WO2020080844A1

WO2020080844A1 - Heat shielding film and method for manufacturing same

Info

Publication number: WO2020080844A1
Application number: PCT/KR2019/013647
Authority: WO
Inventors: 황태경
Original assignee: 황태경
Priority date: 2018-10-18
Filing date: 2019-10-17
Publication date: 2020-04-23
Also published as: KR102125359B1; KR20200043824A

Abstract

The present invention relates to a heat shielding film and a method for manufacturing same and, more specifically, to a heat shielding film and a method for manufacturing same, wherein the heat shielding film: prevents a problem in which a film, which is completed by fundamentally blocking haze by making a heat shielding layer, to be formed on one surface of a substrate layer, of an oxygen-deficient transition metal oxide, cannot be clearly seen due to a scattering phenomenon; improves visible light transmittance and infrared rejection; and resolves, by means of a passivation film, problems of thermal resistance and durability due to a reaction caused by the introduction of residual oxygen when making the heat shielding layer of the oxygen-deficient transition metal oxide, a reaction caused by residual hydroxyl, a reaction caused by residual radical, etc.

Description

Heat shielding film and its manufacturing method

The present invention relates to a heat shielding film and a method for manufacturing the same, and more specifically, a heat shielding layer formed on one surface of a base layer is composed of an oxygen-deficient type transition metal oxide to block haze in a prominent manner, and in a completed film It prevents the problem of appearing cloudy due to the scattering phenomenon, improves the visible light transmittance and infrared ray blocking rate, and reacts by the influx of residual oxygen, the reaction by residual hydroxyl, and the residual radical when the heat shielding layer is composed of an oxygen-deficient transition metal oxide. The problem of heat resistance and durability due to reaction by the present invention relates to a heat shielding film and a method of manufacturing the solution through a passivation film.

The heat shielding material can be roughly classified into an organic compound type heat shielding material and an inorganic compound type heat shielding material.

The organic compound type heat shielding material shows high visible light transmittance, but absorption occurs only near a single wavelength (≒ 950nm) in the near-infrared region, so it is difficult to effectively block near the thermal energy region felt by the human body. The shielding effect is poor. Therefore, the organic compound type heat shielding material is used as an auxiliary material for heat shielding while being mixed with an inorganic compound type heat shielding material. Organic compounds include LaB ₆ , Phthalocyanine, Carbon Black, Titan Black, Metal Complex, Diimonium Salt, Phthalocyanine, and the like. Among them, organic compounds that are widely used are metal complex, carbon black, and diimonium salt.

On the other hand, the inorganic compound type heat shielding material has a low visible light transmittance, but has superior durability and high heat shielding properties than the organic compound type material. In particular, there are many inorganic oxides as the heat shielding material, and these inorganic oxides include antimony oxide (ATO), indium tin oxide (ITO), silica dioxide (SiO ₂ ), alumina trioxide (Al ₂ O ₃ ), and molybdenum trioxide. (MoO ₃ ), niobium pentoxide (Nb ₂ O ₅ ), vanadium pentoxide (V ₂ O ₅ ), tungsten bronze, tungsten oxide, etc. are used. Among them, the most widely used inorganic oxides having good infrared ray blocking properties are antimony oxide (ATO), indium tin oxide (ITO), and tungsten bronze.

Antimony oxide (ATO) is cheaper than indium tin oxide (ITO), and is widely applied to general heat shielding films. However, as a transmission graph with a gentle slope from 1500nm to 2200nm among the near-infrared transmission peaks, perfect infrared blocking is not achieved, and the input amount is limited to secure a high visible light transmittance. If the amount of antimony oxide (ATO) sol is increased to secure a high near-infrared ray blocking rate, the visible light transmittance will drop significantly to 40-50%, and excessive inorganic content will cause cracks in the heat-shielding coating layer, decrease in adhesion, cloudiness, change over time, etc. Causes As described above, even with antimony oxide (ATO) having a particle size of 30 nm, the near-infrared ray blocking property has a limitation as compared to visible light, so its utilization range is narrow and it cannot be easily applied to manufacturing high-performance heat shielding films.

Indium tin oxide (ITO) has higher visible light transmittance and infrared ray blocking properties than antimony oxide (ATO). However, indium (Indium) price is well known as a high-priced raw material in the world, most of the electronics industry is developing a material that can replace indium tin oxide (ITO). In addition, it is inevitable to use such expensive raw materials in the production of heat shielding films. Therefore, it is urgent to develop a material having higher visible light transmittance and higher near-infrared ray blocking properties than indium tin oxide (ITO).

In addition, antimony oxide (ATO) and indium oxide (ITO) are manufactured through very difficult processes in the synthesis of nanoparticle inorganic oxides. In particular, antimony hydroxide (ATO (OH)) and indium hydroxide (ITO (OH)) prepared by the Sol-Gel method and the Autoclave method must undergo a firing process. The firing takes place twice, and after primary firing in air at 300 to 400 ° C, secondary hydrogen reduction firing is performed. At this time, hydrogen gas (Gas) and an inert gas are mixed to perform reduction firing, and even if a little oxygen is added, the possibility of explosion is very high and requires attention, and the equipment is also a very expensive equipment for the gas flow kiln. In this way, there are disadvantages in stability and expensive equipment investment in manufacturing antimony oxide (ATO) and indium oxide (ITO).

Perovskite tungsten bronze is a wide band gap oxide, in which tungsten trioxide is doped with a positive element such as Na, and generally has a perovskite structure (ABO ₃ ). . As a characteristic of tungsten bronze, since light energy absorption is strong from a wavelength of 800 nm or more, and light energy absorption at a wavelength of 380 to 780 nm is weak, it has been actively studied in a field requiring transparency. Tungsten bronze compounds are known to be about 50,000, and in particular, tungsten bronze compounds showing infrared ray blocking properties are in the form of A _x W ₁ O _y , A _x is an alkali metal and alkaline earth metal element, W ₁ is tungsten, O _y is oxygen It consists of. Alkali metal element series have a large element radius compared to other elements, resulting in large particle size. In most cases, the size of the primary particle size is less than 100 nm, and when the primary particle size is 50 nm, the particle size becomes 50 nm or more when actually manufactured with a dispersion sol. Dispersed sols of 50 nm or more have high haze and show scattering. If produced as a film, a problem occurs that is bluish due to scattering. Therefore, a high quality heat shielding film having a low haze value and high transparency is required by applying an improved tungsten bronze or tungsten oxide.

Tungsten oxide is a wide band gap oxide, WO ₃ (tungsten trioxide) has a yellow color, and WO _2.81 to WO _2.95 (named WO _3-x ) have a blue color. In particular, WO _3-x has a reduced amount of oxygen and has infrared shielding properties. WO ₃ having a complete oxygen content has no infrared shielding properties and can be obtained by calcining several precursors obtained through various manufacturing methods in air. On the other hand, blue WO _3-x can be obtained by reducing calcination. Reduction firing is made after firing with an inert gas instead of oxygen. WO _3-x is oxidized again under certain conditions due to the vacancies of oxygen, and is easily changed to tungsten trioxide, so that the color changes or the infrared shielding properties disappear. Due to this problem, the use of WO _3-x is limited or not used as a heat shielding material. If this problem is not solved and applied to the heat shielding film, deformation may occur in the coated infrared shielding layer according to environmental conditions.

