KR100810738B1 - Preparation method of multi structural film using slot die and anti pollutant-heat cutting film prepared from them - Google Patents

Abstract

The present invention relates to a method for producing a multilayer film using a slot die and an antifouling insulation film prepared therefrom, and more particularly, to coating a surface of a polymer substrate using a slot-die coater. After placing the electromagnet on the guide roll, which is the lower end of the polymer substrate, and passing the solution containing particles having different average particle diameters through each slot, the solution passing through the slot is discharged and laminated under inclined conditions. As a result, it is possible to simultaneously form a plurality of multilayer films on the surface of the polymer, and rearrangement of the particles is induced by the magnetic field formed by the electromagnet to form an inclined structure in which particles having a relatively average particle diameter are located at the bottom of the surface of the polymer. Of multi-layered film using slot die, which has excellent interfacial compatibility, interfacial adhesion, and long-term physical properties due to unclear interface. The present invention relates to an antifouling-insulating film in which an infrared blocking layer containing antimony-tin dioxide and a photocatalyst layer containing titanium dioxide are laminated using the same method.

Average particle size, slot die coater, particle rearrangement, inclined structure, multilayer structure

Description

Method for manufacturing multilayer film using slot die and antifouling insulation film manufactured therefrom {PREPARATION METHOD OF MULTI STRUCTURAL FILM USING SLOT DIE AND ANTI POLLUTANT-HEAT CUTTING FILM PREPARED FROM THEM}

1 is a film prepared in Example 1 according to the present invention, which shows a film of a two-layer structure in which an infrared ray blocking layer 1 and a photocatalytic layer 2 are laminated on a substrate.
2 is a film prepared in Example 2 according to the present invention, a four-layer structure in which a surfactant layer (1), an infrared ray blocking layer (2), a surfactant layer (3), a photocatalytic layer (4) is laminated on a substrate It shows a film.

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Figure 3 is an electron scanning microscope photograph of the film prepared in Example 3, Figure 3a is a photocatalyst sol in a single layer injection solution, Figure 3b is a photocatalyst as a single layer injection solution and then used an infrared barrier sol as a two-layer injection solution I used it.

Figure 4 shows a schematic diagram of a conventionally used slot die, 1, 2, 3 and 4 represents the ejection slot, respectively.

Figure 5 shows an electron scanning micrograph of a four-layer structure prepared in Example 2 according to the present invention.

Figure 6 shows a schematic diagram of a slot die using a guide roll with an electromagnet used in the present invention, 1, 2, 3 and 4 represents the ejection slot, respectively.

Figure 7 shows an electron scanning microscope photograph of a four-layer structure prepared in Example 4 in accordance with the present invention.

The present invention relates to a method for producing a multilayer film using a slot die and an antifouling insulation film prepared therefrom, and more particularly, to coating a surface of a polymer substrate using a slot-die coater. After placing the electromagnet on the guide roll, which is the lower end of the polymer substrate, and passing the solution containing particles having different average particle diameters through each slot, the solution passing through the slot is discharged and laminated under inclined conditions. As a result, it is possible to simultaneously form a plurality of multilayer films on the surface of the polymer, and rearrangement of the particles is induced by the magnetic field formed by the electromagnet to form an inclined structure in which particles having a relatively average particle diameter are located at the bottom of the surface of the polymer. Of multi-layered film using slot die, which has excellent interfacial compatibility, interfacial adhesion, and long-term physical properties due to unclear interface. The present invention relates to an antifouling-insulating film in which an infrared blocking layer containing antimony-tin dioxide and a photocatalyst layer containing titanium dioxide are laminated using the same method.

In general, photocatalysts including titanium dioxide, or photocatalytic active materials are excited when irradiated with energy above the band gap to generate electrons in the conduction band and holes in the valence band. Photocatalytic activity of these photocatalysts was first discovered by Professor Fujishima.

When light is irradiated to a battery composed of a titanium dioxide electrode and a platinum electrode, water decomposition occurs at about -0.5 V, oxygen is generated on the surface of the titanium dioxide electrode, and hydrogen is generated around the platinum electrode. This is a peculiar phenomenon that occurs at a potential far lower than +1.23 V, which is the normal oxidative decomposition potential of water. The valence band of titanium dioxide is transferred to the conduction band by ultraviolet rays. It was explained that oxidation occurs to generate hydrogen.

