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WO2013146447A1 - Film contenant des particules d'argent et son procédé de fabrication, et matériau de protection contre les rayonnements thermiques - Google Patents

Film contenant des particules d'argent et son procédé de fabrication, et matériau de protection contre les rayonnements thermiques Download PDF

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Publication number
WO2013146447A1
WO2013146447A1 PCT/JP2013/057753 JP2013057753W WO2013146447A1 WO 2013146447 A1 WO2013146447 A1 WO 2013146447A1 JP 2013057753 W JP2013057753 W JP 2013057753W WO 2013146447 A1 WO2013146447 A1 WO 2013146447A1
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Prior art keywords
silver
particle
tabular
heat ray
layer
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English (en)
Japanese (ja)
Inventor
威史 濱
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Fujifilm Corp
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Fujifilm Corp
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/068—Flake-like particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting filters

Definitions

  • the present invention relates to a silver particle-containing film, a production method thereof, and a heat ray shielding material. More specifically, the present invention relates to a natural color silver particle-containing film and a method for producing the same, and a heat ray shielding material capable of reflecting infrared light using the silver particle-containing film.
  • Silver particle-containing films containing silver particles in the film plane are applied to various fields by taking advantage of the characteristics of silver.
  • a silver particle-containing film in recent years, as one of energy saving measures for reducing carbon dioxide, it has been known to apply to a heat ray shielding material for automobiles and windows of buildings.
  • re-radiation is more effective than a heat ray absorption type in which re-radiation of absorbed light into the room (about 1/3 of the absorbed solar radiation energy) is present.
  • a heat ray reflective heat ray shielding material without re-radiation can be obtained by using a silver particle-containing film.
  • Patent Document 1 includes 60% by number or more of hexagonal or circular tabular silver particles, and the main plane of the hexagonal or circular tabular silver particles is one surface of the silver particle-containing film.
  • a heat ray shielding material having a plane orientation in an average range of 0 ° to ⁇ 30 ° is disclosed, and it is described that it has visible light transparency and can shield heat rays in the near infrared region. .
  • the heat ray shielding material is mainly used by sticking to a windshield of a car or a window glass for a building, and the heat ray shielding material having a large a * value or b * value in the L * a * b * color system.
  • the heat ray shielding material is required to have practical chromaticity adjustment of chromaticity and color balance from the viewpoint of ensuring visual safety and securing a natural field of view when pasted on the windshield of an automobile.
  • a heat ray shielding material having a natural (grayscale) color tone with a small b * value There has been a demand for a heat ray shielding material having a natural (grayscale) color tone with a small b * value.
  • Patent Document 2 discloses a color tone in the L * a * b * color system in a configuration containing at least an organic infrared absorbing dye such as diimonium or phthalocyanine and a transparent resin. Describes an example in which ⁇ 3 ⁇ a * ⁇ 3 and ⁇ 3 ⁇ b * ⁇ 3.
  • organic infrared absorbing dye such as diimonium or phthalocyanine
  • a transparent resin Describes an example in which ⁇ 3 ⁇ a * ⁇ 3 and ⁇ 3 ⁇ b * ⁇ 3.
  • chromaticity was adjusted or an example in which suitable chromaticity was suggested.
  • the problem to be solved by the present invention is to provide a silver particle-containing film whose color tone in the L * a * b * color system is
  • the present invention which is means for solving the above problems is as follows.
  • the silver particle-containing film according to [1] preferably has a color tone of
  • [3] including a step of preparing a silver nanoparticle dispersion from a silver seed crystal solution, the silver nitrate-containing solution being added to the silver seed crystal solution in an addition time of 5 minutes or more, and the addition of the silver nitrate-containing solution
  • a method for producing a silver particle-containing film comprising: adding a solution containing silver sulfite to a silver seed crystal solution; and controlling the pH of the silver nanoparticle dispersion after adding the solution containing silver sulfite to 8.0 or less.
  • [4] A silver particle-containing film produced by the method for producing a silver particle-containing film according to [3].
  • a heat ray shielding material comprising the silver particle-containing film according to any one of [1], [2] and [4] as a heat ray reflective layer.
  • the tabular silver nanoparticles in the silver particle-containing film are hexagonal tabular silver nanoparticles.
  • the heat ray shielding material according to [5] or [6] is such that a main plane of the tabular silver nanoparticles in the silver particle-containing film is on one surface of the silver tabular grain-containing layer.
  • the plane orientation is preferably in the range of 0 ° to ⁇ 30 ° on average.
  • the heat ray shielding material according to any one of [5] to [7] preferably has a visible light transmittance of 65% or more.
  • the silver tabular grain-containing layer in the silver particle-containing film is disposed on at least one surface of the substrate. preferable.
  • the metal oxide particle-containing layer is on the side opposite to the surface on which the silver tabular grain-containing layer of the substrate is disposed. It is preferable to arrange on the surface.
  • FIG. 1A is a schematic perspective view showing an example of the shape of tabular grains contained in the silver particle-containing film of the present invention, and shows circular tabular silver nanoparticles.
  • FIG. 1B is a schematic perspective view showing an example of the shape of a tabular grain contained in the silver particle-containing film of the present invention, and shows hexagonal tabular silver nanoparticles.
  • FIG. 1A is a schematic perspective view showing an example of the shape of tabular grains contained in the silver particle-containing film of the present invention, and shows circular tabular silver nanoparticles.
  • FIG. 1B is a schematic perspective view showing an example of the shape of a tabular grain contained in the silver particle-containing film of the present invention, and shows hexagonal tabular silver nanoparticles.
  • FIG. 1A is a schematic perspective view showing an example of the shape of tabular grains contained in the silver particle-containing film of the present invention, and shows circular tabular silver nanoparticles.
