JP6877180B2 - Method for manufacturing a base material with an infrared reflective multilayer film and a base material with an infrared reflective multilayer film - Google Patents

Description

The present invention relates to a substrate with an infrared reflective multilayer film.

In recent years, an infrared cut film has been used as a heat shield / energy saving measure for a base material such as an outer wall or glass. Generally, the infrared cut film includes an infrared absorbing film and an infrared reflecting film. The infrared absorbing film is a type that also absorbs heat and has a high heat shielding effect, but the temperature of the base material itself becomes high, and if the base material is glass or the like, the risk of heat cracking increases. There is a drawback that the usable applications are limited. In addition, since the infrared cut film itself is a mixture with resin or made into a film, the surface is often insulated and has a structure that is water repellent and easily soiled. Will decrease.

The infrared reflective film is a surface treatment material used for surface treatment of a surface treatment target, and is an aqueous dispersion or an aqueous solution containing a heat ray reflective metal compound as a component without containing a binder for the surface treatment target. Surface-treated glass (claims 1, 2, and 9 of Patent Document 1) surface-treated with a surface-treating material (titanium oxide) is reported.

However, since the above-mentioned surface-treated glass does not contain a binder, the adhesive force between the glass and the surface-treating agent is low, the surface hardness is low, and in addition, due to the photocatalytic action of titanium oxide contained substantially, the surroundings There is a drawback that organic substances tend to deteriorate.

Further, as a base material using the infrared reflective film having a multilayer structure, a first transparent base material arranged at intervals from a parallel second transparent base material, the first transparent base material, and the second transparent base material. Includes a closed space defined between the transparent substrates and at least one infrared reflective multilayer polymer film disposed between the first transparent substrate and the second transparent substrate. In a heat insulating glass unit, the infrared reflective multilayer polymer film has a plurality of alternating polymer layers of a first polymer material and a second polymer material, and at least one of the alternating polymer layers is A heat insulating glass unit (claim 1 of Patent Document 2), which is oriented by double refraction and in which the alternating polymer layers cooperate to reflect infrared rays, has been reported.

However, since the heat insulating glass unit uses a polymer, there is a problem in long-term weather resistance, and since the structure is complicated, there are problems that the manufacturing process becomes long and the cost becomes high. Moreover, it is not considered to be used outside as a film.

As a film using another multilayer structure infrared reflective film, it is a laminated film formed by laminating a visible light antireflection layer on at least one side of a transparent conductive heat ray reflective film, and has a visible light reflectance of 5% or less and infrared rays. A transparent laminated film having a reflectance of 75% or more, wherein the transparent conductive heat ray reflective layer is a layer formed by laminating a metal layer and a dielectric layer, and the metal layers are Au and Ag. , Cu and Al, and the dielectric layer is TiO ₂ , Ta ₂ O ₅ , ZrO ₂ , SnO ₂ , SiO, SiO ₂ , In ₂ O ₃ and A transparent laminated film (claims 1 and 2 of Patent Document 3), which is a layer composed of one or more kinds selected from ZnO, has been reported.

However, since the transparent laminated film contains a metal layer, it is inferior in transparency, the metal layer is oxidized, and the film is a thermoplastic resin (paragraphs 0008 to 0012), so that it has long-term weather resistance. There is a problem that it is inferior to. That is, it is not suitable for outdoor use.

As a similar heat ray reflecting film, a laminated film in which a weather-resistant biaxially oriented polyester film is used as a base material (A) and a heat ray reflecting layer (B) and a surface protective layer (C) are provided on at least one surface of the base material. A heat ray reflective film suitable for outdoor use, characterized in that the visible light transmittance of the laminated film is 50% or more, the near infrared reflectance is 50% or more, and the haze value is 5% or less. , The heat ray reflecting layer (B) is a layer formed by alternately laminating metal layers and dielectric layers, and the metal constituting the metal layer is one or more metals selected from Au, Ag and Cu. A heat ray reflecting film (claims 1 and 5 of Patent Document 4) suitable for outdoor use according to claim 1 which is an alloy has been reported.

However, since the heat ray reflecting film also contains a metal layer, there are problems that the transparency is inferior, the metal layer is oxidized, and the film is polyester, so that the long-term weather resistance is inferior.

Japanese Unexamined Patent Publication No. 2011-246293 Special Table 2009-539648 Japanese Unexamined Patent Publication No. 2001-310407 Japanese Unexamined Patent Publication No. 2000-117918

The problem to be solved by the present invention is the outdoors composed of an inorganic substance having high infrared reflection, excellent transparency of visible light, excellent heat insulating property, high heat dissipation effect, high hardness, and long-term weather resistance. It is an object of the present invention to provide a base material having an infrared reflective multilayer film having an antifouling function that can be used in the above.