Types of photocatalysts include titanium dioxide, iron oxide, tungsten oxide, zinc oxide, cadmium sulfide, etc., but titanium dioxide has the highest photocatalytic activity because it has the best ability to absorb specific wavelength light in the ultraviolet region included in sunlight. Known. Titanium dioxide-based photocatalysts are widely used as white pigments, high frequency capacitor materials, low reflection coating materials, and the like. Titanium dioxide is an environmentally improved material that exhibits strong oxidizing power and is effective in deodorization, antifouling, antibacterial, sterilization, and decomposition of various environmental pollutants. Recently, titanium dioxide has been applied to water treatment, air cleaning, and various living materials.

An example of this will be described in detail below.

According to International Patent Publication No. 96/29375, a photocatalyst is photoexcited, and the contact angle between the surface of the photocatalyst and water is 10 degrees or less, and superhydrophilization is known. By using the superhydrophilic property of the photocatalyst, it is attempting to be used in the side mirror film of the automobile, antifog film for the bathroom, self-cleaning glass and the like. If the photocatalyst is directly coated on an organic substrate such as polypropylene and polyethylene terephthalate film, the organic substrate deteriorates in a short time due to the photocatalytic action, resulting in poor adhesion of the coated surface and inferior superhydrophilic properties, thereby preventing its function. Therefore, in order to solve this problem, an intermediate layer is usually formed on an organic substrate film. As the intermediate layer, a silicone resin, an acrylic modified silicone resin, or the like is generally used.

However, such a photocatalyst coating film deteriorates after 1 to 3 years, resulting in poor transparency and antifouling properties of the film. The reason for this is that the intermediate layer has an organic substituent, so that an intermediate layer crack occurs due to the decomposition of these substituents due to the photocatalytic action, or the photocatalytic layer and the intermediate layer, the intermediate layer and the film interface are floated, or partial peeling occurs.

According to Japanese Patent Application No. Hei 11-264592, when forming a photocatalyst layer on an organic substrate, it is necessary to improve adhesion between an organic layer and an inorganic or metallic material, and an intermediate layer or inorganic or metallic material layer to prevent deterioration of the organic substrate. For intermediate layers, we developed organic-inorganic composite warp materials that allow the composition to change continuously in the thickness direction. However, since the composite inclined film is made of a transparent material, the shielding effect of solar light including ultraviolet light cannot be expected, and thus there is a problem in that weather resistance of the organic substrate itself is inferior, and coating using an organic solvent is essential to form the composite inclined film. There is a drawback to shortening the life of this product.

In order to solve the above problem, Korean Patent Publication No. 10-2005-0026555 proposed a material and method for improving the durability and weather resistance of a photocatalyst and an organic substrate by mixing a UV absorber or a light stabilizer with a composite inclined material.

On the other hand, in general, a method for producing titanium dioxide is known sulfuric acid method and chlorine method.

The sulfuric acid method is a method of dissolving an illuminite ore with concentrated sulfuric acid, hydrolyzing the dissolved titanium ions with TiO (OH) ₂ , separating it from iron, and heat-treating at high temperature to convert to titanium dioxide. In the chlorine method, rutile ore is reacted with chlorine gas at a high temperature furnace at 1000 ° C. to produce titanium tetrachloride, and then purified titanium tetrachloride and then reacted with oxygen at high temperature to produce titanium dioxide powder. By applying this method, it is possible to obtain high purity titanium dioxide having a very small particle size and a high specific surface area.

Titanium dioxide is largely divided into anatase type, rutile type, and brookite type according to the crystal structure. Anatase type in low temperature phase and rutile type in high temperature phase are generally used. These two crystalline forms have a tetragonal system in common, but their structure appears different depending on the position of the oxygen ligand. In the rutile type, the oxygen ligand is located at the vertex, whereas the anatase type shows different physical and chemical properties because the oxygen ligand is located at the edge. Titanium dioxide photocatalysts thus prepared are generally known to contain about 75% of anatase and 25% of rutile.

Recently, the sol-gel process through hydrolysis and condensation reaction has been widely applied as a titanium alkoxide raw material to produce nanoparticle photocatalyst titanium dioxide, and it is possible to manufacture titanium dioxide powder having a particle diameter of less than 5 nm with a 100% anatase composition. Known as Titanium dioxide particles are dispersed in water or alcohol solvents at a high concentration of 30% or more in solid content, so that they can be dissolved and thin film coated on organic materials.