  • FIG. 1B is a schematic perspective view showing an example of the shape of
  • FIG. 2A is a schematic cross-sectional view showing the existence state of a silver tabular grain-containing layer containing tabular silver nanoparticles in the silver particle-containing film of the present invention, and is a silver tabular grain containing tabular silver nanoparticles
  • the figure explaining the angle ((theta)) which the containing layer (parallel also with the plane of a base material) and the main plane (plane which determines circle equivalent diameter D) of hexagonal flat silver nanoparticles is shown.
  • FIG. 2B is a schematic cross-sectional view showing the state of existence of a silver tabular grain-containing layer containing tabular silver nanoparticles in the silver particle-containing film of the present invention, wherein the silver grain-containing film of the silver tabular grain-containing layer is shown.
  • FIG. 2C is a schematic cross-sectional view showing an example of the presence state of a silver tabular grain-containing layer containing tabular silver nanoparticles in the silver particle-containing film of the present invention.
  • FIG. 2D is a schematic cross-sectional view showing another example of the presence state of a silver tabular grain-containing layer containing tabular silver nanoparticles in the silver particle-containing film of the present invention.
  • FIG. 2E is a schematic cross-sectional view showing another example of the existence state of the silver tabular grain-containing layer containing tabular silver nanoparticles in the silver particle-containing film of the present invention.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the silver particle-containing film of the present invention has a silver tabular grain-containing layer containing tabular silver nanoparticles having an average equivalent circle diameter of 70 nm to 500 nm, and the color tone is L * a * b * color system,
  • the heat ray shielding material of this invention is characterized by including the silver particle containing film
  • membrane of this invention and its preferable aspect are the same as the description and preferable aspect of the heat ray reflective layer in the heat ray shielding material of this invention.
  • the color tone in the L * a * b * color system is
  • the color tone in the L * a * b * color system is preferably
  • the color tone in the L * a * b * color system is preferably
  • the color tone in the L * a * b * color system is more preferably
  • the color tone in the L * a * b * color system is
  • the silver particle-containing film of the present invention particularly preferably has a color tone in the L * a * b * color system of
  • the color tone in the L * a * b * color system is more preferably
  • the solar reflectance of the silver particle-containing film of the present invention preferably has a maximum value in the range of 800 nm to 2,500 nm (preferably 800 nm to 1,800 nm) from the viewpoint of increasing the efficiency of heat ray reflectance. .
  • the visible light transmittance of the silver particle-containing film of the present invention is preferably 60% or more, more preferably 65% or more, and particularly preferably 70% or more. When the visible light transmittance is less than 60%, for example, when used as automotive glass or building glass, the outside may be difficult to see.
  • the solar reflectance of the silver particle-containing film of the present invention is preferably 13% or more, more preferably 17% or more, and particularly preferably 20% or more.
  • the silver particle-containing film of the present invention preferably has a wavelength band having a reflectance of 25% or more over a wavelength band of 800 nm to 2,500 nm over 800 nm, over 1000 nm, more preferably over 1200 nm. Is particularly preferred.
  • the ultraviolet transmittance of the silver particle-containing film of the present invention is preferably 5% or less, and more preferably 2% or less. When the ultraviolet transmittance exceeds 5%, the color of the silver nanoparticle layer may change due to ultraviolet rays of sunlight.
  • the haze of the silver particle-containing film of the present invention is preferably 20% or less. When the haze exceeds 20%, it may be unfavorable in terms of safety, for example, when it is used as glass for automobiles or glass for buildings, it becomes difficult to see the outside.
  • the silver particle-containing film of the present invention has a silver tabular grain-containing layer containing tabular silver nanoparticles having an average equivalent-circle diameter of 70 nm to 500 nm, and if necessary, an adhesive layer, an ultraviolet absorbing layer, a base layer
  • an adhesive layer if necessary, an adhesive layer, an ultraviolet absorbing layer, a base layer
  • the silver particle-containing film of the present invention preferably has a polymer layer 1 as a substrate.
  • membrane of this invention is demonstrated.
  • Silver tabular grain-containing layer The silver tabular grain-containing layer is not particularly limited except that it contains tabular silver nanoparticles having an average equivalent-circle diameter of 70 nm to 500 nm, and can be appropriately selected according to the purpose.
  • the silver tabular grain-containing layer when the thickness of the silver tabular grain-containing layer is d, 80% or more of the hexagonal silver nanoparticles are d / 2 from the surface of the silver tabular grain-containing layer. It is preferable that it exists in the range.
  • the present invention is not limited to any theory, and the silver particle-containing film of the present invention is not limited to the following production method, but a specific polymer (preferably latex) is preferably used when producing the silver tabular grain-containing layer. ) Can be segregated on one surface of the silver tabular grain-containing layer.
  • the silver nanoparticles are not particularly limited as long as they have a flat plate shape with an average equivalent circle diameter of 70 nm to 500 nm, and can be appropriately selected according to the purpose.
  • one surface of the said silver tabular grain content layer is a flat plane.
  • membrane of this invention has a base material, it is preferable that it is a substantially horizontal surface with the surface of a base material.
  • the silver particle-containing film may or may not have the base material, and may or may not have a temporary support.
  • the shape of the flat silver nanoparticles is a particle composed of two main planes (see FIGS. 1A and 1B), and the shape in the plane can be appropriately selected according to the purpose. Examples include a shape, a circular shape, and a triangular shape. Among these, in terms of high visible light transmittance, it is more preferably a hexagonal or more polygonal shape to a circular shape, particularly preferably a hexagonal shape or a circular shape, and more preferably a hexagonal shape. .
  • the hexagonal shape means a shape in which the number of sides having a length of 20% or more of the average equivalent circle diameter of tabular silver nanoparticles is 6 per silver tabular grain. .
  • the hexagonal silver nanoparticles are not particularly limited as long as they are hexagonal when the silver nanoparticles are observed from above the main plane with a transmission electron microscope (TEM) or SEM, and are appropriately selected according to the purpose.
  • the hexagonal corner may be acute or dull, but the corner is preferably dull in that the absorption in the visible light region can be reduced.
  • the corner is preferably dull in that the absorption in the visible light region can be reduced.