1 is a view of a conventional thermal barrier film, the prior art is disclosed in Korean Patent Registration No. 10-1681614 (2016.12.01). Referring to FIG. 1, the prior art of FIG. 1 applied tungsten oxide to a thermal barrier shrink film, but the particles used are considerably larger to 1 to 6 μm, thereby reducing visible light transmittance and increasing heat shielding effect. In order to increase the input amount of tungsten oxide in order to make the synthetic resin film used as a substrate, there is a problem that the original physical properties such as dimensional stability and elasticity, elongation, etc., which are fragile or synthetic resin film characteristics, must be deteriorated.

Therefore, in the related industry, it is required to develop a new type of heat shielding film that can effectively block infrared rays distributed in sunlight, has heat resistance and durability, has a simple manufacturing process, and does not require much cost for manufacturing. Is in

(Patent Document 1) Korean Registered Patent Publication No. 10-1681614 (2016.12.01)

The present invention was made to solve the above problems,

The object of the present invention is to block the haze by making the heat shielding layer formed on one surface of the base layer made of an oxygen-deficient transition metal oxide so that the average particle size is less than 100 nm, due to scattering in the finished film. It is to provide a heat shielding film that prevents the appearance of blurring and improves the visible light transmittance and infrared light blocking rate.

Another object of the present invention, the oxygen-deficient transition metal oxide is configured to form a rutile (Rutile) -type structure of AO _(3-X) , thereby having a relatively small primary particle size, thereby firing during compound production It is to provide a heat shielding film that prevents the problem that the particle size increases during the process.

Another object of the present invention is to prepare a uniform nano-sized particle by easily producing a particle and controlling particle size by preparing an oxygen-deficient transition metal oxide by a simple liquid deposition method with synthetic conditions.

Another object of the present invention is to calcinate the synthesized transition metal oxide in a range of 300 to 600 ° C. to remove hydroxyl groups and water molecules to form rutile crystals having a small particle size.

Another object of the present invention is to induce the oxygen deficiency of the transition metal oxide forming a rutile type crystal through reduction calcination to have infrared absorption characteristics due to crystal defects or vacancies of oxygen, and such reduced calcination instead of hydrogen gas By making it under the inert gas input, it is possible to reduce the operational risk and to easily use the existing firing equipment.

Another object of the present invention, by forming the organic acid metal chelate compounds (Organic Acid Metallic Chelate Compounds) that do not have heterogeneous reactivity while having selective reactivity first, on the surface of the oxygen-deficient transition metal oxide or distributed in the dispersion sol, residual oxygen O ₂ ) The organic acid metal chelate compound effectively blocks the reaction by inflow, the reaction by residual hydroxyl (-OH), and the reaction by residual radicals, such as heat resistance, durability, etc. of the oxygen-deficient transition metal oxide Is to complement the problem.

Another object of the present invention is to prepare an organic acid metal chelate compound serving as an immobilized film by a reflux method so that a compound suitable for a desired purpose can be easily produced in an existing facility.

Another object of the present invention, when the hot air drying and UV irradiation for drying and curing the coated film is a problem that deformation may occur as the substrate layer is exposed to a temperature of 120 ° C. or higher, the heat deformation temperature is high and the dimensions are high. It is to solve the problem by constructing the base layer with polyethylene terephthalate, which has excellent stability.

Another object of the present invention is to configure the content of the oxygen-deficient transition metal oxide in the dispersion sol to be 20 to 30% by weight, so that sufficient optical properties are expressed, and dispersion time is reduced to prevent deformation of the dispersant.

Another object of the present invention, the content of the dispersant in the dispersion sol is 1 to 10% by weight, to obtain a sufficient dispersion sol, when drying the coated surface, the dispersant that is not dried remains on the coating surface of the coating surface It does not cause defects.

Another object of the present invention is to configure the content of the organic acid metal chelate compound in the dispersion sol to 5 to 10% by weight, without significantly reducing optical properties such as visible light transmittance and infrared shielding rate, oxygen-deficient transition metal oxide It is to greatly improve the heat resistance and durability of.

Another object of the present invention is to form a dispersion sol by a ball mill method, thereby easily dispersing the agglomerated powder, simplifying the formation of a dispersion sol, and enabling mass production.

Another object of the present invention is to increase the optical properties of the film and the adhesion of the coating film, and improve the scratch resistance of the surface by making the content of the dispersion sol in the coating sol to be 40-50% by weight.

Another object of the present invention, as an oligomer (Oligomer), which causes photopolymerization by ultraviolet irradiation as a photopolymer, a monomer (Monomer), including a photoinitiator in the coating sol, to enhance the bonding strength of the coating sol and the base layer, the thickness of the coating film It is to be able to finely adjust.

Another object of the present invention, by configuring the thickness of the coating film applied to the base layer to 3 ~ 4㎛, while maintaining the optical properties to improve the surface scratch resistance, prevent surface cracking, adhesion to the base layer Is to improve.

Another object of the present invention is to configure the adhesive layer on one surface of the heat shielding layer, so that the film can be easily adhered to buildings or vehicles.

Another object of the present invention is to attach a release paper to one surface of the adhesive layer so that one surface of the adhesive layer is protected by the release paper.

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

According to an embodiment of the present invention, the present invention includes a base layer and a heat shielding layer formed on one surface of the base layer, wherein the heat shielding layer includes an oxygen-deficient transition metal oxide, and has a haze phenomenon. It is characterized by improving the visible light transmittance and the infrared light blocking rate.

According to another embodiment of the present invention, the present invention is characterized in that the oxygen-deficient transition metal oxide forms an AO _(3-X) type rutile structure.

According to another embodiment of the present invention, the present invention is characterized in that the A comprises at least one element of Cu, Ag, Zn, Ni, W and Co.

According to another embodiment of the present invention, the present invention is characterized in that the oxygen-deficient transition metal oxide is calcined in a range of 300 to 600 ° C. to remove hydroxyl groups and water molecules and form crystals.

According to another embodiment of the present invention, the present invention is characterized in that the oxygen-deficient transition metal oxide, for oxygen deficiency, is subjected to reducing calcination under the introduction of an inert gas.

According to another embodiment of the present invention, the present invention is characterized in that the inert gas includes N ₂ , Ar, Ne and CO ₃ .

According to another embodiment of the present invention, the present invention is characterized in that the heat shielding layer further includes a passivation film to improve the heat resistance and durability of the oxygen-deficient transition metal oxide.

According to another embodiment of the present invention, the present invention is characterized in that the passivation film comprises an organic acid metal chelate compound.

According to another embodiment of the present invention, the present invention, the organic acid metal chelate compound, has a R1-M-R2 structure, the M is Cu, Ag, Zn, Ni, W, and any one element of Co , And R1 and R2 are characterized by any one of low molecular weight glutamic acid and high molecular weight sodium poly aspartate.

According to another embodiment of the present invention, the present invention, the base layer is characterized in that the polyethylene terephthalate (Polyethylene Terephthalate).

According to another embodiment of the present invention, the present invention includes a substrate layer providing step of providing a substrate layer, and a heat shield layer forming step of forming a heat shielding layer on one surface of the substrate layer after the substrate layer providing step. And, the thermal barrier layer forming step, the oxygen-deficient transition metal oxide forming step of generating a transition metal oxide deficient in oxygen, and after the oxygen-deficient transition metal oxide forming step passivated film on the oxygen-deficient transition metal oxide It characterized in that it comprises a passivation film forming step of forming, and a coating step of forming a coating film on the base layer after the passivation film step.