Looking at an example for this in detail, according to the Republic of Korea Patent Publication No. 2001-0073712, a method of forming a thin film using a polystyrene substrate using a crystalline anatase type titanium dioxide nanosol under an acid catalyst. The manufacturing of the thin film is a method of dip-coating a dilute titanium dioxide nanosol solution on a polymer support, and the use of the prepared thin film is characterized in that it is capable of decomposing refractory toxic organic substances such as phenol and pigment compounds such as methylene blue. have.

In Korean Utility Model Application No. 20-2004-0017333, a thermal barrier adhesive is formed on one side of a polyester layer, and a silicon (silica) coating layer and a photocatalytic layer are formed on the other side to form an empty space of the silicon (silica) coating layer. A part of the photocatalyst solution is impregnated to propose the production of an insulating solar film. This has a disadvantage in that it is difficult to express stable photocatalytic properties because the silicon coating surface is not likely to be uniform or the empty space is unevenly distributed.

In addition, as a method of directly fixing a photocatalyst on a substrate, Korean Patent Application No. 2002-0022735 proposes a method of semi-permanently fixing by irradiating microwaves after forming a nano-sized photocatalyst particles on the surface of the substrate by directly spraying a titanium precursor in the gas phase. It was. This is a direct coating without using the organic and inorganic binders used in the prior art has the advantage that most of the photocatalyst is exposed to the surface can show a high photocatalyst efficiency.

The photocatalyst mentioned above has been attempted to develop technologies such as thinning and membrane-forming a photocatalyst for application in various fields, and a technique for immobilizing the photocatalyst on various supports has also been studied. Representative examples of these supports include glass, silica, glass / optical fibers, cellulose, zeolite, alumina, aluminosilicate, stainless steel, polycin-based resin, and the like. In this case, when fixing the photocatalyst particles on various supports, an important factor is to provide strong adhesion between the catalyst and the support to ensure stability and to prevent the catalyst from being modified during the process. Particularly, in case of the exterior material, the transparency and gloss of the coating film Also securing is an important factor.

Among the photocatalysts, typical applications for exterior materials are researches such as window films for vehicles, thermal insulation films including coloring for architectural exteriors, and road traffic signs. The photocatalyst properties required for these applications are exposed to the external environment, so they must be excellent in durability, and it is necessary to secure long-term physical properties of at least 1 to 2 years. Such long-term physical properties are necessary to control the antifouling properties related to the activity of the photocatalyst and the coating structure to maintain the properties.

In addition, the thermal insulation properties should be excellent because it is exposed to sunlight as the exterior material, the thermal insulation properties expressed in the commonly used exterior material is obtained by dispersing organic or inorganic particles in the coating solution and coating it uniformly. Although the solar thermal insulation property by such a film is considered to be comparatively good, it cannot fully express its function as an exterior material because of the incompatibility with the coating liquid in which the photocatalyst particle was disperse | distributed, and a surface activity.

The present inventors have tried to manufacture a functional film that is matched with a film for exterior use while improving the above problems. As a result, in coating the surface of the polymer substrate by using a slot-die coater, an electromagnet is disposed on the guide roll, which is the lower end of the polymer substrate, and a solution containing particles having different average particle diameters is prepared. After passing through the slot, the solution passing through the slot is a single process of ejecting and stacking in a specific range of inclined conditions, it is possible to simultaneously form a multi-layered film on the surface of the polymer, the magnetic field formed by the electromagnet The rearrangement of the particles is induced to find that the particles having a relatively large average particle diameter form a slanted structure located at the bottom of the polymer surface to complete the present invention.

In addition, the polymer produced by the above method is a layer formed by the magnetic field, the interface between the layers is unclear, so that the compatibility and interfacial adhesion between the layers and the long-term physical properties can be obtained to complete the present invention.

Therefore, the present invention uses a slot-die coater with an electromagnet disposed on a guide roll, and has a multi-layer antifouling-insulating film capable of ensuring excellent compatibility and interfacial adhesion power and long-term physical properties in a single process, and a method of manufacturing the same. The purpose is to provide.