The present invention relates to a base material with an infrared reflective multilayer film that solves the above problems by having the following configuration.
[1] A base material with an infrared reflective multilayer film, which comprises a base material, an infrared blocking inorganic film, a low refractive index inorganic film, and a high refractive index inorganic film in this order.
[2] The group with an infrared reflective multilayer film according to the above [1], wherein the infrared blocking inorganic film and the low refractive index inorganic film contain silica nanoparticles, and the high refractive index inorganic film contains niobium oxide nanoparticles and diamond nanoparticles. Material.
[3] A step of applying an infrared blocking inorganic film forming dispersion liquid for forming an infrared blocking inorganic film on at least one surface of the base material at a humidity of 50% or less, and forming an infrared blocking inorganic film. A step of drying a base material coated with a dispersion liquid for forming an infrared blocking inorganic film at a temperature of 0 to 40 ° C.
A step of applying a dispersion liquid for forming a low refractive index inorganic film for forming a low refractive index inorganic film on an infrared blocking inorganic film formed on a base material at a humidity of 50% or less, and a low refractive index inorganic film. A step of drying a base material coated with a dispersion liquid for forming a low refractive index inorganic film at a temperature of 0 to 40 ° C.
A step of applying a dispersion liquid for forming a high-refractive-index inorganic film for forming a high-refractive-index inorganic film on a low-refractive-index inorganic film formed on a base material at a humidity of 50% or less, and a high-refractive index inorganic film. A step of drying a substrate coated with a film-forming dispersion at a temperature of 0 to 100 ° C.
The method for producing a base material with an infrared reflective multilayer film according to the above [1] or [2], which comprises the above in this order.

According to the present invention [1], an infrared reflective multilayer film composed of an inorganic substance having high infrared reflection and excellent visible light transparency, thus having a high heat dissipation effect, high hardness, and long-term weather resistance. A substrate having the above can be provided.

According to the present invention [3], a substrate with an infrared reflective multilayer film having an infrared blocking inorganic film, a low refractive index inorganic film, and a high refractive index inorganic film can be easily produced at a low temperature. Further, by making each dispersion liquid water-based, a base material with an infrared reflective multilayer film can be easily manufactured at a low temperature by an environment-friendly manufacturing method.

This is an example of a schematic cross-sectional view of the infrared reflective multilayer film of the present invention.

The base material with an infrared reflective multilayer film of the present invention is characterized by comprising a base material, an infrared blocking inorganic film, a low refractive index inorganic film, and a high refractive index inorganic film in this order. Here, the infrared blocking inorganic film is adjusted to have the same refractive index as the base material (when the base material is glass, for example, 1.51 to 1.59, particularly 1.52), and has a lower refractive index than the base material. The refractive index of a low refractive index inorganic film is 1.29 to 1.50, preferably 1.29 to 1.40, and the refractive index of a high refractive index inorganic film having a higher refractive index than that of the base material is , 1.6 to 2.0, preferably 1.8 to 2.0. Since this infrared reflective multilayer film is entirely made of an inorganic material and has higher thermal conductivity and thermal radioactivity than the base material, it has a high heat dissipation effect and can suppress the coefficient of thermal expansion. Therefore, especially when the base material is glass, thermal cracking of the glass can be suppressed. By increasing the reflectance in a specific wavelength range (800 to 1200 nm in near infrared rays) with this infrared reflective multilayer film, it is possible to reduce the solar heat absorption rate of the base material and suppress the temperature rise of the base material. .. For example, unlike the commercially available Low-E (Low Emissivity) double glazing, the metal film does not oxidize, so this infrared reflective multilayer glass can also be used for single glass, and is on the outer wall side. Can also be used for. In addition, since the surface has conductivity and is hydrophilic, it is possible to have a surface that is hard to get dirty and easy to remove.

FIG. 1 shows an example of a schematic cross-sectional view of the infrared reflective multilayer film of the present invention. As shown in FIG. 1, the base material 1 with an infrared reflective multilayer film of the present invention includes a base material 10, an infrared blocking inorganic film 20, a low refractive index inorganic film 30, and a high refractive index inorganic film 40 in this order. It is a feature.

The base material with an infrared reflective multilayer film of the present invention is
A step of applying an infrared blocking inorganic film forming dispersion liquid for forming an infrared blocking inorganic film on at least one surface of a substrate at a humidity of 50% or less, and infrared rays for forming an infrared blocking inorganic film. A step of drying a base material coated with a dispersion liquid for forming a blocking film at a temperature of 0 to 40 ° C.
A step of applying a dispersion liquid for forming a low refractive index inorganic film for forming a low refractive index inorganic film on an infrared blocking inorganic film formed on a base material at a humidity of 50% or less, and a low refractive index inorganic film. A step of drying a base material coated with a dispersion liquid for forming a low refractive index inorganic film at a temperature of 0 to 40 ° C.
A step of applying a dispersion liquid for forming a high-refractive-index inorganic film for forming a high-refractive-index inorganic film on a low-refractive-index inorganic film formed on a base material at a humidity of 50% or less, and a high-refractive index inorganic film. A step of drying a substrate coated with a film-forming dispersion at a temperature of 0 to 100 ° C.
Can be easily produced by a method containing the above in this order.