According to another embodiment of the present invention, the present invention, the oxygen-deficient transition metal oxide forming step, in the synthesis step of synthesizing the transition metal oxide by a liquid precipitation method, and the transition metal oxide synthesized after the synthesis step In order to remove hydroxyl groups and water molecules and to form crystals, a primary calcination step of calcining in a range of 300 to 600 ° C., and reducing calcination under inert gas for oxygen deficiency of transition metal oxides after the first calcination step It characterized in that it comprises a secondary reduction firing step.

According to another embodiment of the present invention, the present invention, the passivation coating step, an organic acid metal chelate compound manufacturing step for producing an organic acid metal chelate compound, and the dispersion to form a dispersion sol after the organic acid metal chelate compound manufacturing step Characterized in that it comprises a sol-forming step.

According to another embodiment of the present invention, the present invention, the organic acid metal chelate compound production step, the precursor containing the transition metal is dissolved in an organic acid solvent, stirred at 60 to 80 ℃ for 4 to 5 hours to reflux (Reflux) It is characterized by.

According to another embodiment of the present invention, the present invention, the dispersion sol forming step, oxygen-deficient transition metal oxide 20 to 30% by weight, dispersing agent 1 to 10% by weight, organic acid metal chelate compound 5 to 10% by weight It characterized in that to form a dispersion sol containing a percent.

According to another embodiment of the present invention, the present invention, the coating step, coating sol forming step of forming a coating sol, and coating sol coating to apply the coating sol to the base layer after the coating sol forming step And a drying curing step of drying the base layer on which the coating sol is applied, followed by hot air drying and ultraviolet curing after the coating sol application step.

According to another embodiment of the present invention, the present invention, the coating sol forming step, a coating sol comprising 40 to 50% by weight of a dispersion sol, 40 to 50% by weight of a binder, and 10 to 20% by weight of an organic solvent It is characterized by forming.

According to another embodiment of the present invention, the present invention is characterized in that the binder comprises an oligomer (Oligomer), a monomer (Monomer), a photoinitiator that causes photopolymerization by irradiation with ultraviolet light as a photopolymer.

According to another embodiment of the present invention, the present invention, the organic solvent, methyl ethyl ketone (Methyl Ethyl Ketone), toluene (Toluene), ethyl acetate (Ethyl Acetate), isopropyl alcohol (Iso Propyl Alcohol), ethyl Ethyl Cellosolve, Iso butyl Alcohol, Dimethylformamide, Ethanol, Butyl Cellosolve, Xylene, 1-Octanol ), Diethylene glycol (Diethylene Glycol), nitrobenzene (Nitrobenzene) characterized in that it contains any one or more of.

According to another embodiment of the present invention, the present invention, the coating sol coating step, using a micro gravure (Micro Gravure) coating, knife (Knife) coating and roll to roll (Roll to Roll) coating using any one of It is characterized by.

According to another embodiment of the present invention, the present invention, the coating sol coating step, characterized in that the thickness of the coating film is 3 ~ 4㎛.

According to another embodiment of the present invention, the present invention, the heat shielding film manufacturing method further comprises an adhesive layer forming step of forming an adhesive layer on one surface of the heat shield layer after the heat shield layer forming step It is characterized by.

According to another embodiment of the present invention, the present invention, the heat shielding film manufacturing method is characterized in that it further comprises a release paper attaching step of attaching a release paper to one side of the adhesive layer after the adhesive layer forming step do.

According to the present invention, the following effects can be obtained according to the configuration, combination, and use relationship described above with respect to the present embodiment.

In the present invention, the heat shielding layer formed on one surface of the base layer is composed of an oxygen-deficient transition metal oxide so that the average particle size is less than 100 nm, haze is prevented, and the finished film appears cloudy due to scattering phenomenon. It has the effect of preventing a problem and providing a heat shielding film with improved visible light transmittance and infrared blocking rate.

In the present invention, the oxygen-deficient transition metal oxide is configured to form an AO _(3-X) -type rutile (Rutile) -type structure, thereby having a relatively small primary particle size, particles during the firing process during compound preparation The effect of providing a heat shielding film that prevents the problem of increasing size is derived.

According to the present invention, by preparing the oxygen-deficient transition metal oxide by a liquid phase sedimentation method with simple synthesis conditions, it is possible to easily generate particles and control particle sizes, thereby obtaining uniform nano-sized particles.

The present invention has the effect of calcining the synthesized transition metal oxide in a range of 300 to 600 ° C to remove hydroxyl groups and water molecules to form rutile crystals having small particle diameters.

The present invention, by inducing oxygen deficiency of the transition metal oxide formed rutile-type crystals through reducing calcination to have infrared absorption characteristics due to crystal defects or vacancies of oxygen, such reducing calcination is performed by introducing an inert gas instead of hydrogen gas By making it work underneath, it reduces the risk of work and derives the effect of easily using existing firing equipment.

According to the present invention, residual oxygen (O, O ₂ ) is introduced by forming organic acid metal chelate compounds on the surface of an oxygen-deficient transition metal oxide or distributing it in a dispersion sol, with selective reactivity first and no heterogeneous reactivity. The organic acid metal chelate compound effectively blocks the reaction by, residual hydroxyl (-OH) reaction, and residual radical reaction, thereby compensating for problems such as heat resistance and durability of the oxygen-deficient transition metal oxide. It has the effect.

The present invention has the effect of making the organic acid metal chelate compound serving as the passivation film by the reflux method so that the compound suitable for the desired purpose can be easily produced even in existing facilities.

The present invention, a problem that deformation may occur as the substrate layer is exposed to a temperature of 120 ° C or higher when hot air drying and ultraviolet irradiation is performed for drying and curing of the applied coating film, polyethylene having high thermal deformation temperature and excellent dimensional stability The effect of solving the problem by constructing the base layer with terephthalate is derived.

The present invention has an effect of preventing the deformation of the dispersant by making the content of the oxygen-deficient transition metal oxide in the dispersion sol to be 20 to 30% by weight, so that sufficient optical properties are exhibited and the dispersion time is reduced.

In the present invention, the content of the dispersant in the dispersion sol is 1 to 10% by weight, so that a sufficient dispersion sol is obtained, and when the coated surface is dried, the dispersant that is not dried remains on the coating surface and does not cause defects in the coating surface. It has the effect.

The present invention, the content of the organic acid metal chelating compound in the dispersion sol is 5 to 10% by weight, heat resistance and durability of the oxygen-deficient transition metal oxide without significantly reducing optical properties such as visible light transmittance and infrared shielding rate Elicits an effect that greatly improves.

The present invention has an effect of easily dispersing agglomerated powder, simplifying dispersion sol formation, and enabling mass production by forming a dispersion sol by a ball mill method.

The present invention has an effect of increasing the optical properties of the film and adhesion of the coating film and improving the scratch resistance of the film by making the content of the dispersion sol in the coating sol to be 40 to 50% by weight.

The present invention includes an oligomer, a monomer, and a photoinitiator that causes photopolymerization by irradiation with ultraviolet rays as a photopolymer, to enhance the bonding strength between the coating sol and the base layer, and to finely control the coating film thickness. It produces an effect that can help.

The present invention has the effect of increasing the surface scratch resistance, preventing surface cracking, and improving adhesion to the substrate layer by configuring the thickness of the coated coating film applied to the substrate layer to 3 to 4 μm while maintaining optical properties. There is.