The present invention provides a film manufacturing method comprising the step of coating a flowable material on the surface of the polymer substrate using a slot-die coater, the electromagnet is disposed on the guide roll which is the lower end of the polymer substrate, the slot Using a die-die coater, a sol containing metal particles of different particle diameters was released on the surface of the polymer substrate under inclined conditions in the range of 30 to 60 °, and the average particle diameter was relatively caused by the magnetic field of the electromagnet. There is a feature of the method for producing a film in which a multilayer structure is formed while being sequentially laminated on the surface of a polymer substrate from the large metal particles.

In addition, the present invention is a film in which a functional layer containing titanium dioxide and antimony-tin dioxide or a metal mixture thereof is laminated on a polymer substrate,

The antifouling-insulating film is formed by sequentially stacking metal particles having a relatively large average particle diameter on the surface of the polymer substrate to form a multilayer structure.

Hereinafter, the present invention will be described in detail.

The present invention relates to a method for producing a multilayer film and a antifouling-insulating film prepared therefrom which form a multilayer coating film on a surface of a polymer substrate using a slot-die coater in a single process.

In general, in order to form a multi-layer coating film on the surface of the substrate, as many coating processes as the number of layers have to be performed. In this case, a slot-die coater is commonly used in a large-scale coating process. However, when carried out in this way there is a limit that the long-term sustainability is lowered due to intercompatibility and interfacial adhesion.

However, the present invention uses a slot-die coater in which an electromagnet is disposed on a guide roll, which is a lower end of a polymer substrate, and each solution for forming a layer uses particles containing different average particle diameters. Upon release of the solution, the multilayers are formed in a single process in which the slots are maintained under a certain range of tilt angles. That is, when the particles contained in the solution have different average particle diameters and are exposed to a magnetic field formed by an electromagnet, the particles having a larger average particle diameter are closer to the surface of the polymer substrate, and as the particle size decreases, the inclined structure is formed. To form. The layer formed as described above has an unclear interface and thus has excellent compatibility and interfacial adhesion depending on the material between the layers, thereby improving physical properties of the film.

Hereinafter, the present invention will be described in more detail using specific examples, but the present invention is not limited to these examples.

1 shows an antifouling-insulating film having a two-layer structure in which an infrared ray blocking layer 1 and a photocatalytic layer 2 are laminated on a substrate according to the present invention. The infrared blocking layer is an infrared blocking sol, the photocatalyst layer is formed using a photocatalyst sol. At this time, the titanium dioxide is contained in the photocatalyst sol, and the antimony-tin dioxide is a metal particle component contained in the infrared blocking sol. The sol component is not important in the solution injection and the position of the slot. Therefore, the particles having a large particle diameter are sequentially arranged on the surface of the polymer substrate.

The polymer base layer is generally used in the art, but is not particularly limited, but has excellent transparency and acrylic surface-treated polyester (PET), polypropylene (PP), polyvinyl chloride (PVC), and polyimide (PI). ) Can be used.

The photocatalyst sol contains a component having activity by light, and is not particularly limited, but uses titanium dioxide (TiO ₂ ) effective in terms of handling and performance. The titanium dioxide is known in the art as having a strong oxidative power to prevent contamination, purification, sterilization and deodorization, it can be used a known one. The photocatalyst sol is a hydrolysis reaction of titanium alkoxide and water under an acid catalyst to form a transparent anatase crystalline titanium dioxide sol. At this time, titanium dioxide maintains the average particle size in the range of 30 to 50 nm, if the particle size is less than 30 nm, the particle size is small, the specific gravity is relatively low in the solution, which is an inhibitory factor to form a gradient structure, 50 When it exceeds nm, there exists a problem that a photocatalyst efficiency falls. In addition, the photocatalyst sol maintains specific gravity of 0.5 to 1.8 g / cm 3. When the photocatalyst sol is less than 0.5 g / cm 3, the particle flow rate is slowed in the solution. It sinks under the solution layer.

When the photocatalyst sol is used in the range of 1.0 to 3.0% by weight based on 100% by weight of the polymer substrate, if it is less than 1.0% by weight, there is a problem in that the adhesion is inferior according to the type of the substrate used, and when it exceeds 3.0% by weight There is a problem that can damage the substrate with a large number of optically active components.

The infrared blocking sol contains a component having an activity for blocking infrared rays, and is not particularly limited, but a mixture of antimony-tin dioxide (Sb-SnO ₂ ) and indium-tin dioxide (In-SnO ₂ ) may be used. In the case of the mixed use, the antimony-tin dioxide content is 75% by weight or more, preferably 75-100% by weight, and it is preferable to use a spherical particle.