  • hexagonal tabular silver nanoparticles are preferably 60% by number or more, and 65% by number or more based on the total number of silver nanoparticles. Is more preferable, and 70% by number or more is more preferable. If the ratio of the hexagonal tabular silver nanoparticles is less than 60% by number, the visible light transmittance may be lowered.
  • the method for synthesizing the tabular silver nanoparticles is not particularly limited as long as it can synthesize tabular silver nanoparticles having a specific size (preferably hexagonal shape), and is appropriately selected depending on the purpose.
  • Examples thereof include liquid phase methods such as chemical reduction method, photochemical reduction method, and electrochemical reduction method.
  • a liquid phase method such as a chemical reduction method or a photochemical reduction method is particularly preferable in terms of shape and size controllability.
  • hexagonal to triangular tabular silver nanoparticles After synthesizing hexagonal to triangular tabular silver nanoparticles, for example, by performing etching treatment with a dissolved species that dissolves silver such as nitric acid and sodium sulfite, aging treatment by heating, etc., hexagonal to triangular shape Hexagonal to circular tabular silver nanoparticles may be obtained by dulling the corners of the silver nanoparticles.
  • the silver nanoparticles may be grown in a tabular form.
  • the method for controlling the color tone of the silver particle-containing film is not particularly limited, and can be achieved by, for example, synthesizing tabular silver nanoparticles under specific conditions during the production conditions of the silver particle-containing film. Can do.
  • the silver nitrate addition time during the preparation of the silver nanoparticle dispersion from the seed crystal solution if the scale during the preparation of the silver nanoparticle dispersion is the same condition, the silver nitrate addition rate In a specific range, or by adjusting the pH of the silver nanoparticle dispersion after addition of the silver sulfite precipitate mixture.
  • it is preferably produced by the method for producing a silver particle-containing film of the present invention.
  • the method includes a step of preparing a silver nanoparticle dispersion from a silver seed crystal solution, and a silver nitrate-containing solution is added to the silver seed crystal solution for 5 minutes or more, preferably 7 minutes or more, more preferably 15 minutes or more.
  • the solution containing silver sulfite is added to the silver seed crystal solution after the addition of the silver nitrate-containing solution, and the pH of the silver nanoparticle dispersion after the addition of the solution containing silver sulfite is 8.0 or less (preferably 3
  • the silver particle-containing film of the present invention is not limited by the production method described above, and those produced by other methods are also included in the silver particle-containing film of the present invention.
  • the tabular silver nanoparticles may be subjected to further treatment in order to impart desired characteristics.
  • the further treatment is not particularly limited and may be appropriately selected depending on the purpose.
  • the formation of a high refractive index shell layer the addition of various additives such as a dispersant and an antioxidant may be included. Can be mentioned.
  • the flat silver nanoparticles may be coated with a high refractive index material having high visible light region transparency in order to further enhance the visible light region transparency.
  • a high refractive index material is not particularly limited and may be appropriately selected depending on the purpose, for example, TiO x, BaTiO 3, ZnO, etc. SnO 2, ZrO 2, NbO x and the like.
  • an appropriate SiO 2 or polymer shell layer is formed. Further, the metal oxide layer may be formed on the shell layer.
  • TiO x is used as the material for the high refractive index metal oxide layer, since TiO x has photocatalytic activity, there is a concern that the matrix in which the silver nanoparticles are dispersed may be deteriorated. After forming the TiO x layer on the nanoparticles, an SiO 2 layer may be appropriately formed.
  • the tabular silver nanoparticles may contain an antioxidant such as mercaptotetrazole or ascorbic acid in order to prevent oxidation of metals such as silver constituting the tabular silver nanoparticles. It may be adsorbed.
  • an oxidation sacrificial layer such as Ni may be formed on the surface of the silver nanoparticles. Further, it may be covered with a metal oxide film such as SiO 2 for the purpose of blocking oxygen.
  • the tabular silver nanoparticles are, for example, a quaternary ammonium salt, a low molecular weight dispersant containing at least one of N element, S element, and P element such as amines, and high molecular weight dispersion. You may add dispersing agents, such as an agent.
  • the hexagonal tabular silver nanoparticles are such that the main plane is one surface of the silver tabular particle-containing layer (if the silver particle-containing film has a substrate, the substrate surface ) Is preferably in the range of 0 ° to ⁇ 30 ° on average, more preferably in the range of 0 ° to ⁇ 20 ° on average, more preferably 0 ° to ⁇ 10 on average. It is particularly preferable that the orientation is in the range of °.
  • the presence state of the silver nanoparticles is not particularly limited and may be appropriately selected according to the purpose. However, the silver nanoparticles are preferably arranged as shown in FIGS. 2D and 2E described later.
  • FIGS. 2A to 2E are schematic cross-sectional views showing the existence state of the silver tabular grain-containing layer containing silver nanoparticles in the silver particle-containing film of the present invention.
  • FIG. 2A is a diagram for explaining the angle ( ⁇ ⁇ ) formed by the surface plane of the silver particle-containing film (the plane of the substrate 1 when a substrate is included) and the plane of the silver nanoparticles 3.
  • FIG. 2B shows the existence region in the depth direction of the silver particle-containing film of the silver tabular grain-containing layer 2.
  • 2C, FIG. 2D, and FIG. 2E show the presence state of the tabular silver nanoparticles 3 in the silver tabular grain-containing layer 2.
  • FIG. 2A is a diagram for explaining the angle ( ⁇ ⁇ ) formed by the surface plane of the silver particle-containing film (the plane of the substrate 1 when a substrate is included) and the plane of the silver nanoparticles 3.
  • FIG. 2B shows the existence region in the depth direction of the silver particle-containing film of the silver tab
  • the angle ( ⁇ ⁇ ) formed between the surface of the substrate 1 and the like and the main plane of the tabular silver nanoparticles 3 or an extension line of the main plane corresponds to a predetermined range in the plane orientation. That is, the plane orientation refers to a state in which the tilt angle ( ⁇ ⁇ ) shown in FIG. 2A is small when the cross section of the silver particle-containing film is observed.