The present invention has an effect of forming an adhesive layer on one surface of the heat shielding layer, so that the film can be easily adhered to buildings or vehicles.

The present invention derives an effect of attaching a release paper to one surface of the adhesive layer so that one surface of the adhesive layer is protected by the release paper.

1 is a view of a conventional thermal barrier film.

2 is a view of a heat shielding film according to an embodiment of the present invention.

3 is a view of a heat shielding film according to another embodiment of the present invention.

4 is a view of a heat shielding film according to another embodiment of the present invention.

5 is a view of a heat shielding film manufacturing method according to an embodiment of the present invention.

6 is a view of the thermal barrier layer forming step of FIG. 5;

7 is a view of a method of manufacturing a heat shielding film according to another embodiment of the present invention.

8 is a view of a method for manufacturing a heat shielding film according to another embodiment of the present invention.

9 is an SEM photograph of oxygen-deficient tungsten oxide particles synthesized by the liquid precipitation method of Test Example 1.

10 is a SEM photograph of oxygen-deficient cobalt oxide particles synthesized by the liquid precipitation method of Test Example 3.

11 is an XRD graph showing crystals of oxygen-deficient tungsten oxide synthesized by the liquid precipitation method of Test Example 1.

Hereinafter, preferred embodiments of the heat shielding film and its manufacturing method according to the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, when it is determined that a detailed description of known functions or configurations may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted. Unless otherwise specified, all terms in this specification are the same as the general meaning of the term understood by a person skilled in the art to which the present invention belongs, and if there is a conflict with the meaning of the term used herein It follows the definition used in the specification.

2 is a view of a heat shielding film according to an embodiment of the present invention. Referring to FIG. 2, the present invention, the heat shielding film 1, includes a base layer 10 and a heat shield layer 30. do.

The base layer 10 is configured to provide a surface on which the heat shield layer 30 is coated, and supports the heat shield layer 30 to be described later. Polyethylene terephthalate, polycarbonate, nylon, polypropylene, and the like may be used as the base layer 10. In general, after the thermal barrier layer 30 to be described later is applied to the base layer 10, hot air drying and ultraviolet irradiation are performed to dry and cure the coated film. At this time, the base layer 10 may be exposed to a temperature of 120 ° C. or higher, and a deformation may occur in the base layer 10 itself due to an intrinsic heat deformation temperature only with a typical plastic substrate. Therefore, the base layer 10 is preferably composed of a polyethylene terephthalate (PET) having a high thermal deformation temperature and excellent dimensional stability.

The heat shield layer 30 is formed on one surface of the base layer 10 and refers to a configuration that prevents external heat radiation and internal radiation heat from entering or discharging. The heat shield layer 30 includes an oxygen-deficient transition metal oxide. The oxygen-deficient transition metal oxide forms an AO _(3-X) type rutile structure, and in the AO _(3-X) form a rutile type structure, A is a transition metal, Cu, Ag, Zn, Ni, W and Co may include any one or more elements. In the AO _(3-X) form of the rutile (Rutile) type structure, X represents the number of oxygens depending on the reductive plasticity.

Inorganic heat shielding materials, such as antimony oxide (ATO), indium tin oxide (ITO), and tungsten bronze, have an average particle size distribution of 100 nm or more when actually manufactured with a dispersion sol when the primary particle size is within 100 nm. This is often the case. Dispersion sols having an average particle size distribution of more than 100 nm have haze and appear hazy due to scattering when made into a film.

However, the AO _(3-X) -type rutile (Rutile) -type structure has a relatively small primary particle size, and thus there is no problem of an increase in particle size during the firing process during compound preparation. Therefore, the AO _(3-X) type rutile (Rutile) type structure solves the problem of appearance that is bluish while maximizing the optical properties of the existing inorganic heat shielding material. Actually, the particle size of the oxygen-deficient transition metal oxide is 20 to 30 nm, which fundamentally blocks haze generated at a particle size of 100 nm.

The oxygen-deficient transition metal oxide may be synthesized by a liquid phase precipitation method. According to the liquid precipitation method, precipitation and precipitation occur when a predetermined amount of an acid value (pH) opposite to a dissolved reactant is introduced by easily dissolving a precursor of a desired element in a solvent, and during this process, temperature, solvent, loading material, reaction time, etc. The desired inorganic compound can be synthesized by regulation. At this time, the reactor is not particularly limited, and the facility of the heat source is also not limited, so that the existing facility can be sufficiently utilized.

The oxygen-deficient transition metal oxide synthesized by the liquid precipitation method exists in the presence of a hydroxyl group (-0H), so that the hydroxyl group and water molecules are completely removed, and primary calcination is performed to form rutile crystals. Will go through. Calcination refers to an operation of heating a substance to a high temperature to remove some or all of its volatile components, and the temperature of the primary calcination is preferably maintained in the range of 300 to 600 ° C. When the calcination temperature is less than 300 ° C, hydroxyl groups (-OH) and water molecules cannot be completely removed, whereby hydroxyl groups and water molecules may remain, and a rutile crystal phase cannot be formed. In addition, when the calcination temperature exceeds 600 ° C, the growth of particles proceeds, so that nano-sized particles cannot be obtained, and haze may occur in the final product. Therefore, the temperature of the primary calcination can be preferably maintained in the range of 300 to 600 ° C, and more preferably in the range of 400 to 500 ° C.

The crystal defect of the oxygen-deficient transition metal oxide can be induced by secondary reduction calcination. Reduction firing refers to a firing method in which, when insufficient air is supplied during combustion, incomplete combustion occurs and hydrogen in the decomposition products of carbon dioxide or fuel causes a reduction effect on the heated object. It is preferable to give oxygen deficiency to the metal oxide by reducing the secondary reducing calcination by introducing an inert gas (N ₂ , Ar, Ne, CO ₃ ) that does not have an explosive risk, without using an explosive hydrogen gas. . If hydrogen gas is used, not only does it require expensive special equipment to inject gas, but if the hydrogen gas injection conditions are not met, a large explosion may occur with only a little oxygen. This is to reduce and to make it easy to use existing firing equipment. The powder formed by the secondary reduction firing may have a dark blue color.

The oxygen-deficient transition metal oxide is a crystal having oxygen-deficient defects, which may have problems such as heat resistance and durability, and problems such as heat resistance and durability can be solved by an immobilization film. The passivation film refers to a metal oxide film in a state where normal chemical reactivity is lost. Specifically, by forming the organic acid metal chelate compounds (organic acid chelate compounds) having no selective reactivity and preferential reactivity on the surface of the oxygen-deficient transition metal oxide or distributing it in the dispersion sol, the residual oxygen (O, O ₂ ) is introduced into the surface. The organic acid metal chelate compound effectively blocks the reaction by, residual hydroxyl (-OH) reaction, residual radical (Radical) reaction, and can solve problems such as heat resistance and durability of the oxygen-deficient transition metal oxide. There will be.

The organic acid metal chelate compound serving as the passivation film may have an R ₁ -MR ₂ structure. Each of R ₁ and R ₂ may be any one of low molecular weight glutamic acid or high molecular weight sodium poly aspartate, which are the main body of the organic acid, and R ₁ and R ₂ may be the same or different from each other. have. Preferably, the M may be any one of Cu, Ag, Zn, Ni, W, and Co, which are transition metals.