The antimony-tin dioxide (Sb-SnO ₂ ) is used in a sol form by dispersing in a highly polar alcoholic solvent, specifically isopropyl alcohol, the solvent is 75 to 85% by weight based on 100% by weight of antimony-tin dioxide It is used in the% range so that sol formation is advantageous. The antimony-tin dioxide maintains an average particle size in the range of 60 to 80 nm. If the particle size is less than 60 nm, coagulation occurs after dispersing, resulting in agglomeration and difficulty in redispersing. Is slightly elliptical and irregular, causing particles to obstruct flow in small sized solutions. In addition, the infrared barrier sol has a specific gravity of 0.5 to 1.5 g / cm 3, and if it is less than 0.5 g / cm 3, the difference in specific gravity with the surfactant layer is small, making it difficult to form an inclined structure with the infrared barrier layer. When the specific gravity exceeds 1.5 g / cm 3, the photocatalyst particles are difficult to move to the upper substrate, thereby inhibiting photoactivity.

The infrared barrier sol is used in 3 to 15% by weight with respect to the polymer substrate, if outside the above range, the thermal barrier properties are less than 40%, or the adhesion to the substrate is reduced.

In this case, it is preferable that the solution forming each layer maintains specific gravity in a similar range. The smaller the difference in specific gravity between the two solutions, the more effectively rearrangement of the particles contained in the solution occurs.

The photocatalyst sol and infrared ray blocking sol are then used to form a multilayer film using the slot die coater shown in FIG. 6 specifically composed of ejection slots of 1, 2, 3 and 4, pick-up rolls and electromagnets. At this time, the slot through which the layer forming solution passes is ejected while maintaining an inclination angle of 30 to 60 °, preferably 40 to 50 °, with respect to the surface of the polymer substrate. When the lower layer solution is mixed with the upper layer solution too quickly and is transferred to the drying oven, the drying speed of the solvent is high in the exposed surface area with air, making it difficult to form the inclined structure easily, and when it exceeds 60 °, the PICK-UP roll A problem arises that it is difficult to control the uniform coating surface from the substrate passed through.

The film in which the multilayer is formed by the above process is dried in a multi-stage guide roll installed at 5 to 15 m / min, preferably 8 to 10 m / min moving speed and 5 m section. In the case where the length of the guide roll is more than 5 m, a section in which the electromagnet is not installed increases, which causes a problem in that a coating film having no inclined structure is formed. At this time, the inclination characteristic of the particles is smoothly expressed by the electromagnet disposed on the guide roll which is the lower end of the polymer substrate. The electromagnet uses a magnetic field in the range of 600 to 1500 mG. If the magnetic field is less than 600 mG, the magnetic field is weak and the particles in the solution cannot flow sufficiently. If the electromagnet exceeds 1500 mG, the magnetic field is too strong. As a result, many particles having a high specific gravity are distributed to form a two-layer structure instead of an inclined structure. In other words, it satisfies the magnetic field in the above range and does not have much relation with the number of electromagnets. Preferably, three to five electromagnets are arranged at intervals, and more preferably, three are maintained.

In one process as described above, the particles exhibit an inclined structure in which antimony-tin dioxide having a relatively large particle diameter is laminated on the polymer substrate surface, and titanium dioxide is laminated on the antimony-tin dioxide, as shown in FIG. 7. A multi-layered antifouling-insulating film is formed with an unclear interface and improved compatibility between particles. The formed antifouling-insulating film has an infrared ray blocking rate of 65 to 75% and a surface adhesion of 40/100 to 100/100.

In order to improve surface adhesion between the layers, a surfactant may be additionally used, and the surfactant may be generally used in the art and may use nonionic, cationic and anionic surfactants. More preferably, those having excellent dispersibility with alcohol solvents may be used. Specifically, Triton X-100 (Sigma) and NP # 8 (Sigma) may be used. When the specific gravity of the surfactant is less than 0.2, the specific gravity of 0.2 or more is used, since it activates the interface between the substrate and the sol component for forming a functional layer such as a photocatalyst sol and an infrared blocking sol. There is a problem of poor dispersibility with the solvent.

Since the surfactant is used in an amount of 0.1 to 0.3% by weight with respect to the polymer substrate, if the surfactant is out of the above range, the surfactant may occur even after passing through the drying oven, thereby causing secondary coating properties.