  • FIG. A state where the main plane of the particle 3 is in contact that is, a state where ⁇ is 0 ° is shown.
  • the main plane of the tabular silver nanoparticles is plane-oriented with respect to one surface of the silver tabular grain-containing layer (or the base material surface when the silver particle-containing film has a substrate)
  • it can be appropriately selected according to the purpose.
  • an appropriate cross-section slice is prepared, and a silver tabular grain-containing layer in this slice (if the silver particle-containing film has a substrate, the substrate ) And plate-like silver nanoparticles may be observed and evaluated.
  • a cross-section sample or a cross-section sample of the silver particle-containing film is prepared from the silver particle-containing film using a microtome or a focused ion beam (FIB), and this is used for various microscopes (for example, field emission scanning electrons). And a method of evaluating from an image obtained by observation using a microscope (FE-SEM, etc.).
  • FIB focused ion beam
  • the cross-section sample or the cross-section section is obtained by cutting a sample frozen in liquid nitrogen by a diamond cutter mounted on a microtome. A sample may be made.
  • membrane does not swell with water, you may produce the said cross-section sample or a cross-section slice sample.
  • the sample is flat with respect to one surface of the silver tabular grain-containing layer in the sample (or the base material surface when the silver particle-containing film has a base).
  • the sample can confirm whether or not the main plane of the silver nanoparticles is plane-oriented, and can be appropriately selected according to the purpose.
  • FE-SEM FE-SEM
  • TEM optical microscope
  • the observations used are mentioned.
  • observation may be performed by FE-SEM
  • observation may be performed by TEM.
  • TEM observation may be performed by TEM.
  • Variation coefficient of average particle size (average equivalent circle diameter) and average particle size (average equivalent circle diameter) particle size distribution The flat silver nanoparticles have an average particle diameter (average equivalent circle diameter) of 70 nm to 500 nm, preferably 100 nm to 400 nm.
  • average particle diameter (average equivalent circle diameter) is less than 70 nm, the contribution of the absorption of the tabular silver nanoparticles becomes larger than the reflection, so that sufficient heat ray reflectivity may not be obtained, which exceeds 500 nm. And haze (scattering) becomes large, and transparency may be impaired.
  • the average particle diameter is a main plane diameter (maximum length) of 200 tabular silver nanoparticles arbitrarily selected from images obtained by observing particles with a TEM. Mean value.
  • Two or more kinds of tabular silver nanoparticles having different average particle diameters can be contained in the silver tabular grain-containing layer.
  • the average particle diameter of the tabular silver nanoparticles ( The average circle equivalent diameter) peak may have two or more.
  • the silver particle-containing film of the present invention preferably has a coefficient of variation of 13% or more in the particle size distribution of tabular silver nanoparticles.
  • the coefficient of variation is 13% or more, the reflection wavelength region of heat rays in the silver particle-containing film can be broadened, and infrared light can be reflected over a wide band, which is preferable.
  • the upper limit of the coefficient of variation in the particle size distribution of the tabular silver nanoparticles is preferably 200% or less, more preferably 150% or less, and particularly preferably 100% or less.
  • the coefficient of variation in the particle size distribution of the silver nanoparticles is plotted, for example, by plotting the particle size distribution range of the 200 silver nanoparticles used for calculating the average value obtained as described above, and the standard deviation of the particle size distribution is It is the value (%) obtained by dividing the average value (average particle diameter (average equivalent circle diameter)) of the main plane diameter (maximum length) obtained as described above.
  • the aspect ratio of the tabular silver nanoparticles is not particularly limited and may be appropriately selected depending on the intended purpose. However, the reflectance in the infrared light region having a wavelength of 800 nm to 2,500 nm is increased. 8 to 40 are preferable, and 10 to 35 are more preferable. When the aspect ratio is less than 8, the reflection wavelength becomes smaller than 800 nm, and when it exceeds 40, the reflection wavelength becomes longer than 1,800 nm and sufficient heat ray reflectivity may not be obtained.
  • the aspect ratio means a value obtained by dividing the average particle diameter (average equivalent circle diameter) of tabular silver nanoparticles by the average particle thickness of tabular silver nanoparticles.
  • the average particle thickness corresponds to the distance between main planes of tabular silver nanoparticles, for example, as shown in FIGS. 1A and 1B, and was cut by an atomic force microscope (AFM) or a focused ion beam (FIB). It can be measured by observing the cross section of the particle by FE-SEM or TEM.
  • the method for measuring the average particle thickness is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a particle dispersion containing silver nanoparticles is dropped on a glass substrate and dried to obtain particles 1 The method of measuring the thickness of an individual etc. is mentioned.
  • the thickness of the flat silver nanoparticles is preferably 5 to 20 nm.
  • the silver particle-containing film of the present invention it is preferable that 80% by number or more of the hexagonal tabular silver nanoparticles are present in a range of d / 2 from the surface of the silver tabular particle-containing layer, d / 3 More preferably, 60% by number or more of the hexagonal tabular silver nanoparticles are exposed on one surface of the silver tabular grain-containing layer. That the tabular silver nanoparticles are present in the range of d / 2 from the surface of the silver tabular grain-containing layer means that at least a part of the tabular silver nanoparticles is in the range of d / 2 from the surface of the silver tabular grain-containing layer. Means included.
  • FIG. 2E means that only a part of the thickness direction of each silver nanoparticle is buried in the silver tabular grain-containing layer, and each silver nanoparticle is stacked on the surface of the silver tabular grain-containing layer. Do not mean.
  • the tabular silver nanoparticles are exposed on one surface of the silver tabular grain-containing layer, a part of one surface of the tabular silver nanoparticles is from the surface of the silver tabular grain-containing layer. Also means that it protrudes.