In the film formation at room temperature (0 to 40 ° C.), due to the volatilization of the solvent in each dispersion, the thicker the film thickness, the more the influence of volatile bubbles remains on the film surface, and the film strength becomes brittle. , Cracks tend to occur easily. In the case of a low refraction inorganic film alone and a high refraction inorganic film alone, if the film thickness exceeds 300 nm, cracks are likely to occur in the film and the film strength decreases, but the total film thickness is increased by forming a multilayer film. The film strength can be increased even when the thickness is 1 μm or more. For example, in the pencil hardness test, the infrared blocking inorganic film is 6H, the low refraction inorganic film is 7H, the high refraction inorganic film is 9H, and the multilayer film layer is 10H or more. Further, in particular, when carbon nanofibers, graphene nanoparticles and the like are contained in the film, cracks are less likely to occur in the film, and the film thickness can be further increased.

〔Base material〕
Examples of the base material include glass, polycarbonate resin, acrylic resin, polyethylene terephthalate resin, polymethylmethacrylate resin, vinyl chloride resin and the like, and glass is preferable from the viewpoint of weather resistance. However, since the infrared reflective multilayer inorganic film itself has an ultraviolet blocking ability, the weather resistance of these resins is improved by forming the infrared reflective multilayer inorganic film.

[Infrared blocking inorganic film]
Infrared blocking inorganic film forming dispersion, preferably to include silica particles and hollow nanosilica, further, cesium tungsten oxide nanoparticles, indium tin oxide (ITO) nanoparticles oxide, ATO nanoparticles, metallic ruthenium particles, Ti0 ₂ nanoparticles, It is more preferable to contain at least one selected from the group consisting of ZnO nanoparticles, InZNO nanoparticles, and CeO2 nanoparticles, and a solvent. Here, the nanoparticles refer to those having a particle size (n = 50) measured by a transmission electron microscope of less than 20 nm. The average particle size of the nanoparticles is the mass average particle size measured with a transmission electron microscope (n = 50). However, only the hollow nanosilica particles have an average particle size of 50 to 300 nm. The silica nanoparticles have a particle size of 1 to 9 nm: 100 parts by mass with respect to 100 parts by mass of the single nanoparticles measured by a transmission electron microscope. Here, the silica single nanoparticles refer to those having a particle size (n = 50) measured by a transmission electron microscope of less than 10 nm. When silica nanoparticles of 10 nm or more are used, the transmittance of the infrared blocking inorganic film tends to be low. It is confirmed by X-ray diffraction that it is amorphous. Hollow nanosilica with a diameter of 100 nm or more is preferable to have a hardness of less than 100 nm because the heat insulating performance is improved, the haze is likely to increase, and the hardness is also lowered. An example of the thermal conductivity mp of 50 nm hollow silica is 0.06 w / mk.

Cesium tungsten oxide nanoparticles, the general _formula: (wherein, 0.30 ≦ x / y ≦ 0.33,2.2 ≦ z / y ≦ 3.0) Cs x W y O z those represented by ,preferable. An example of the particle size of the cesium tungsten oxide nanoparticles is 20 nm, and an example of the particle size of the indium tin oxide nanoparticles is 10 nm. An example of the average particle size of ATO nanoparticles is 20 nm. An example of the particle size of metallic ruthenium particles is 4 nm.

Examples of the solvent include water, but water is preferable from the viewpoint of the dispersibility of the silica nanoparticles and the drying rate after coating. When the solvent is water, it is subjected to plasma treatment, UV treatment, and corona treatment, and can be applied to resins such as PET, acrylic, and PC on a hydrophilic surface. Optionally, a small amount of a high boiling point solvent such as a glycol may be added.

It is preferable that the dispersion liquid for forming an infrared blocking film further contains carbon nanofibers and graphene nanoparticles in order to improve heat dissipation and conductivity and prevent cracks in the film. By containing carbon nanofibers and graphene, the surface resistance value (measurement method will be described later) ^{can be made conductive to 1 × 10 3} Ω or less while maintaining the transparency of the infrared blocking film, and energization is possible. Allows heat generation and anti-fog.