In this case, when the surfactant is configured on the substrate, the adhesion between the substrate and the particles is increased, and when configured between the two layers, the surfactant helps the flow of particles due to the difference in specific gravity by helping the activity between the two layers. Through this process, the surfactant acts as a ligand that connects the nanoparticles with the substrate or nanoparticles. Such a surfactant is distributed between the polymer substrate, the functional layer and the functional layer, and for this purpose, the specific gravity is preferably adjusted to 0.2 or less. For example, as shown in FIG. 2, the surfactant is used as two slots of a slot die, one slot of an infrared blocking sol, and one slot of a photocatalyst sol. 2) A four-layer antifouling-insulating film composed of the surfactant layer 3 and the photocatalyst layer 4 can be produced.

Such a present invention will be described in more detail based on the following examples, but the present invention is not equivalent thereto.

Production Example

Preparation Example 1 Preparation of Titanium Dioxide

12.5 mL of Ti (OCH (CH ₃ ) ₂ ) ₄ was added to 10 mL of isopropanol to prepare a titanium starting solution. Separately, 4.4 mL of acetylacetone was added to 75 mL of distilled water to prepare a hydrolysis solution. Thereafter, the titanium raw material solution was slowly added dropwise to the hydrolysis solution to induce hydrolysis of titanium. In this case, 2 mL of 70% nitric acid was added to promote the hydrolysis reaction and stirred at 60 ° C. for 20 hours to synthesize a transparent TiO ₂ sol solution (hereinafter referred to as photocatalyst sol). TiO ₂ particles contained in this solution contained 80% or more of particles having an average particle diameter of 20 to 30 nm.

Preparation Example 2 Preparation of Antimony-Tin Dioxide Sol

Sb-SnO ₂ (ATO) having an average particle diameter of 70 to 80 nm was added to 10 mL of isopropanol and dispersed, and 30 mL of methyl ethyl ketone (MEK) was added to prepare a solution (hereinafter referred to as infrared blocking). Called pawns).

Preparation Example 3 Surfactant

Triton X-100 (Sigma) and NP # 8 (Sigma) were used as surfactants, and the coating thickness was estimated by 5 cc / m 2 from each coating solids.

Preparation Example 4 Preparation of Titanium Dioxide Sol and Antimony-Tinazole Sol Solution

The titanium dioxide sol of Preparation Example 1 and the antimony-tin dioxide sol solution of Preparation Example 2 were quantified in a 50 mL container, and the blending ratio of the titanium dioxide sol and antimony-tin dioxide sol was 1: 1 by weight, 1: 2 by weight, 1: Prepared to be 3 weight ratio, 1: 4 weight ratio. At this time, as a result of measuring the specific gravity (g / cm 3) of the compound solution was 1.23, 1.27, 1.33, 1.41, each layer was used to form a variety of layers.

Example: Film production of multilayer structure

Example 1 Film Preparation of Two-Layer Structure

In order to coat the titanium dioxide sol of Preparation Example 1 and the antimony-tin dioxide sol of Preparation Example 2 on PET (Toray Sae, XG545B, 25 μm), an electromagnet having a magnetic field in the range of 600 to 1500 mG at the bottom of the guide roll was 1 m. Surface coating of the polymer was performed using a slot-die coater method provided with three at intervals. At this time, the titanium dioxide sol and antimony-tin dioxide sol was used to maintain a 3: 1 weight ratio. In addition, the solution inlet was made up of seven holes, and the solution injected through each solution inlet having a width of 1 m was adjusted at an angle of inclination of 45 ° through the slot die inner flow path to simultaneously coat each solution in multiple layers. Since the infrared block sol should be cured by irradiation with ultraviolet light, the ultraviolet light amount was irradiated at 200 mJ / cm ² , the line speed was 15 m / min, and the drying condition was cured at 60 ° C. for 40 seconds.

Initially, the composition of the film formed of a PET substrate / antimony-tin dioxide layer (infrared shielding layer) / titanium dioxide layer (photocatalyst layer) is finally achieved by a PET substrate / antimony-tin dioxide layer (infrared shielding layer) / dioxide. The film which laminated | stacked the titanium layer (photocatalyst layer) order was manufactured.