  • the presence distribution of silver nanoparticles in the silver tabular grain-containing layer can be measured, for example, from an image obtained by SEM observation of a cross-sectional sample of the silver particle-containing film.
  • the plasmon resonance wavelength ⁇ of the metal constituting the tabular silver nanoparticles in the silver tabular grain-containing layer is not particularly limited and can be appropriately selected according to the purpose, but in terms of imparting heat ray reflection performance,
  • the thickness is preferably 400 nm to 2,500 nm, and more preferably 700 nm to 2,500 nm from the viewpoint of imparting visible light transmittance.
  • the silver particle-containing film of the present invention preferably contains a polymer as a medium in the silver tabular grain-containing layer.
  • a polymer as a medium in the silver tabular grain-containing layer.
  • the polymer include polyvinyl acetal resin, polyvinyl alcohol resin, polyvinyl butyral resin, polyacrylate resin, polymethyl methacrylate resin, polycarbonate resin, polyvinyl chloride resin, (saturated) polyester resin, polyurethane resin, gelatin resin and cellulose.
  • polymers such as natural polymers.
  • the main polymer of the polymer is preferably a polyvinyl alcohol resin, a polyvinyl butyral resin, a polyvinyl chloride resin, a (saturated) polyester resin, a polyurethane resin, and preferably the polyester resin and the polyurethane resin. More preferably, 80% by number or more of hexagonal or circular silver nanoparticles are easily present in the range of d / 2 from the surface of the silver tabular grain-containing layer, and the polyester resin contains the silver particles of the present invention. This is particularly preferable from the viewpoint of further improving the cross-cut adhesion of the film.
  • the main polymer of the said polymer contained in the said silver tabular grain content layer means the polymer component which occupies 50 mass% or more of the polymer contained in the said silver tabular grain content layer.
  • the content of the polyester resin with respect to the tabular silver nanoparticles contained in the silver tabular particle-containing layer is preferably 1 to 10,000% by mass, and preferably 10 to 1000% by mass. More preferred is 20 to 500% by mass.
  • the refractive index n of the medium is preferably 1.4 to 1.7.
  • the thickness of the hexagonal tabular silver nanoparticles when the thickness of the hexagonal tabular silver nanoparticles is a, 80% by number or more of the hexagonal silver nanoparticles have a thickness of a / 10 or more.
  • the polymer is covered with a / 10 to 10a in the thickness direction, more preferably the polymer is covered with a / 8 to 4a, and particularly preferably a / 8 to 4a is covered with the polymer.
  • the silver particle-containing film of the present invention is preferably in the embodiment of FIG. 2D rather than the embodiment of FIG. 2E.
  • the silver nanoparticles are arranged in the form of a silver tabular grain-containing layer containing tabular silver nanoparticles, as shown in FIGS. 2A to 2E.
  • the silver tabular grain-containing layer may be composed of a single layer as shown in FIGS. 2A to 2E, or may be composed of a plurality of silver tabular grain-containing layers. When comprised with a several silver tabular grain content layer, it becomes possible to provide the shielding performance according to the wavelength range which wants to provide thermal insulation performance.
  • the silver particle-containing film of the present invention contains at least the outermost silver tabular grain-containing layer in the outermost silver tabular grain-containing layer.
  • the thickness of the layer is d ′, 80% by number or more of the hexagonal to circular tabular silver nanoparticles are in the range of d ′ / 2 from the surface of the outermost silver tabular grain-containing layer. It is preferable to do.
  • Thickness of silver tabular grain containing layer The thickness of the silver tabular grain-containing layer is preferably 10 to 160 nm, and more preferably 20 to 80 nm.
  • the thickness d of the silver tabular grain-containing layer is preferably a to 10a, more preferably 2a to 8a, where a is the thickness of the hexagonal to circular tabular silver nanoparticles. .
  • the thickness of each layer of the silver tabular grain-containing layer can be measured, for example, from an image obtained by SEM observation of a cross-sectional sample of the silver particle-containing film. Further, even when other layers such as an overcoat layer described later are provided on the silver tabular grain-containing layer of the silver particle-containing film, the boundary between the other layer and the silver tabular grain-containing layer is the same method. The thickness d of the silver tabular grain-containing layer can be determined. In addition, when coating on the said silver tabular grain content layer using the same kind of polymer as the polymer contained in the said silver tabular grain content layer, it is usually with the said silver tabular grain content layer by the image observed by SEM. The boundary can be discriminated, and the thickness d of the silver tabular grain-containing layer can be determined.
  • the silver particle-containing film of the present invention preferably has a base material.
  • the silver particle-containing film has a substrate on the surface opposite to the surface of the silver tabular particle-containing layer on which 60% by number or more of the hexagonal tabular silver nanoparticles are unevenly distributed. Is preferred.
  • the substrate is not particularly limited as long as it is an optically transparent substrate, and can be appropriately selected according to the purpose.
  • the substrate has a visible light transmittance of 70% or more, preferably 80% or more. And those with high transmittance in the near infrared region.
  • the shape include a flat plate shape, and the structure may be a single layer structure or a laminated structure, and the size may be the size of the silver particle-containing film. It can be appropriately selected depending on the size.
  • the material of the base material used in the silver particle-containing film of the present invention is not particularly limited, but is preferably a polymer film.
  • the polymer film is appropriately selected from various transparent plastic films depending on the situation. You can choose.
  • the transparent plastic film include polyolefin resins such as polyethylene, polypropylene, poly-4-methylpentene-1 and polybutene-1, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate resins, and polyvinyl chloride.
  • Polyethylene terephthalate film is particularly preferable.
  • the thickness of the base film is not particularly limited and can be appropriately selected depending on the purpose of use of the solar shading film. Usually, the thickness is about 10 ⁇ m to 500 ⁇ m, preferably 12 ⁇ m to 300 ⁇ m, more preferably 16 ⁇ m to 125 ⁇ m. preferable.
  • the silver particle-containing film of the present invention preferably has an adhesive layer.
  • the adhesive layer may include an ultraviolet absorber.