The carbon nanofibers are not particularly limited, but the carbon nanofibers have a fiber diameter of 1 to 100 nm, an aspect ratio of 5 or more, and an interval of [002] planes of the graphite layer measured by X-ray diffraction is 0. It is preferably .35 nm or less. The carbon nanofibers having a fiber diameter and an aspect ratio can be uniformly dispersed in a solvent and can form sufficient contact points with each other. Since carbon nanofibers having a lamination interval of [002] planes of the graphite layer measured by X-ray diffraction within the above range have high crystallinity, it is possible to obtain a highly conductive material having low electrical resistance from the carbon nanofibers. it can. Further, when the volume resistivity of the compacted body of the carbon nanofiber is 1.0 Ω · cm or less, good conductivity can be exhibited.

The fiber diameter of the carbon nanofiber is a mass average particle diameter obtained by observing a transmission electron micrograph (magnification: 100,000 times) (n = 50). The aspect ratio of carbon nanofibers is obtained by observing a transmission electron micrograph (magnification of 100,000 times) and calculating (major axis average particle size / minor axis average particle size) (n = 50). CuKα rays are used in the measurement by X-ray diffraction. The volume resistivity of the compacted body of carbon nanofibers is measured by pressurizing at ^{100 kgf / cm 2} using a powder measuring unit manufactured by Mitsubishi Chemical Corporation Loresta HP and Dia Instruments.

Further, it is more preferable that the carbon nanofibers contain single-walled carbon nanotubes and multi-walled carbon nanotubes and can be dispersed in a solvent without using a dispersant. Examples of the treatment for making carbon nanofibers dispersible in a solvent include treatment with a strong acid such as sulfuric acid. In addition, a carbon nanofiber dispersion liquid that does not use a dispersant is also commercially available.

Examples of graphene nanoparticles include graphene nanoparticles having a thickness (c-axis direction) of 50 nm or less and a radial (a-axis direction) diameter of 2 μm or less dispersed in water.

Infrared shielding film-forming dispersions further in order to improve the ultraviolet blocking ratio, TiO ₂ nanoparticles, ZnO nanoparticles, InZnO nanoparticles to include CeO2 nanoparticles, more preferably. By containing these, it is possible to improve the ultraviolet blocking rate while maintaining the transparency of the infrared blocking film.

An example of the average particle size of TiO _{2 nanoparticles is 10 nm.} An example of the average particle size of ZnO nanoparticles is 20 nm. An example of the average particle size of InZNO nanoparticles is 20 nm. An example of the average particle size of CeO2 nanoparticles is 10 nm.

Additives and the like can be further added to the dispersion liquid for forming an infrared blocking inorganic film as needed within a range that does not impair the object of the present invention, but in order to form an infrared blocking inorganic film at 100 ° C. or lower. , It is preferable not to contain a dispersant.

The infrared blocking inorganic film dispersion can be obtained, for example, by stirring, melting, mixing, and dispersing silica single nanoparticles, a solvent, and other additives simultaneously or separately, with heat treatment if necessary. it can. The apparatus for mixing, stirring, dispersing, etc., is not particularly limited, but a Raikai machine, a ball mill, a planetary mixer, a bead mill, or the like can be used. Moreover, you may use these devices in combination as appropriate.

The infrared blocking inorganic film is formed by applying a dispersion liquid for forming an infrared blocking inorganic film to a base material at a humidity of 50% or less, and a base material coated with the dispersion liquid for forming an infrared blocking inorganic film at a temperature of 0 to 0. It can be formed by a step of drying at 100 ° C.

If the temperature of the infrared blocking inorganic film-forming dispersion is less than 0 ° C, the water content in the film-forming dispersion may freeze, and if it exceeds 100 ° C, the film-forming dispersion will volatilize faster, during mass production. There is a risk that the solid content concentration in the film-forming dispersion will increase during long-term coating. When the humidity when applying the dispersion liquid for forming a low refractive index inorganic film exceeds 50%, it becomes easy to take in the moisture of the atmosphere into the coating film of the dispersion liquid for forming a low refractive index inorganic film, and the low refractive index inorganic film is formed. The coating film of the dispersion liquid may become cloudy. In particular, when the humidity is 60% or more, the coating film of the dispersion liquid for forming a low refractive index inorganic film tends to become cloudy. The ambient temperature at the time of coating is a room temperature of 0 to 40 ° C. Next, the temperature at which the substrate coated with the dispersion liquid for forming a low refractive index inorganic film is dried is a room temperature of 0 to 40 ° C, preferably 5 to 20 ° C, preferably 10 to 15 ° C. And more preferable. The hardness and adhesion of the coating film are improved by defoaming the air dissolved in the solution by using ultrasonic stirring, vacuum defoaming, centrifugation, or the like for the solution before molding. By coating in a reduced pressure environment under a nitrogen purge also under the coating environment, it is possible to accelerate the volatilization rate of the solvent and improve the defoaming effect, so that the hardness and adhesion are improved.