In another method, the order of the titanium dioxide sol of Preparation Example 1 and the antimony-tin dioxide sol of Preparation 2 was changed. As a result, the PET substrate / titanium dioxide layer (photocatalytic layer) / antimony-tin dioxide layer ( The film formed of the infrared blocking layer) was finally laminated in the order of PET substrate / antimony-tin dioxide layer (infrared blocking layer) / titanium dioxide layer (photocatalyst layer).

Example 2 Film Preparation of Four Layer Structure

Triton X-100 (Sigma) having a specific gravity of 0.2 as the titanium dioxide sol of Preparation Example 1 having a specific gravity of 1.3 and the antimony-tin dioxide sol of Preparation Example 2 having a specific gravity of 1.5 and a surfactant. Or NP # 8 (Sigma) using a weight ratio of 3: 1: 0.5.

Initially, the PET substrate / surfactant / antimony-tin dioxide layer (infrared blocking layer) / surfactant / titanium dioxide layer (photocatalyst layer) was laminated in the same order to produce a film laminated in the same order.

In another method, the order of the titanium dioxide sol of Preparation Example 1 and the antimony-tin dioxide sol of Preparation 2 was changed, and as a result, the PET substrate / surfactant / titanium dioxide layer (photocatalytic layer) / surfactant / What was laminated with an antimony-tin dioxide layer (infrared blocking layer) finally produced a film laminated with a PET substrate / surfactant / antimony-tin dioxide layer / surfactant / titanium dioxide layer in that order.

5 and 7 show the scanning electron micrographs of the film prepared above, the interface between the layers was uncertain, and it was confirmed that the inclination structure was excellent.

The surface adhesion of the film prepared in Example 2 was measured and the results are shown in the following table. At this time, the surface adhesion was determined by forming 100 lattice on the surface of the coating surface by 1 mm interval by the colossal cut method according to ASTM D3359, and then subjected to five peel tests using a cellophane tape to determine the number of uncoated cells.

Initial stacking order Surface Adhesion (Number) 1, 3 layer injection ingredients 2 layer injection ingredients 4-layer injection ingredient Surfactant Triton X-100 Infrared sunscreen Photocatalyst sol 40/100 Surfactant NP # 8 Infrared sunscreen Photocatalyst sol 40/100 Surfactant Triton X-100 Photocatalyst sol Infrared sunscreen 100/100 Surfactant NP # 8 Photocatalyst sol Infrared sunscreen 80/100

Example 3 Measurement of Properties of Films According to Various Layer Structures

The same process as in Example 1, except that the functional coating layer (photocatalyst sol, photocatalyst sol + surfactant (Triton X-100, NP # 8), infrared blocking agent) of each monolayer on the surface of the polymer substrate to form a surface adhesion Measured.

Thereafter, a functional coating layer (photocatalyst sol, infrared ray blocking sol) was recoated on the coating layer of the single layer to measure surface adhesion. At this time, one layer and two layers constituted different functional layers.

division 1st layer injection ingredient 2 layer injection ingredients Surface Adhesion (Number) Example 3 Photocatalyst sol - 40/100 Photocatalyst Sol + Triton X-100 - 40/100 Photocatalyst Sol + NP # 8 - 40/100 Infrared ray shield - 40/100 Example 4 Infrared sunscreen Photocatalyst sol 60/100 Infrared Blocker + Triton X-100 Photocatalyst sol 60/100 Infrared Blocker + NP # 8 Photocatalyst sol 60/100 Photocatalyst Sol + Triton X-100 Infrared sunscreen 100/100 Photocatalyst Sol + NP # 8 Infrared sunscreen 100/100

As shown in Table 2, both of the films formed on the film layer did not produce shrinkage and obtained a good leveling coating film. FIG. 3 shows a scanning electron micrograph of the photocatalyst coated with the photocatalyst (FIG. 3A) and the surface of the coated surface treated with the photocatalyst (FIG. 3B) directly on the surface coated with the infrared blocking sol. In the case of FIG. 3B, a recessed portion is seen on the surface, and it is interpreted that the infrared ray blocker particles having a high specific gravity moved to the lower layer by the difference in specific gravity.

Example 4 Measurement of Physical Properties of Films Different in Solution Injection Speed

In the same manner as in Example 2, the surfactant is 15 cc / min, photocatalyst sol and infrared blocking sol is injected into the solution at a rate of 30 cc / min to prepare a film to measure its surface adhesion and workability The results are shown in Table 3 below.

division Solution injection speed (cc / min) Surface Adhesion (Number) Workability 4-layer injection ingredient First floor Second floor 3rd Floor 4th floor Infrared sunscreen 30 30 30 30 60/100 △ Photocatalyst sol 15 15 30 30 80/100 ○

Example 5 Transmittance and Infrared Blocking Rate According to UV Curing Time

The same process as in Example 2, except that UV curing time is different from the following Table 4 to form a film, and the transmittance and UV blocking rate were measured and the results are shown in Table 4 below.

