/m ³ 19.32 Bq/m ³ 19.55 Bq/m ³ 18.66 Bq/m ³ 20.23 Bq/m ³

division Comparative Example 1 Comparative Example 2 becquerel strength 18.73 Bq/m ³ 20.23 Bq/m ³

In conclusion, through the above experiment, in addition to the fact that ^(y) A _x ^(z) WO _(3-n) type particles do not emit harmful radiation, they induce amplification of molecular vibrations such as polymers in light absorption exothermic properties. A new use of excellent heat generating properties by inducing a resonance effect was confirmed.

The above detailed description is illustrative of the present invention. In addition, the above description shows and describes preferred embodiments of the present invention, and the present invention can be used in various other combinations, modifications, and environments. That is, changes or modifications are possible within the scope of the concept of the invention disclosed herein, the scope equivalent to the written disclosure, and/or within the scope of skill or knowledge in the art. The written embodiment describes the best state for implementing the technical idea of the present invention, and various changes required in the specific application field and use of the present invention are possible. Therefore, the detailed description of the present invention is not intended to limit the present invention to the disclosed embodiments. Also, the appended claims should be construed as including other embodiments.

1: Eco-friendly light-heat conversion particle dispersion
10: medium
30: Eco-friendly light-to-heat conversion particles
31: high energy unsensitized composite tungsten oxide
S1: Method for manufacturing eco-friendly light-to-heat conversion particle dispersion
S10: Media providing step
S30: Particle providing step
S31: oxide formation step
S311: hydrate synthesis step
S3111: precursor providing step
S3113: dissolution purification step
S3115: precipitation step
S313: first calcination step
S315: Second reduction firing step
S33: dispersion sol formation step
S50: dispersion formation step

Claims (26)