The thickness of the infrared blocking inorganic film is preferably 90 nm to 5 μm, preferably 200 nm to 2 μm, from the viewpoint of ease of forming the infrared blocking inorganic film. As described above, the refractive index of the infrared blocking inorganic film needs to be adjusted to the same level as that of the base material. In addition, by containing hollow silica, a heat insulating effect is imparted to the infrared blocking film layer, and the infrared reflecting function and heat dissipation effect are enhanced through a low refractive index inorganic film and a high refractive index film having higher radioactivity and thermal conductivity. , It becomes possible to block heat more effectively.

[Low refractive index inorganic film]
The dispersion liquid for forming a low refractive index inorganic film preferably contains silica nanoparticles and a solvent.

The silica nanoparticles and the solvent are as described above.

If the amount of the solvent is 95 to 99 parts by mass with respect to 100 parts by mass of the dispersion liquid for forming a low refraction inorganic film, the stability of the dispersion liquid tends to deteriorate if it is less than 95 parts by mass, and if it exceeds 99 parts by mass, the solvent of the solvent is used. The volatilization rate becomes slow, and it may be difficult to dry at room temperature.

The dispersion liquid for forming a low refractive index inorganic film preferably further contains carbon nanofibers and graphene nanoparticles in order to improve heat dissipation and conductivity and prevent cracks in the film. The carbon nanofibers and graphene nanoparticles are as described above.

The dispersion liquid for forming a low refractive index inorganic film can further contain additives and the like as necessary within a range that does not impair the object of the present invention, but for forming a low refractive index inorganic film at 40 ° C. or lower. It is preferable that the dispersant is not contained.

The dispersion liquid for forming a low refractive index inorganic film is prepared by, for example, stirring, melting, mixing, and dispersing silica single nanoparticles, a solvent, and other additives at the same time or separately, with heat treatment if necessary. Obtainable. The apparatus for mixing, stirring, dispersing, etc., is not particularly limited, but a Raikai machine, a ball mill, a planetary mixer, a bead mill, or the like can be used. Moreover, you may use these devices in combination as appropriate.

The low refractive index inorganic film is a step of applying the above-mentioned dispersion liquid for forming a low refractive index inorganic film on at least one surface of a base material at a humidity of 50% or less, and a dispersion liquid for forming a low refractive index inorganic film. Can be formed by a step of drying the substrate coated with the above at a temperature of 0 to 40 ° C.

The temperature of the dispersion liquid for forming a low refractive index inorganic film is the same as that of the dispersion liquid for forming an infrared blocking inorganic film.

The thickness of the low refractive index inorganic film is preferably 10 to 200 nm from the viewpoint of improving the transmittance of the low refractive index inorganic film.

[High refractive index inorganic film]
The dispersion liquid for forming a high refractive index inorganic film preferably contains niobium oxide nanoparticles and diamond nanoparticles, and more preferably contains graphene, carbon nanotubes, titanium oxide nanoparticles, tungsten oxide nanoparticles, and a solvent. The solvent is as described above.

Examples of the nanoparticles contained in the dispersion liquid for forming a high refractive index inorganic film include niobium oxide particles, diamond particles, zirconium oxide particles, titanium oxide particles, tungsten oxide particles, tin oxide particles, and phosphorus-doped tin oxide particles. Particles and diamond nanoparticles are preferable from the viewpoint of the refractive index, hardness, and adhesion to the substrate of the high refractive index inorganic film. Here, as an example of the measurement result of the refractive index, niobium oxide particles: 2.3, diamond particles: 2.8, zirconium oxide particles: 2.4, titanium oxide particles: 2.7, tin oxide particles: 2. 0, phosphorus-doped tin oxide particles: 2.0. When these particles are made into a thin film, the refractive index decreases, and examples of the measurement results of the refractive index of the thin film are zirconium oxide thin film: 1.73, niobium oxide thin film: 1.78, and titanium oxide thin film: 1. 85, tin oxide thin film: 1.62, diamond thin film: 2.0. It is considered that this is because there are pores in the thin film.

Examples of the particle size of the nanoparticles are niobium oxide particles: 6 nm, diamond particles: 3 to 5 nm, zirconium oxide particles: 7 nm, titanium oxide particles: 10 to 15 nm, and tin oxide particles: 2 nm.

The dispersion liquid for forming a high refractive index inorganic film preferably further contains carbon nanofibers and graphene nanoparticles in order to improve heat dissipation and conductivity and prevent cracks in the film. The carbon nanofibers and graphene nanoparticles are as described above.