  • the material that can be used for forming the adhesive layer is not particularly limited and may be appropriately selected depending on the intended purpose.
  • An adhesive layer made of these materials can be formed by coating.
  • an antistatic agent, a lubricant, an antiblocking agent and the like may be added to the adhesive layer.
  • the thickness of the adhesive layer is preferably 0.1 ⁇ m to 30 ⁇ m.
  • the adhesive layer is preferably formed by coating.
  • it can be laminated on the surface of the lower layer such as the base material, the metal particle-containing layer, or the ultraviolet absorbing layer.
  • the coating method at this time A well-known method can be used.
  • a film in which the pressure-sensitive adhesive is previously coated and dried on the release film is prepared, and the film is left in a dry state by laminating the pressure-sensitive adhesive surface of the film and the heat ray shielding material surface of the present invention. It is possible to laminate an adhesive layer.
  • the laminating method at this time is not particularly limited, and a known method can be used.
  • Hard coat layer In order to add scratch resistance, it is also preferable to include a hard coat layer having hard coat properties.
  • the hard coat layer can contain metal oxide particles.
  • the kind and formation method can be selected suitably according to the objective, for example, acrylic resin, silicone resin, melamine resin, urethane resin, alkyd resin And thermosetting or photocurable resins such as fluorine-based resins.
  • the thickness of the hard coat layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 ⁇ m to 50 ⁇ m.
  • the hard coat layer may contain the metal oxide particles.
  • the silver particle-containing film of the present invention has a hexagonal shape to a circular shape in order to prevent oxidation and sulfidation of tabular silver nanoparticles due to mass transfer and to impart scratch resistance. You may have the overcoat layer closely_contact
  • an overcoat layer may be provided for prevention or the like.
  • the overcoat layer may contain an ultraviolet absorber.
  • the overcoat layer is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the overcoat layer contains a binder, a matting agent, and a surfactant, and further contains other components as necessary. It becomes.
  • the binder is not particularly limited and may be appropriately selected depending on the purpose.
  • the thickness of the overcoat layer is preferably 0.01 ⁇ m to 1,000 ⁇ m, more preferably 0.02 ⁇ m to 500 ⁇ m, particularly preferably 0.1 to 10 ⁇ m, and particularly preferably 0.2 to 5 ⁇ m.
  • the layer containing the ultraviolet absorber can be appropriately selected according to the purpose in addition to the overcoat layer, and may be an adhesive layer, or between the adhesive layer and the silver tabular grain-containing layer. It may be a layer. In any case, the ultraviolet absorber is preferably added to a layer disposed on the side irradiated with sunlight with respect to the silver tabular grain-containing layer.
  • the ultraviolet absorber is not particularly limited and may be appropriately selected depending on the purpose.
  • a benzophenone ultraviolet absorber a benzotriazole ultraviolet absorber, a triazine ultraviolet absorber, a salicylate ultraviolet absorber, Examples include cyanoacrylate ultraviolet absorbers. These may be used individually by 1 type and may use 2 or more types together.
  • the benzophenone-based ultraviolet absorber is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 2,4droxy-4-methoxy-5-sulfobenzophenone.
  • the benzotriazole ultraviolet absorber is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the triazine ultraviolet absorber is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include mono (hydroxyphenyl) triazine compounds, bis (hydroxyphenyl) triazine compounds, and tris (hydroxyphenyl) triazine compounds. Etc. Examples of the mono (hydroxyphenyl) triazine compound include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethyl).
  • Phenyl) -1,3,5-triazine 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) ) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy- 4-isooctyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis ( 2,4-dimethylphenyl) -1,3,5-triazine, etc.
  • Examples of the bis (hydroxyphenyl) triazine compound include 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2 , 4-Bis (2-hydroxy-3-methyl-4-propyloxyphenyl) -6- (4-methylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl) -4-hexyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2-phenyl-4,6-bis [2-hydroxy-4- [3- (methoxyheptaethoxy ) -2-hydroxypropyloxy] phenyl] -1,3,5-triazine and the like.
  • tris (hydroxyphenyl) triazine compound examples include 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2 , 4,6-Tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropyloxy) ) Phenyl] -1,3,5-triazine, 2,4-bis [2-hydroxy-4- [1- (isooctyloxycarbonyl) ethoxy] phenyl] -6- (2,4-dihydroxyphenyl) -1 , 3,5-triazine, 2,4,6-tris [2-hydroxy-4- [1- (isooctyloxycarbonyl) ethoxy] phenyl] -1,3,5-triazine, 2,4-bis [2 -Hydroxy-4
  • the salicylate-based ultraviolet absorber is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, Examples include 2-ethylhexyl salicylate.
  • the cyanoacrylate-based ultraviolet absorber is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the binder is not particularly limited and may be appropriately selected depending on the intended purpose, but preferably has higher visible light transparency and higher solar transparency, and examples thereof include acrylic resin, polyvinyl butyral, and polyvinyl alcohol. .
  • the ultraviolet absorbing layer formed between the heat ray source and the silver nanoparticles is absorbed in the region of 450 nm to 1,500 nm. It is preferable to select a material that does not have a thickness, or to reduce the thickness of the ultraviolet absorbing layer.
  • the ultraviolet transmittance is preferably 5% or less, and more preferably 2% or less. When the ultraviolet transmittance exceeds 5%, the color of the silver nanoparticle layer may change due to ultraviolet rays of sunlight.
  • the silver particle-containing film of the present invention preferably contains at least one metal oxide particle in order to absorb long-wave infrared light from the viewpoint of the balance between heat ray shielding and manufacturing cost.
  • the layer containing the metal oxide particles is the silver flat plate on which the hexagonal to circular flat plate silver nanoparticles of the silver flat plate particle-containing layer are exposed. It is preferable to have on the surface side opposite to the surface of the particle-containing layer.
  • the overcoat layer preferably contains metal oxide particles.