The organic acid metal chelate compound may be prepared by a reflux method. Specifically, the precursor containing one element of Cu, Ag, Zn, Ni, W, and Co is dissolved in an organic acid solvent and stirred at a reaction temperature of 60 to 80 ° C. for agitation for 4 to 5 hours to ripple. It can be prepared by refluxing.

3 is a view of a heat shielding film according to another embodiment of the present invention, it will be referred to below 3.

The adhesive layer 50 refers to a configuration formed on one surface of the heat shield layer 30. The adhesive layer 50 is configured to easily adhere the heat shielding film 1 including the heat shield layer 30 to a building or a vehicle. The tackiness of the adhesive layer 50 mainly depends on the molecular chain, molecular weight distribution or the amount of molecular structure present in the polymer chain, and is determined by molecular weight in particular, so the acrylic copolymer (Acrylic Copolymer) has a weight average molecular weight of 800,000-20 It is preferable that it is ten thousand. On the other hand, it is preferable that the methacrylate monomer having an alkyl group having 1 to 12 carbon atoms is included in an acrylic copolymer at 90 to 99.9% by weight. This is because if the methacrylate monomer is less than 90% by weight of the acrylic copolymer, there is a problem that the initial adhesive strength is lowered, and when it exceeds 99.9% by weight, durability may be caused by a decrease in cohesion.

4 is a view of a heat shielding film according to another embodiment of the present invention, will be described below with reference to FIG. 4.

The release paper 70 is configured to be formed on one surface of the adhesive layer 50 to protect the outer surface of the adhesive layer 50. The release paper 70 is preferably a film coated with a silicone coating on a PET substrate. This is because the release paper 70 may not be separated from the adhesive layer 50 when the final manufactured heat shielding film is applied to the glass if the silicone coating is not performed.

5 is a view of a method for manufacturing a heat shielding film according to an embodiment of the present invention, hereinafter, a heat shielding film manufacturing method (S1) will be described with reference to FIG. 5. In order to avoid overlapping descriptions, in the process of describing the heat shielding film manufacturing method (S1), the aforementioned contents will be omitted or simplified.

The method for manufacturing a heat shield film (S1) according to the present invention includes a substrate layer providing step (S10), a heat shield layer forming step (S30), an adhesive layer forming step (S50), and a release paper attaching step (S70).

The base layer providing step (S10) refers to a step of providing the base layer 10 to which the heat shield layer 30 is to be combined.

The heat shield layer forming step (S30) refers to a step of forming the heat shielding layer 30 on one surface of the substrate layer 10 after the substrate layer providing step (S10). 6 is a view of the thermal barrier layer forming step of FIG. 5, referring to FIG. 6, the thermal barrier layer forming step (S30) includes an oxygen-deficient transition metal oxide forming step (S31) and a passivation coating step (S33). And, coating step (S35).

The oxygen-deficient transition metal oxide forming step (S31) refers to a step of generating a transition metal oxide deficient in oxygen. The oxygen-deficient transition metal oxide forming step (S31) includes a synthesis step (S311), a primary calcination step (S313), and a secondary reduction firing step (S315).

The synthesizing step (S311) is a step of synthesizing transition metal oxides, and may be preferably performed by a liquid phase precipitation method. By preparing the oxygen-deficient transition metal oxide by a liquid precipitation method with simple synthesis conditions, it is easy to generate particles and control particle sizes, thereby obtaining uniform nano-sized particles.

The first calcination step (S313), after the synthesis step (S311), to remove hydroxyl groups (-OH) and water molecules from the synthesized transition metal oxide and calcined in the range of 300 ~ 600 ℃ to form rutile crystals Refers to the steps.

The secondary reduction firing step (S315) refers to a step of reducing firing under an inert gas input for oxygen deficiency of the transition metal oxide after the primary firing step (S313). The inert gas used in the secondary reduction firing step (S315) includes N ₂ , Ar, Ne and CO ₃ .

The passivation film step (S33) refers to a step of forming a passivation film on the oxygen-deficient transition metal oxide after the oxygen-deficient transition metal oxide forming step (S31). The passivation coating step (S33) includes an organic acid metal chelate compound manufacturing step (S331) and a dispersion sol forming step (S333).

The organic acid metal chelate compound manufacturing step (S331) is a step of preparing an organic acid metal chelate compound, and the organic acid metal chelate compound may be prepared by a reflux method. Specifically, a precursor containing one element of the transition metal selection group may be dissolved in an organic acid solvent and stirred at a reaction temperature of 60 to 80 ° C. for 4 to 5 hours to be refluxed. According to the reflux method, the organic acid metal chelate compound serving as the passivation film can be easily produced even in existing facilities.

The dispersion sol forming step (S333) refers to a step of forming a dispersion sol after the organic acid metal chelate compound manufacturing step (S331). The dispersion sol may include an oxygen-deficient transition metal oxide, a dispersant, an organic acid metal chelate compound, and a solvent (organic solvent).

The content of the oxygen-deficient transition metal oxide in the dispersion sol is preferably 20 to 30% by weight. When the content of the oxygen-deficient transition metal oxide is less than 20% by weight, when the final coating film is formed, sufficient optical properties cannot be expressed at a low thickness, and when the content of the oxygen-deficient transition metal oxide exceeds 30% by weight, a high solid content is obtained. This is because relatively large dispersion time is required to reach the desired particle size of the nano-dispersed sol. Prolonged dispersion time may cause deformation of the dispersant, which may cause problems in the next step, coating sol production. In order to prepare a coating sol to be described later, a polymer binder is included. When the dispersion sol prepared through excessive dispersion time and the polymer binder are mixed, compatibility with each other decreases, resulting in separation of layers, fine shock, and change over time. A problem such as gelation occurs.

The content of the dispersant in the dispersion sol is preferably 1 to 10% by weight. When the dispersant is less than 1% by weight, a sufficient dissolving sol cannot be obtained, and when the dispersant exceeds 10% by weight, the dispersant that is not dried when drying the coated surface remains on the coating surface, causing defects in the coating surface. can do.

The content of the organic acid metal chelate compound in the dispersion sol is preferably 5 to 10% by weight. When the content of the organic acid metal chelate compound is less than 5% by weight, the passivation film phenomenon is not properly expressed, so that the heat resistance and durability of the oxygen-deficient transition metal oxide cannot be greatly improved, and the content of the organic acid metal chelate compound is 10% by weight. When exceeded, among the optical properties of the oxygen-deficient transition metal oxide, visible light transmittance may be reduced, making it difficult to manufacture a high-transmittance and high-efficiency heat shielding film.

The film should be able to transmit visible light, and the powder of the oxygen-deficient transition metal oxide has an agglomerated form, so it is preferable to disperse the particles. To this end, the dissolving sol forming step (S333) may form a dissolving sol while dispersing particles by a ball mill method that is simple and easy to mass-produce.

Specifically, the oxygen-deficient transition metal oxide powder, a solvent (organic solvent), and a dispersing agent in an agglomerated state are introduced into a cylindrical disperser, and after the zirconium beads are added 60% or more of the volume of the cylindrical disperser, the This is achieved by rotating the cylindrical disperser at a constant speed. At this time, all the contents inside the cylindrical disperser are rotated. In particular, the zirconium beads transmit physical shock and surface shear force directly to the powder to be dispersed and apply physical energy while inducing surface grinding. Bar, after a certain period of time, it is dispersed as nanoparticles of a size smaller than the primary particle size, and finally, it is possible to express optical properties.