Additives and the like can be further added to the dispersion liquid for forming a high refractive index inorganic film as needed within a range that does not impair the object of the present invention, but a high refractive index inorganic film is formed at 100 ° C. or lower. Therefore, it is preferable not to contain a dispersant.

The method for producing the dispersion liquid for forming a high refractive index inorganic film is the same as the method for producing the dispersion liquid for forming an infrared blocking inorganic film.

The high-refractive-index inorganic film is a step of applying a dispersion liquid for forming a high-refractive-index inorganic film to a low-refractive-index inorganic film formed on a base material at a humidity of 50% or less, and for forming a high-refractive-index inorganic film. The base material coated with the dispersion liquid can be formed by a step of drying at a temperature of 0 to 100 ° C.

The lower limits of the humidity at the time of application and the temperature at the time of drying are as described above. A high refractive index inorganic film can be formed at a drying temperature of 40 ° C., but the refractive index of the high refractive index inorganic film may be increased by drying at 100 ° C.

The thickness of the high-refractive-index inorganic film is preferably 20 to 200 nm from the viewpoint of easy formation of the high-refractive-index inorganic film and improvement of the reflectance of the high-refractive-index inorganic film.

The high refractive index inorganic film may further contain tungsten oxide and titanium oxide having a photocatalytic function.

The present invention will be described with reference to Examples, but the present invention is not limited thereto. In the following examples, parts and% indicate parts by mass and% by mass unless otherwise specified.
As the silica nanoparticle dispersion liquid 1, a low refraction binder made by Japan Nanocoat (product name: LR-30, a mixture of 3 parts by mass of single nanoparticles of silica having a diameter of 2 to 9 nm and 97 parts by mass of water) was used.
As the silica nanoparticle dispersion liquid 2, a silica binder manufactured by JGC Catalysts and Chemicals Co., Ltd. (product name: Si-550, average particle size: 5 nm, solid content: 20%) was used.
KJNANOCOAT's water dispersion (product name: SIO-50, average particle size 50 nm, solid content 10%) was used as the hollow nanosilica dispersion, and Japan Nanocoat's water dispersion (product name: Japan Nanocoat) was used as the niobium nanoparticle dispersion. Niobium oxide dispersion, average particle size: 6 nm, solid content: 3%) was used.
As the diamond nanoparticle dispersion liquid, a water dispersion liquid manufactured by New Metals End Chemicals Corporation (product name: nanoamand, average particle size: 3 to 5 nm, solid content: 5%) was used.
UV-TIO2 (average particle size 10 nanosolid content 10%) manufactured by Japan Nanocoat was used as the titanium oxide nanoparticle dispersion liquid.
IRWPO-15 (average particle size 20 nm, solid content 15%) manufactured by KJNANOCOAT Co., Ltd. was used as the cesium oxide tungsten nanoparticles dispersion liquid.
As the indium tin oxide nanoparticle dispersion liquid, ITO-20 (average particle size 10 nm, solid content 20%) manufactured by Japan Nanocoat was used.
As the graphene dispersion, GF-01 manufactured by Japan Nanocoat (thickness (c-axis direction): 50 nm or less, radial direction (axial direction): 2 μ or less, solid content: 0.1%) was used.
As the InZNO dispersion, an InZNO aqueous dispersion manufactured by KJNANOCOAT (average particle size: 20 nm, solid content: 20%) was used.

The transmittance was measured with a measuring instrument manufactured by EDTM (model number: Windows Energy Profiler WP4500).
The refractive index was calculated from a reflection graph measured by a spectrophotometer manufactured by Shimadzu Corporation (model number: SolidSpec-3700DUV). At the time of this measurement, the surface reflectance was measured by contacting a plate having a reflectance of 0 on an area of 50% of the surface opposite to the high-refractive-index thin film of the glass substrate on which the high-refractive-index thin film was formed, and the refractive index was measured. Calculated. The degree of cloudiness was measured with a spectroscopic haze meter SH7000SP manufactured by Nippon Denshoku Kogyo Co., Ltd.
The surface resistance value was measured with a surface resistance meter manufactured by Taiyo Denki Sangyo (model number: WA-400, two-point resistance method, distance between probes: 50 mm) (unit: Ω). However, for those with 10 3 Ω or less, measurement was performed with a digital multimeter manufactured by Sanwa Electric Instrument Co., Ltd. (model number: PM-3, distance between probes: 50 mm) (unit: Ω).
The hardness of the pencil was determined by scratching the film formed on the glass substrate with a pencil having a hardness of HB to 10H and visually observing the hardness of the hardest pencil without chipping of the film.
The tape peeling test conforms to JIS K5400, and 100 1 mm x 1 mm cuts are made in various films formed on the glass substrate with a cutter knife, Nichiban cellophane tape is attached, and then the cellophane tape is peeled off visually. For the hydrophilicity test in which the presence or absence of peeled parts of various films was observed, the surface contact angle was measured using a portable contact angle meter (model number: PCA-11) manufactured by Kyowa Interface Science Co., Ltd.