  • the said metal oxide particle content layer may be laminated
  • the silver particle-containing film of the present invention when the silver particle-containing film of the present invention is arranged so that the silver nanoparticle-containing layer is on the incident direction side of heat rays such as sunlight, a part of the heat rays in the silver nanoparticle-containing layer After reflecting (or all), the overcoat layer will absorb part of the heat rays, and it will not be absorbed by the metal oxide-containing layer, but will be caused by the heat rays that have passed through the silver particle-containing film.
  • the amount of heat directly received inside the film and the amount of heat absorbed by the metal oxide-containing layer of the silver particle-containing film and indirectly transmitted to the inside of the silver particle-containing film can be reduced.
  • a tin dope indium oxide (henceforth "ITO"), a tin dope antimony oxide (henceforth).
  • ATO tin dope indium oxide
  • CWO tungsten oxide
  • LaB 6 lanthanum hexaboride
  • ITO infrared rays of 1,200 nm or more are shielded by 90% or more and the visible light transmittance is 90% or more.
  • the volume average particle size of the primary particles of the metal oxide particles is preferably 0.1 ⁇ m or less in order not to reduce the visible light transmittance.
  • a shape of the said metal oxide particle According to the objective, it can select suitably, For example, spherical shape, needle shape, plate shape, etc. are mentioned.
  • the content of the metal oxide particles in the metal oxide particle-containing layer is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 0.1 g / m 2 to 20 g / m 2 , 0.5 g / m 2 to 10 g / m 2 is more preferable, and 1.0 g / m 2 to 4.0 g / m 2 is more preferable. If the content is less than 0.1 g / m 2 , the amount of solar radiation felt on the skin may increase, and if it exceeds 20 g / m 2 , the visible light transmittance may deteriorate.
  • the content of the metal oxide particles in the metal oxide particle-containing layer is, for example, from the observation of the super foil section TEM image and surface SEM image of the heat ray shielding layer, and the number of metal oxide particles in a certain area and It can be calculated by measuring the average particle diameter and dividing the mass (g) calculated based on the number and average particle diameter and the specific gravity of the metal oxide particles by the constant area (m 2 ). .
  • metal oxide fine particles in a certain area of the metal oxide particle-containing layer are eluted in methanol, and the mass (g) of the metal oxide fine particles measured by fluorescent X-ray measurement is divided by the constant area (m 2 ). This can also be calculated.
  • distribution which has the said silver nanoparticle on the surface of lower layers, such as the said base material examples include a method in which the liquid is applied by a dip coater, a die coater, a slit coater, a bar coater, a gravure coater, or the like, and a method in which the liquid is aligned by a method such as an LB film method, a self-assembly method, or a spray coating method.
  • the composition of the silver tabular particle-containing layer used in the examples described later is used, and the hexagonal or circular tabular silver nanoparticles 80 are added by adding latex or the like. It is preferable that several% or more exist in a range of d / 2 from the surface of the silver tabular grain-containing layer. More preferably, 80% by number or more of the hexagonal or circular tabular silver nanoparticles are present in a range of d / 3 from the surface of the silver tabular grain-containing layer.
  • the amount of the latex added is not particularly limited.
  • the method for controlling the coefficient of variation of the average particle diameter (average equivalent circle diameter) of tabular silver nanoparticles in the silver tabular grain-containing layer is not particularly limited, and the average particle diameter (average equivalent circle diameter)
  • the shape of the flat silver nanoparticles contained in the dispersion containing silver nanoparticles may be controlled so that the coefficient of variation is large, and the silver nanoparticles with a small coefficient of variation of the average particle diameter (average equivalent circle diameter) You may control by mixing 2 or more types of dispersion liquid which has.
  • the variation coefficient of the average grain size (average equivalent circle diameter) is Prepare two or more kinds of small silver nanoparticle dispersions (average equivalent circle equivalent diameters) so that the average particle diameter (average equivalent circle diameter) of tabular silver nanoparticles has two or more peaks. It is preferable to form a silver tabular grain-containing layer. Such a configuration is preferable because infrared light can be easily shielded over a wide band.
  • the silver tabular grain-containing layer contains one kind of tabular silver nanoparticles having an average grain diameter (average equivalent circle diameter)
  • the coefficient of variation of the average grain diameter (average equivalent circle diameter) is It is preferable to prepare such that the silver tabular grain-containing layer is prepared by increasing the average equivalent circle diameter (not so uniform). Such a configuration is preferable because infrared light can be easily shielded over a wide band.
  • the heat ray shielding material of the present invention When using the heat ray shielding material of the present invention to provide functionality to the existing window glass, it is preferable to laminate an adhesive and attach it to the indoor side of the window glass. In that case, it is preferable that the infrared reflection layer is installed on the sunlight side as much as possible because it can reflect the infrared rays to be incident on the room in advance. From this viewpoint, the metal particle-containing layer is installed on the sunlight incidence side. It is preferable to laminate an adhesive layer on the substrate. Specifically, an adhesive layer is provided on a metal particle-containing layer or a functional layer such as an overcoat layer provided on the metal particle-containing layer, and is bonded to the window glass via the adhesive layer. Is preferred.
  • a heat ray shielding material provided by coating or laminating the adhesive layer, and pre-surfactant (mainly on the surface of the window glass and the adhesion layer surface of the heat ray shielding material)
  • pre-surfactant mainly on the surface of the window glass and the adhesion layer surface of the heat ray shielding material
  • the surface of the window glass is swept away from the center of the glass toward the edge using a squeegee or the like to leave moisture between the window glass and the heat ray shielding material.
  • the heat ray shielding material is fixed to the surface. In this way, it is possible to install the heat ray shielding material on the window glass.
  • laminated glass body using heat ray shielding material For the production of the laminated glass body, two glass plates, two polyvinyl butyral interlayer films (PVB sheet) for laminated glass, and the heat ray shielding material are prepared, and the glass plate (first sheet), PVB sheet (1 Sheet), heat ray shielding material, PVB sheet (second sheet), glass plate (second sheet).