As a result, in the dispersion sol forming step (S333), the organic acid metal chelate compound that separates the aggregation of the compound and improves the heat resistance and durability of the oxygen-deficient transition metal oxide is distributed in the liquid state or formed on the surface.

The coating step (S35) refers to a step of forming a coating film on the base layer 10 after the passivation film step (S33). The coating step (S35) includes a coating sol forming step (S351), a coating sol coating step (S353), and a dry curing step (S355).

The coating sol forming step (S351) is a step of forming a coating sol, and the coating sol may include a dispersion sol, a binder, and an organic solvent.

The content of the dispersion sol in the coating sol is preferably 40 to 50% by weight. When the content of the dispersion sol is less than 40% by weight, the optical properties of the film are deteriorated, and when the content of the dispersion sol exceeds 50% by weight, the proportion of the binder is lowered, so that adhesion to the coating film may be lowered or surface scratch resistance may be deteriorated. Because. More preferably, the dispersion sol is 40 to 50% by weight, the binder is 40 to 50% by weight, and the organic solvent may be composed of 10 to 20% by weight.

In the coating sol, the binder facilitates bonding with a plastic film as a base material, and allows the thickness of a coating film to be adjusted. The binder, as a photopolymer, may be composed of an oligomer, a monomer, and a photoinitiator that cause photopolymerization by irradiation with ultraviolet rays.

In the coating sol, the organic solvent is methyl ethyl ketone, toluene, ethyl acetate, isopropyl alcohol, ethyl cellosolve, isobutyl Alcohol (Iso butyl Alcohol), Dimethylformamide, Ethanol, Butyl Cellosolve, Xylene, 1-Octanol, Diethylene Glycol , Nitrobenzene (Nitrobenzene).

The coating sol coating step (S353) refers to a step of applying the coating sol to the base layer 10 after the coating sol forming step (S351). Preferably, the coating sol coating step (S353) may use any one of a micro gravure coating, a knife coating, and a roll to roll coating, and more preferably a large area coating. In view of this, it is possible to use a micro gravure coating that exhibits the flattest coating surface and has a relatively high productivity.

It is preferable that the thickness of the coated coating film is 3 to 4 μm. When the thickness of the coated coating film is less than 3 µm, optical properties are not expressed and surface scratch resistance is deteriorated. When the thickness of the coated coating film exceeds 4 µm, a hard UV coating layer is formed and cracks are generated on the surface. The adhesive strength with the base layer 10 may be reduced.

The dry curing step (S355) refers to a step of hot air drying and ultraviolet curing the base layer 10 coated with the coating sol after the coating sol coating step (S353).

The adhesive layer forming step (S50) refers to a step of forming the adhesive layer 50 on one surface of the heat shield layer 30 after the heat shield layer forming step (S30). The heat shielding film 1 can be easily adhered to a building or a vehicle by the adhesive layer 50.

The release paper attaching step (S70) refers to a step of attaching the release paper 70 to one surface of the adhesive layer 50 after the adhesive layer forming step (S50). One surface of the adhesive layer 50 may be protected through the release paper 70 through the release paper attaching step S70.

Hereinafter, a specific test example is that when the heat shielding film is composed of an oxygen-deficient transition metal oxide, visible light transmittance and infrared ray blocking rate are improved, and heat resistance and durability of the oxygen-deficient transition metal oxide are improved through an immobilized film. I'll explain by listening.

(1) Preparation of the specimen

1) Test Example 1

-Oxygen deficiency type transition metal oxide

Sodium tungstate dihydrate (Na ₂ WO ₄ · 2H ₂ O), copper chloride dihydrate (CuCl ₂ · 2H ₂ O), silver nitrate (AgNO ₃ ), ammonium zinc chloride (Zn) (NH ₄ ) 2Cl ₄ ), 30 wt% of sodium tungstate dihydrate (Na ₂ WO ₄ · 2H ₂ O) as a white powder in cobalt chloride hexahydrate (CoCl ₂ · 2H ₂ O) and distilled water in a 4-neck flask reactor After putting in, it is completely dissociated into a colorless and transparent liquid by slowly stirring for 3 hours while maintaining 80 ° C using a heating mantle, and dissociating 50% by weight of organic acid fumaric acid as a loading material in distilled water , When the dropping was performed for 20 minutes at a constant rate using a dropping funnel in the flask reactor in which the precursor was dissolved, the colorless and transparent solution gradually formed into a yellow viscous solution. After aging for a certain period of time, the reaction was terminated to wash the filter and by-products to obtain 35% by weight of the yellow reactant.

After obtaining the hydrate-state tungsten oxide obtained as described above, it was fired at a temperature of 400 ° C. for about 1 hour for primary calcination.

The obtained tungsten oxide is then filled with nitrogen (N ₂ ) gas inside the electric furnace to form lattice defects and rutile crystals, maintained at a temperature of 700 ° C. for 2 hours, and then naturally cooled to terminate secondary reduction firing. Then, 33% by weight of blue oxygen-deficient tungsten oxide was obtained.

-Generation of organic acid metal chelate compounds

The precursor of the organic acid metal chelate compound is 30% by weight of ammonium zinc chloride and ethanol (ethanol) is added to the Reflux reactor and stirred to form a colorless and transparent liquid. At this time, 40% by weight of low-molecular glutamic acid is added and the reaction temperature is 60. Maintaining ℃ and reacting for 4 hours, gradually forms an off-white viscous liquid, and after the reaction is completed, the filter and by-products are washed and dried to obtain 34% by weight of off-white powder.

-Dispersion sol production

20% by weight of tungsten oxide powder that has been calcined to prepare the powders thus obtained in the form of a dispersion sol. 5% by weight of an organic acid zinc chelate, 0.5% by weight of a dispersant and 74.5% by weight of an organic solvent were added, and 0.5mm zirconium beads were added to 60% of the total volume to perform ball milling. At this time, the dispersion time was performed for 72 hours, and the obtained dispersion sol had a solid content of 25% by weight.

-Coating sol production

After adding 40% by weight of the dispersion sol to 50% by weight of the photopolymer binder, 10% by weight of MEK is added as an organic solvent to complete the coating sol.

-Formation of coating film

The finished coating sol is coated on a PET film, which is a base layer, so that the thickness of the coating film is 3-4 µm.

-Formation of adhesive layer and adhesion of release paper

An adhesive layer with a thickness of 6 to 7 µm is formed on the back side coated with the heat shielding layer to be laminated with release paper to complete the final heat shielding film.

-Preparation of heat shielding film

Test Example 1 was prepared by cutting the heat shielding film to a width of 145 mm * a length of 145 mm.

2) Test Example 2

In Test Example 1, 30% by weight of copper chloride dihydrate (CuCl ₂ · 2H ₂ O) instead of sodium tungstate dihydrate (Na ₂ WO ₄ · 2H ₂ O) as a starting material during the synthesis process of the oxygen-deficient transition metal oxide powder Test Example 2 was prepared under the same conditions as in Test Example 1 except for inputting. That is, in the composition of the oxygen-deficient tungsten oxide, the transition metal was replaced with copper from the existing tungsten.

3) Test Example 3

In Test Example 1, 30% by weight of cobalt hexahydrate (CoCl ₂ · 2H ₂ O) instead of sodium tungstate dihydrate (Na ₂ WO ₄ · 2H ₂ O) as a starting material during the synthesis process of oxygen-deficient transition metal oxide powder Test Example 3 was prepared under the same conditions as in Test Example 1 except for inputting. That is, in the oxygen-deficient metal oxide composition, the transition metal was replaced with tungsten to cobalt.