[Example 1]
[Preparation of infrared blocking inorganic film]
Silica nanoparticle dispersion 1:30 parts by mass, silica nanoparticle dispersion 2:10 parts by mass, hollow nanosilica dispersion: 10 parts by mass :, titanium oxide nanoparticle dispersion: 15 parts by mass, indium tin oxide nanoparticles dispersion solid content 10% by mass diluted aqueous solution: 10 parts by mass, cesium oxide tungsten oxide nanoparticle dispersion diluted to 20% solid content: 20 parts by mass, graphene dispersion: 5 parts by mass were mixed and dispersed for forming an infrared blocking inorganic film. The solution was prepared.

A dispersion liquid for forming an infrared blocking inorganic film at 15 to 20 ° C. was applied to a base material using a coating device manufactured by Tokyo Roller Industry Co., Ltd. at an ambient temperature of 15 to 20 ° C., a humidity of 36 to 48%, and a width of 155 mm. , Length: 155 mm. The coated glass substrate (refractive index: 1.52) is dried at a temperature of 15 to 20 ° C. for 5 minutes to obtain a glass substrate with an infrared blocking inorganic film having a thickness of about 1 μm and a refractive index of 1.52. ,Obtained.

As a result of measuring the obtained glass substrate with an EDTM measuring instrument, the visible light transmittance was 64%, the ultraviolet transmittance was 0%, and the infrared transmittance was 10%. The refractive index: 1.52, surface resistivity: 10 ⁵ Omega stand, pencil hardness: 6H, tape peeling were: None.

[Preparation of low refractive index inorganic film]
On the obtained infrared blocking film, a silica nanoparticle dispersion liquid 1 at 15 to 20 ° C. was applied to an atmospheric temperature of 15 to 20 ° C., a humidity of 36 to 48%, and a width of 155 mm using a coating device manufactured by Tokyo Roller Industries. , Length: 155 mm. The coated glass substrate was dried at a temperature of 15 to 20 ° C. for 5 minutes to obtain a glass substrate with a low refractive index inorganic film having a thickness of 140 nm.

As a result of measuring the obtained glass substrate with a high-priced measuring instrument manufactured by EDTM, the visible light transmittance was 67%, the ultraviolet transmittance was 0%, and the infrared transmittance was 13%. The refractive index: 1.3, surface resistivity: 10 ⁹ Omega stand, pencil hardness: 7H, tape peeling were: None.

[Preparation of high refractive index inorganic film]
Niobium oxide nanoparticle dispersion: 69 parts by mass, diamond nanoparticle dispersion: 1 part by mass, graphene dispersion: 30 parts by mass were mixed to prepare a dispersion for forming a highly refractory inorganic film.

On the obtained low-refractive-index inorganic film, a dispersion liquid for forming a high-refractive-index inorganic film at 15 to 20 ° C. was applied to an atmospheric temperature of 15 to 20 ° C. and a humidity of 36 to 48% using a coating device manufactured by Tokyo Roller Industries. Then, the coating was applied to a width of 155 mm and a length of 155 mm. The coated glass substrate was dried at a temperature of 15 to 20 ° C. for 5 minutes to obtain a glass substrate with a high refractive index inorganic thickness of 140 nm.

As a result of measuring the obtained glass substrate with an infrared reflective multilayer inorganic film with an optical measuring instrument manufactured by DTM, the visible light transmittance was 66%, the ultraviolet transmittance was 0%, and the infrared transmittance was 5%. The refractive index: 1.9, surface resistivity: 10 ³ Omega table below, pencil hardness: 10H, tape peeling were: None. The contact angle was 5 ° or less, and the haze value was 0.5. The infrared reflectance at 800 nm was 20% or more.

[Example 2]
[Preparation of infrared blocking inorganic film]
Silica nanoparticle dispersion: 60 parts by mass, hollow nanosilica dispersion: 10 parts by mass, InZNO nanoparticle dispersion: 10 parts by mass, cesium tungsten nanoparticles 20 parts by mass in the same manner as in Example 1. , A glass substrate with an infrared blocking inorganic film was obtained. The infrared blocking inorganic film had a visible light transmittance of 67%, an ultraviolet transmittance of 0%, and an infrared transmittance of 10%.

[Preparation of low refractive index inorganic film]
Using 100 parts by mass of the silica nanoparticles dispersion liquid, a glass substrate with a low refractive index inorganic film was obtained in the same manner as in Example 1. The visible light transmittance of the substrate with a low refractive index inorganic film was 69%, the ultraviolet transmittance was 0%, and the infrared transmittance was 12%.