Contains high energy unsensitized complex tungsten oxide that is not harmful by radiation, absorbs light on behalf of the medium, and converts the absorbed light into thermal energy to deliver it to the medium,
The high-energy unsensitized composite tungsten oxide is in the form of ^(y) A _x ^(z) WO _(3-n) , wherein ^(y) A and ^(z) W are stable isotopes without radiation toxicity, Wherein x is the number of elements doped to ^(y) A according to reduction plasticity, y is the mass number of A, z is the mass number of W, and (3-n) is the number of oxygen means,
^(y) A includes at least one of a non-radioactive alkali metal stable isotope, a non-radioactive alkaline earth metal stable isotope, and a non-radioactive rare earth stable isotope,
Wherein ^(z) W, ¹⁸² W, ¹⁸³ W, ¹⁸⁴ W, and ¹⁸⁶ W, characterized in that it comprises any one or more, eco-friendly light-to-thermal conversion particles. delete delete According to claim 1,
Wherein ^(y) A is, ¹³³ Cs, ³⁹ K, ²³ Na, ⁹⁸ Mo, ¹²⁰ Sn, ²⁷ Al, ⁸⁵ Rb, ⁶³ Cu and ⁶⁴ Zn, characterized in that it contains any one or more of, eco-friendly light-to-thermal conversion particulates. According to claim 1,
The high-energy unsensitized composite tungsten oxide includes at least one of a cubic type, a hexagonal type, a tetragonal type, an orthorhombic type, and a monoclinic type Characterized in that, eco-friendly light-to-thermal conversion particles. According to claim 1,
^(y) A _x ^(z) x in WO _(3-n) is 0.01 or more and less than 2, environmentally friendly light-to-heat conversion microparticles. According to claim 1,
^(y) A _x ^(z) n of WO _(3-n) is 0 or more and 1.5 or less, Eco-friendly light-to-heat conversion microparticles. delete According to any one of claims 1 and 4 to 7, environmental-friendly light-to-heat conversion fine particles,
The eco-friendly light-to-heat conversion particle dispersion, characterized in that it comprises a medium for accumulating or radiating heat energy converted from the eco-friendly light-to-heat conversion particles. 10. The method of claim 9,
The eco-friendly light-to-heat conversion particulate dispersion has the exothermic characteristics after light absorption, T _l - T ₀ = ΔT _l' , T ₀ < T _l (T ₀ : initial temperature, T _l : later temperature, ΔT _l' : Eco-friendly light-heat conversion particulate dispersion, characterized in that it is the later temperature - the first temperature). 11. The method of claim 10,
The eco-friendly light-to-heat conversion particulate dispersion, characterized in that the heat conversion efficiency compared to light absorption is 1.1 times or more, the eco-friendly light-heat conversion particulate dispersion. 10. The method of claim 9,
The eco-friendly light-to-heat conversion particulate dispersion, characterized in that the radiation intensity is 148 Bq/m ³ or less, eco-friendly light-to-heat conversion particulate dispersion. A medium providing step of providing a medium containing particulates for eco-friendly light-to-heat conversion;
Eco-friendly light-to-heat conversion microparticles that contain high-energy unsensitized complex tungsten oxide, have no harmful effects from radiation, absorb light on behalf of the medium, and convert the absorbed light into thermal energy and deliver it to the medium. A step of providing particulates to provide,
and a dispersion forming step of forming an eco-friendly light-to-heat conversion particle dispersion comprising the medium and the eco-friendly light-heat conversion microparticles,
The step of providing fine particles includes an oxide forming step of forming a high-energy unsensitized complex tungsten oxide in the form of oxygen-deficient ^(y) A _x ^(z) WO _(3-n) , wherein ^(y) A and ^(z) W is a stable isotope that is not harmful by radiation, x is the number of elements doped to ^(y) A according to the reductive property, y is the mass number of A, and z is is the mass number of W, and (3-n) means the number of oxygen,
^(y) A includes at least one of a non-radioactive alkali metal stable isotope, a non-radioactive alkaline earth metal stable isotope, and a non-radioactive rare earth stable isotope,
Wherein ^(z) W, ¹⁸² W, ¹⁸³ W, ¹⁸⁴ W, and ¹⁸⁶ W, characterized in that it comprises at least any one of, environmentally friendly light-to-heat conversion method for fine particle dispersion manufacturing method. delete 14. The method of claim 13,
The oxide forming step, characterized in that it comprises a hydrate synthesis step of synthesizing a high-energy unsensitized complex tungsten hydrate, an environmentally friendly light-to-heat conversion method for producing a particle dispersion. 16. The method of claim 15,
The hydrate synthesis step includes a precursor providing step of providing a precursor as a stable isotope, and a dissolution purification step of dissolving and purifying the precursor with a solvent of 10 or more times or more after the precursor providing step, and after the dissolution and purification step, A method for producing an eco-friendly light-to-heat conversion particulate dispersion, characterized in that it comprises a precipitation step that causes precipitation by inputting an opposite acid value (pH). 16. The method of claim 15,
The hydrate synthesis step, characterized in that made by the liquid phase co-precipitation method, eco-friendly light-to-heat conversion particulate dispersion manufacturing method. 16. The method of claim 15,
The oxide forming step includes a first calcination step of calcining to remove hydroxyl groups (-OH) and water molecules from the synthesized high-energy unsensitized complex tungsten hydrate after the hydrate synthesis step, and the first calcination step Thereafter, the method for producing an eco-friendly light-to-heat conversion particulate dispersion comprising a secondary reduction calcination step of reducing and calcining under the input of an inert gas for oxygen deficiency of the high-energy unsensitized composite tungsten oxide. 19. The method of claim 18,
The inert gas, N ₂ , Ar, Ne, and CO ₂ Characterized in that it contains any one or more, environment-friendly light-to-heat conversion method for particulate dispersion manufacturing method. 14. The method of claim 13,
The particulate providing step, characterized in that it comprises a dispersed sol forming step of forming a dispersed sol comprising a high energy unsensitized complex tungsten oxide, a dispersing agent, and a solvent after the oxide forming step, eco-friendly light- A method for producing a particulate dispersion for heat conversion. The dispersion sol of claim 20, the binder for the fiber fixing agent, short fibers, long fibers, spun yarns, filament yarns, PF (Polyester Filament Yarn), POY (Pre Oriented Yarn or Partial Orinted Yarn), FDY (Fully Draw Yarn), DTY (Draw Textured Yarn) and ITY (Interlaced Yarn or Irregular Twisted Yarn), characterized in that it contains any one or more of the base fibers, insulation fibers. 22. The method of claim 21,
The thermal insulation fiber, characterized in that it is formed by spraying a mixture of the dispersion sol and the binder for the fiber fixing agent on the surface of the base fiber and drying it, the thermal insulation fiber. The masterbatch, characterized in that the eco-friendly light-to-heat conversion fine particles of any one of claims 1 and 4 to 7, and melt-kneading the medium of any one or more of a synthetic polymer and a natural polymer with an extruder for injection. The thermal insulation fiber, characterized in that the masterbatch of claim 23 is included in 100% by weight of the base thermoplastic polymer masterbatch in an amount of 1% to 30% by weight and spun. The eco-friendly light-to-heat conversion microparticles of any one of claims 1 to 7 and a thermoplastic polymer, but the thickness is 0.1 μm to 50 μm, and the transmittance at a visible light wavelength of 550 nm is 10% or more Characterized in that, a multilayer film. According to any one of claims 1 and 4 to 7, wherein the eco-friendly light-to-heat conversion fine particles and a thermoplastic polymer, the thickness is 0.1 ㎛ to 50 ㎛, and the surface temperature difference after light irradiation is T _l - T ₀ = ΔT _l' , T ₀ < T _l (T ₀ : initial temperature, T _l : later temperature, ΔT _l' : later temperature - initial temperature), characterized in that the multilayer film.

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