Irradiation time (seconds) Transmittance (380-780 nm,%) Infrared cut off rate (800-1800 ㎚,%) 60 85.4 56.6 23 86.1 60.2 15 84.9 63.6

Example 6 Transmittance and Infrared Blocking Rate According to Infrared Blocking Layer Thickness

In the same manner as in Example 2, the thickness of the infrared blocking layer was changed as shown in the following Table 5 to form a film, and the transmittance and UV blocking rate were measured and the results are shown in the following Table 5. At this time, the thickness is controlled by adjusting the infrared blocking layer injection rate as a four-layer injection component.

4-layer injection ingredient Thickness (nm) Transmittance (380-780 nm,%) Infrared cut off rate (800-1800 ㎚,%) Infrared sunscreen 26 56 73 28 75 50 Photocatalyst sol 29 69 65 30 68 56

As shown in Table 5, the coating thickness 26 and 28 ㎛ is the thickness compared to the injection amount of the infrared barrier sol in the four-layer injection. When the infrared blocking sol was injected into four layers and applied, the infrared blocking rates were found to be 73 and 50% in the region of 800 to 1800 nm, respectively. When the photocatalyst layer was injected as a four-layer injection component, the coating thickness was measured to be 29 and 30 μm. When the photocatalyst sol was injected into four layers, the coating thickness was increased, but the infrared ray blocking rate was lower than that of the four-layer injection. Lowered to 65 and 56%.

As described above, by using a slot-die coater to which an electromagnet is added according to the present invention, the multilayer coating film is performed on the surface of the polymer substrate in a single, simplified process. Simultaneous formation is possible, and rearrangement of particles is induced by the magnetic field formed by the electromagnet, forming a slanted structure in which particles having a relatively large average particle size are located at the bottom of the polymer surface. As the interface is unclear, its compatibility and interfacial adhesion are excellent, and long-term physical properties can be secured.

Claims (11)

In the method for producing a film comprising the step of coating a photocatalyst sol and an infrared blocking sol on the surface of the polymer substrate using a slot-die coater, Electromagnet is placed on the guide roll which is the lower end of the polymer substrate, Using the slot-die coater, a photocatalyst sol containing titanium dioxide having an average particle diameter in the range of 30 to 50 nm, and an infrared blocking sol containing antimony-tin dioxide having an average particle diameter in the range of 60 to 80 nm. Or by discharging these sol mixtures on the surface of the polymer base material at a slope of 30 to 60 °. Method of manufacturing a film, characterized in that the multilayer structure is formed by sequentially laminated on the surface of the polymer substrate from the metal particles having a relatively large average particle size by the magnetic field of the electromagnet. delete The method of claim 1, wherein the sol further comprises a surfactant. The method of claim 1, wherein the photocatalyst sol has a specific gravity ranging from 0.5 to 1.8 g / cm 3. The method of claim 1, wherein the infrared blocking sol has a specific gravity in the range of 0.5 to 1.5 g / cm 3. The method of claim 1, wherein the film is dried at a moving speed in a range of 5 to 15 m / min and a guide roll in a range of 5 m in length. The method of claim 1, wherein the electromagnet forms a magnetic field in the range of 600 to 1500 mG. The method of claim 1, wherein the polymer substrate is a film selected from polyester (PET), polypropylene (PP), polyvinyl chloride (PVC), and polyimide (PI). A film in which a functional layer including a photocatalyst layer containing titanium dioxide and an infrared ray blocking layer containing antimony-tin dioxide is laminated on a polymer substrate, Antifouling-insulating film, characterized in that to form a multi-layer structure by sequentially stacking from the metal particles having a relatively large average particle diameter on the surface of the polymer substrate. 10. The antifouling-insulating film according to claim 9, wherein the film has an infrared ray blocking rate of 65 to 75% and a surface adhesion strength in the range of 40/100 to 100/100. 10. The antifouling-insulating film of claim 9, wherein the functional layer contains a surfactant layer containing a surfactant.

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