4) Test Example 4

In Test Example 1, 50% by weight of sodium tungstate dihydrate (Na ₂ WO ₄ · 2H ₂ O) and 60% by weight of fumaric acid were added as starting materials during the synthesis process of the oxygen-deficient transition metal oxide powder. , In the process of synthesizing the organic acid metal chelate compound, Test Example 4 was prepared under the same conditions as in Test Example 1, except that 30 wt% of cobalt chloride hexahydrate was used instead of 30 wt% of ammonium zinc chloride. That is, in the composition of the oxygen-deficient transition metal oxide, the ratio of the existing sodium tungstate dihydrate and fumaric acid among the transition metal elements is different, and the organic acid metal chelate is replaced with zinc to cobalt.

5) Test Example 5

In Test Example 1, argon gas was added instead of nitrogen in the reduction firing step during the synthesis process of the oxygen-deficient transition metal oxide powder, and 30% by weight of copper chloride dihydrate instead of 30% by weight of ammonium zinc chloride during the synthesis of the organic acid metal chelate powder. Test Example 5 was prepared under the same conditions as in Test Example 1, except for doing so. That is, in the reduction and calcination step of the oxygen-deficient transition metal oxide, the existing nitrogen was replaced with argon gas, and the organic acid metal chelate was replaced with zinc from copper.

6) Test Example 6

In Test Example 1, during the process of preparing the oxygen-deficient tungsten oxide dispersion sol, 20% by weight of the reduced calcined powder, 10% by weight of organic acid chelate, 1.0% by weight of dispersant and 70% by weight of organic solvent, the final dispersion sol solid content is 30% by weight Test Example 6 was prepared under the same conditions as in Test Example 1 except for being used. That is, the solid content of the organic acid zinc chelate was increased from 5% by weight to 10% by weight.

7) Test Example 7

In Test Example 1, in the process of preparing the oxygen-deficient tungsten oxide dispersion sol, a test example was performed except that the final dispersion sol solid content was 30% by weight with 30% by weight of the dispersant and 70% by weight of the organic solvent in 30% by weight of the reduced calcined powder. Test Example 7 was prepared under the same conditions as 1. That is, the organic acid zinc chelate contained in the dispersion sol in Test Example 1 was excluded.

(2) Test 1-Observation of particle size

-Test purpose: to measure the particle size of the oxygen-deficient transition metal oxide according to the present invention

-Test conditions: Particle observation pictures are HITACHI (JAPAN) S-2400 SEM (Scanning Electron Microscope) images, taken at a magnification of × 50k to × 100k at 15kw.

-Consideration of Results: FIG. 9 is a SEM photograph of oxygen-deficient tungsten oxide particles synthesized by the liquid precipitation method of Test Example 1. Referring to FIG. 9, Test Example 1 appears to be a group of small particles, but the size per particle unit As a result of observation, it was confirmed that the particle size was 20 to 30 nm, and the particle shape exhibited a uniform spherical shape. On the other hand, FIG. 10 is a SEM photograph of oxygen-deficient cobalt oxide particles synthesized by the liquid precipitation method of Test Example 3. Referring to FIG. 10, the particle size of Test Example 3 is about 100 to 200 nm, and the particle shape is not constant. . That is, it can be seen that the application of the tungsten metal element among the transition metals has better results in particle size and particle shape.

(3) Test 2-Observation of XRD crystallinity

-Test Purpose: Confirmation of rutile-type crystallinity of oxygen-deficient tungsten oxide according to the present invention

-Test conditions: XRD observation was measured using PHILIPS (Netherlands), X'Pert-MPD System.

-Consideration of Results: FIG. 11 is an XRD graph showing crystals of oxygen-deficient tungsten oxide synthesized by the liquid precipitation method of Test Example 1. Referring to FIG. 11, the XRD value is 2θ23.6, 0.2 at 0.0.2 plane. As a value of 2θ28.12 in the 0 plane, 2θ33.82 in the 1.1.2 plane, and 2θ36.91 in the 2.0.2 plane, it was confirmed that the oxygen-deficient tungsten oxide mutant was synthesized well with rutile crystallinity.

(4) Test 3-Observing optical properties and durability

-Test purpose: Compare the visible and infrared transmission characteristics according to the manufacturing process of oxygen-deficient tungsten oxide, and observe the heat resistance and durability to evaluate the performance as a heat shield

-Test conditions: Visible light and infrared transmission observation is measured by setting the Baseline in the air with JASCO (JAPAN) 650 UV / VIS Spectrometer, and heat and durability observation is performed using a hot air dryer (SH-DO-149FG), temperature 120 ℃ After standing for 72 hours, the optical properties were measured again to show the rate of change.

-Result consideration: The test results are shown in Table 1 below. (Visible light transmittance is 400 ~ 780nm transmittance, infrared shielding rate is expressed by subtracting 100 from 780 ~ 2000nm transmittance)

구분division	시험예1Test Example 1	시험예2Test Example 2	시험예3Test Example 3	시험예4Test Example 4	시험예5Test Example 5	시험예6Test Example 6	시험예7Test Example 7
가시광선투과율%(400~780nm)Visible light transmittance% (400 ~ 780nm)	7171	6868	4848	6565	6767	6868	7575
적외선차폐율%(780~2000nm)Infrared shielding rate% (780 ~ 2000nm)	8282	2828	2525	6161	6464	7373	8686
변화율(ΔT%)Rate of change (ΔT%)	3%3%	8%8%	5%5%	7%7%	9%9%	2%2%	21%21%

Referring to Table 1, when comparing Test Example 1 and Test Example 2, in Test Example 1, tungsten was used as a transition metal in an oxygen-deficient transition metal oxide, and in Test Example 2, copper was used as a transition metal. There are differences used. As a result, it can be seen that when tungsten is used as the transition metal, the visible light transmittance is increased, and the infrared shielding rate is greatly improved, compared to when copper is used. Heat resistance and durability were also proved to be superior when tungsten was used as the transition metal than when copper was used as the transition metal.

When comparing Test Example 1 and Test Example 3, in the case of Test Example 1, the transition metal was made of tungsten from the oxygen-deficient transition metal oxide, and in the case of Test Example 3, the transition metal was composed of cobalt. As a result, as shown in Table 1, it was confirmed that the use of tungsten as a transition metal is advantageous in terms of improving optical properties compared to using cobalt. There was no significant difference in heat resistance and durability, but in this case, it was more advantageous to use tungsten as the transition metal.

When comparing the Test Example 1 and the Test Example 4, in the case of Test Example 1, the content of sodium tungstate dihydrate is 30% by weight, the content of fumaric acid is 50% by weight, and in the process of synthesizing an organic acid metal chelate While zinc was used, in the case of Test Example 4, the content of sodium tungstate dihydrate was 50% by weight, the content of fumaric acid was 60% by weight, and there was a difference using cobalt in the process of synthesizing the organic acid metal chelate. As a result, it was confirmed that in the case of Test Example 1, a heat shielding material having superior optical properties and excellent heat resistance and durability was produced compared to Test Example 4.

When the test example 1 and the test example 5 are compared, the test example 1 uses nitrogen gas in the reduction and calcination step of the oxygen-deficient transition metal oxide and uses zinc as an organic acid metal chelate, and the test example 5 is the reduction. The difference is that argon gas is used in the firing step and copper is used as the organic acid metal chelate. As a result, in Test Example 5, the visible light transmittance and the infrared shielding rate were inferior to Test Example 1, and heat resistance and durability were also inferior.