[Preparation of high refractive index inorganic film]
A glass substrate with a high refractive index inorganic film was obtained in the same manner as in Example 1 except that 100 parts by mass of the niobium nanoparticle dispersion was used. The visible light transmittance of the glass substrate with the infrared reflective multilayer inorganic film was 68%, the ultraviolet transmittance was 0%, and the infrared transmittance was 5% (infrared cut rate was 95%). In addition, the pencil hardness of the glass substrate with infrared reflective multilayer inorganic film was 10H, the tape was not peeled off, the haze value was 0.7, the infrared reflectance at 800 nm was 20% or more, and the surface resistance value was 10 in the 10th power Ω. .. In addition, the standard of the general infrared ray blocking function is that the visible light transmittance is 60% or more, the infrared ray cut rate is 90% or more, and the haze value is 1.0 or less.

[Comparative Example 1]
Only a low refractive index film was formed on the glass substrate. The low refractive index film is the same as that produced in Example 1. The optical data of the glass substrate with a low refraction inorganic film is visible light transmittance: 94%, ultraviolet ray transmittance: 89%, infrared transmittance: 94%, pencil hardness: 7H, refractive index 1.3, and infrared ray blocking. No effect was observed.

[Comparative Example 2]
Only a high refractive index film was formed on the glass substrate. The high refractive index film is the same as that produced in Example 1. The optical data of the glass substrate with a highly refractive inorganic film is visible light transmittance: 86%, ultraviolet ray transmittance: 87%, infrared transmittance: 88%, pencil hardness: 9H, refractive index 1.9, and infrared ray blocking. No effect was observed.

[Comparative Example 3]
An infrared blocking film and a low refractive index film were formed on the glass substrate, and a high refractive index inorganic film was not formed. The infrared blocking film and the low refractive index film are the same as those produced in Example 1. Infrared reflection effect, not observed.

[Comparative Example 4]
An infrared blocking film and a high refractive index film were formed on the glass substrate, and a low refractive index inorganic film was not formed. The infrared blocking film and the high refractive index film are the same as those produced in Example 1. In the configuration of Comparative Example 4, since the reflectance in the visible light region was improved, the glare and the haze value became 1.0 or more.

[Comparative Example 5]
A low refractive index film and a high refractive index film were formed on the glass substrate, and an infrared blocking film was not formed. The low refractive index film and the high refractive index film are the same as those produced in Example 1. In the configuration of Comparative Example 5, no effective infrared blocking function was observed.

The present invention has high infrared reflection, excellent visible light transparency, high heat insulating effect and heat dissipation effect, high hardness, and long-term weather resistant infrared reflective multilayer with antifouling function. It is possible to provide a base material having a film, which is very useful for applications such as transparent exterior building materials (glass, polyca, vinyl house, PET film, etc. In particular, an aqueous dispersion is used to form an inorganic film. Therefore, it is possible to easily transport the dispersion liquid to a hot area near the equator such as the Middle East and Africa, and to easily form an infrared reflective multilayer film on site.

1 Base material with infrared reflective multilayer film 10 Base material 20 Infrared blocking inorganic film 30 Low refractive index inorganic film 40 High refractive index inorganic film

Claims (2)

A base material, an infrared blocking inorganic film, a low refractive index inorganic film, and a high refractive index inorganic film are provided in this order, and the infrared blocking inorganic film and the low refractive index inorganic film contain silica nanoparticles, and the high refractive index inorganic film contains silica nanoparticles. A substrate with an infrared reflective multilayer inorganic film, which comprises niobium oxide nanoparticles and diamond nanoparticles. A step of applying an infrared blocking inorganic film forming dispersion liquid for forming an infrared blocking inorganic film on at least one surface of a substrate at a humidity of 50% or less, and infrared rays for forming an infrared blocking inorganic film. A step of drying a base material coated with a dispersion liquid for forming a blocking inorganic film at a temperature of 0 to 40 ° C.
A step of applying a dispersion liquid for forming a low refractive index inorganic film for forming a low refractive index inorganic film on an infrared blocking inorganic film formed on a base material at a humidity of 50% or less, and a low refractive index inorganic film. A step of drying a base material coated with a dispersion liquid for forming a low refractive index inorganic film at a temperature of 0 to 40 ° C.
A step of applying a dispersion liquid for forming a high-refractive-index inorganic film for forming a high-refractive-index inorganic film on a low-refractive-index inorganic film formed on a base material at a humidity of 50% or less, and a high-refractive index inorganic film. A step of drying a substrate coated with a film-forming dispersion at a temperature of 0 to 100 ° C.
The included in this order, a manufacturing method of claim 1 Symbol placement of infrared reflecting multilayer film substrate.

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