When comparing Test Example 1 and Test Example 6, in Test Example 1, the content of the organic acid zinc chelate was 5% by weight, while in Test Example 6, the content of the organic acid zinc chelate was increased to 10% by weight. As a result, when the content of the organic acid metal chelate is increased, the optical properties tend to be slightly lowered, but it has been proved that the heat resistance and durability are better.

When the test example 1 and the test example 7 are compared, in the case of test example 1, the organic acid metal chelate is included, and in the case of test example 7, the organic acid metal chelate is excluded, and the organic acid metal chelate is not added at all. In Example 7, the best visible light transmittance and infrared shielding rate were shown, but it was confirmed that a great problem occurred in heat resistance and durability. After all, in order to supplement the heat resistance and durability of the oxygen-deficient transition metal oxide having excellent optical properties, reaction by inflow of residual oxygen (O, O ₂ ), reaction by residual hydroxyl group (-OH), residual radical (·) It is necessary to add an organic acid metal chelate in order to block reaction and the like.

The above detailed description is to illustrate the present invention. In addition, the foregoing is a description of preferred embodiments of the present invention, and the present invention can be used in various other combinations, modifications and environments. That is, it is possible to change or modify the scope of the concept of the invention disclosed herein, the scope equivalent to the disclosed contents, and / or the scope of the art or knowledge in the art. The embodiments described describe the best conditions for implementing the technical spirit of the present invention, and various changes required in specific application fields and uses of the present invention are possible. Accordingly, the detailed description of the invention is not intended to limit the invention to the disclosed embodiments. In addition, the appended claims should be construed to include other embodiments.

Claims

A base layer,

It includes a heat shielding layer formed on one surface of the base layer,

The heat shielding layer, including an oxygen-deficient transition metal oxide, has no haze phenomenon, and improves visible light transmittance and infrared blocking rate, a heat shielding film.
According to claim 1,

The oxygen-deficient transition metal oxide, AO (3-X) characterized in that it forms a rutile (Rutile) type structure, a heat shielding film. (Small particles, haze blocking)
According to claim 2,

The A, Cu, Ag, Zn, Ni, W, and Co, characterized in that it contains any one or more elements, heat shielding film.
According to claim 3,

The oxygen-deficient transition metal oxide, to remove hydroxyl groups and water molecules and form crystals, characterized in that calcination is performed in a range of 300 to 600 ° C., a heat shielding film.
According to claim 4,

The oxygen-deficient transition metal oxide, for the oxygen deficiency, characterized in that the reduction firing is performed under the inert gas input, heat shielding film.
The method of claim 5,

The inert gas, characterized in that it comprises N 2 , Ar, Ne and CO 3 , heat shielding film.
According to claim 1,

The heat shielding layer, further comprising a passivation film, characterized in that to improve the heat resistance and durability of the oxygen-deficient transition metal oxide, heat shielding film.
The method of claim 7,

The passivation film, characterized in that it comprises an organic acid metal chelate compound, heat shielding film.
The method of claim 8,

The organic acid metal chelate compound has an R1-M-R2 structure,

The M is any one of Cu, Ag, Zn, Ni, W and Co,

The R1 and R2 are low molecular weight glutamic acid (Glutamic Acid) and high molecular weight sodium poly aspartate (Sodium Poly Aspartate), characterized in that any one of, heat shielding film.
According to claim 1,

The base layer, characterized in that the polyethylene terephthalate (Polyethylene Terephthalate), heat shielding film.
A base layer providing step of providing a base layer,

After the step of providing the substrate layer comprises a heat shield layer forming step of forming a heat shield layer on one surface of the substrate layer,

In the thermal barrier layer forming step, an oxygen-deficient transition metal oxide forming step of generating an oxygen-deficient transition metal oxide is formed, and after the oxygen-deficient transition metal oxide forming step, an immobilized film is formed on the oxygen-deficient transition metal oxide. And a passivation coating step, and a coating step of forming a coating layer on the base layer after the passivation coating step.
The method of claim 11,

The oxygen-deficient transition metal oxide forming step is a synthesis step of synthesizing transition metal oxides by a liquid phase precipitation method, and 300 to remove hydroxyl groups and water molecules from the transition metal oxides synthesized after the synthesis step and forming crystals. Characterized in that it comprises a primary calcination step for calcination in the range of 600 ℃, and a secondary reduction calcination step for reducing calcination under the inert gas for oxygen deficiency of the transition metal oxide after the first calcination step, Heat shielding film manufacturing method.
The method of claim 11,

The passivation coating step, characterized in that it comprises an organic acid metal chelate compound manufacturing step for producing an organic acid metal chelate compound, and a dispersion sol forming step for forming a dispersion sol after the organic acid metal chelate compound manufacturing step, the heat shielding film Manufacturing method.
The method of claim 13,

The organic acid metal chelate compound manufacturing step is characterized in that the precursor containing the transition metal is dissolved in an organic acid solvent, and stirred for 4 to 5 hours at 60 to 80 ° C. to reflux. .
The method of claim 13,

The dispersing sol forming step is characterized by forming a dissolving sol comprising 20 to 30% by weight of an oxygen-deficient transition metal oxide, 1 to 10% by weight of a dispersing agent, and 5 to 10% by weight of an organic acid metal chelate compound. Heat shielding film manufacturing method.
The method of claim 11,

The coating step includes a coating sol forming step of forming a coating sol, a coating sol applying step of applying the coating sol to the substrate layer after the coating sol forming step, and a coating sol applied after the coating sol applying step. Characterized in that it comprises a drying hardening step of drying the base layer and hot air drying and UV curing, heat shielding film manufacturing method.
The method of claim 16,

The coating sol forming step, characterized in that to form a coating sol comprising 40 to 50% by weight of a dissolving sol, 40 to 50% by weight of a binder, and 10 to 20% by weight of an organic solvent.
The method of claim 17,

The binder, as a photopolymer, characterized in that it comprises an oligomer (Oligomer), a monomer (Monomer), a photoinitiator that causes photopolymerization by irradiation with ultraviolet rays, a method for manufacturing a heat shielding film.
The method of claim 17,

The organic solvent is methyl ethyl ketone, toluene, ethyl acetate, isopropyl alcohol, ethyl cellosolve, iso butyl alcohol ), Dimethylformamide, Ethanol, Butyl Cellosolve, Xylene, 1-Octanol, Diethylene Glycol, Nitrobenzene ) Characterized in that it comprises any one or more of, heat shielding film manufacturing method.
The method of claim 16,

The coating sol coating step, characterized in that using any one of micro gravure (Micro Gravure) coating, knife (Knife) coating and roll to roll (Roll to Roll) coating, heat shielding film manufacturing method.
The method of claim 20,

The coating sol coating step, characterized in that the thickness of the coating film is 3 ~ 4㎛, heat shielding film manufacturing method.
The method of claim 11,

The heat shielding film manufacturing method, characterized in that it further comprises an adhesive layer forming step of forming an adhesive layer on one surface of the heat shielding layer after the heat shield layer forming step.
The method of claim 22,

The heat shielding film manufacturing method, characterized in that it further comprises a release paper attaching step of attaching a release paper on one side of the adhesive layer after the adhesive layer forming step.