  • This laminated body is preliminarily pressure-bonded at 95 ° C. for 30 minutes under vacuum, and then pressure-bonded with heating under conditions of 1.3 MPa and 120 ° C. in an autoflavor to obtain a laminated glass to which a heat ray shielding material is applied. be able to.
  • the silver particle-containing film of the present invention can be applied to various fields by taking advantage of the characteristics of silver.
  • heat ray shielding materials, antibacterial materials, transparent conductive materials, antistatic materials, packaging materials, heat dissipation materials From the viewpoint of utilizing the natural color tone that is a feature of the silver particle-containing film of the present invention, it can be preferably used for a heat ray shielding material, a transparent conductive material, an antistatic material, and the like.
  • the silver particle-containing film of the present invention can be preferably used for a heat ray shielding material used for selectively reflecting or absorbing heat rays (near infrared rays).
  • films for vehicles, films for building materials, agriculture Films for use For example, films for vehicles, films for building materials, agriculture Films for use.
  • heat rays mean near infrared rays (780 nm to 1,800 nm) contained in sunlight by about 50%.
  • Example 1 ⁇ Synthesis of hexagonal tabular silver tabular grains> (Preparation of seed crystal solution) 2.5 ml of a 0.5 g / l polystyrene sulfonic acid aqueous solution was added to 50 mL of a 2.5 mM sodium citrate aqueous solution and heated to 35 ° C. To this solution, 3 ml of 10 mM sodium borohydride aqueous solution was added, and 50 ml of 0.5 mM silver nitrate aqueous solution was added with stirring at 20 ml / min. This solution was stirred for 30 minutes to prepare a seed crystal solution.
  • Table 1 below shows the silver nitrate addition rate and the pH of the silver nanoparticle dispersion immediately after the addition of the silver sulfite precipitate mixture during the preparation of the silver nanoparticle dispersion from the seed crystal solution.
  • 200 mL of the silver nanoparticle dispersion A1 was extracted, and centrifuged at 7000 rpm for 60 minutes with a centrifuge (H200-N manufactured by Kokusan Co., Ltd.) to precipitate silver nanoparticles.
  • the shape uniformity of silver nanoparticles is the shape of 200 particles arbitrarily extracted from the observed SEM image, and hexagonal silver tabular grains, circular silver tabular grains, and irregular shaped grains such as teardrops. Image analysis was performed while distinguishing them from each other, and shapes containing 60% by number or more were obtained.
  • the silver tabular grain dispersion B1 was dropped on a silicon substrate and dried, and the individual thickness of the silver tabular grains was measured by the FIB-TEM method. Five silver tabular grains in the silver tabular grain dispersion B were measured, and the average thickness was 16 nm. As a result of calculating the average thickness for other examples and comparative examples by the same method, it was confirmed that the average thickness was 8 nm to 16 nm.
  • This coating liquid is applied to the wire coating bar No. 14 (RDS Webster NY Co., Ltd.) was applied onto a 50 ⁇ m thick PET film (A4300, manufactured by Toyobo Co., Ltd.), dried, and a hexagonal flat plate on the surface.
  • a film having a silver tabular grain-containing layer having a dry thickness of 100 nm to which silver tabular grains were fixed was obtained.
  • a silver particle-containing film having a tabular silver particle-containing layer was produced.
  • Example 2 A heat ray shielding material of Example 2 was obtained in the same manner as Example 1 except that 79.6 ml of 0.5 mM silver nitrate aqueous solution was added with stirring at 5 ml / min (addition time 15.9 minutes).
  • Example 3 A heat ray shielding material of Example 3 was obtained in the same manner as in Example 1 except that 79.6 ml of 0.5 mM silver nitrate aqueous solution was added with stirring at 10 ml / min (addition time: 8.0 minutes).
  • Example 4 After adding the silver sulfite precipitate mixed solution, immediately after adding 0.2 M NaOH aqueous solution, the pH of the silver nanoparticle dispersion was adjusted to 5.9. A shielding material was obtained.
  • Example 5 After adding the silver sulfite precipitate mixed solution, immediately after adding 0.2M NaOH aqueous solution, the pH of the silver nanoparticle dispersion was adjusted to 6.5, the heat ray of Example 5 A shielding material was obtained.
  • Example 6 After adding the silver sulfite precipitate mixed solution, immediately after adding 0.2 M NaOH aqueous solution, the pH of the silver nanoparticle dispersion liquid was set to 7.1. A shielding material was obtained.
  • Example 7 To 12.5 L of pure water, 995 mL of a 1% by mass aqueous sodium citrate solution and 678 mL of an 8 g / L aqueous sodium polystyrene sulfonate solution were added and heated to 35 ° C. To this solution, 40.7 mL of a 2.3 mass% sodium borohydride aqueous solution was added, and 10.8 L of a 0.5 mM aqueous silver nitrate solution was added with stirring. After stirring this solution for 20 minutes, 995 mL of 1 mass% sodium citrate aqueous solution, 1.34 L of 10 mM ascorbic acid aqueous solution and 12.5 L of pure water were added.
  • Ag hexagonal tabular grains having an average equivalent circle diameter of 125 nm.
  • a coating solution C2 for a metal particle-containing layer having the composition shown below was prepared using the silver nanoparticle dispersion B2. Moreover, the coating liquid C3 for metal oxide particle content layers of the composition shown below was prepared. The heat ray shielding material was produced by forming and applying these to the equipment. In addition, the solid content concentration in the following preparations was used after appropriately adjusting with pure water or a water-soluble alcohol such as methanol or ethanol.
  • composition of coating liquid C2 for metal particle-containing layer Polyester aqueous solution: Pluscoat Z687 (Saiyo Chemical Co., Ltd., solid concentration 25% by mass) 1.85 parts by mass
  • Crosslinker A Carbodilite V-02-L2 (Nisshinbo Co., Ltd., solid concentration 20% by mass) 1.15 parts by mass
  • Crosslinking agent B Epocross K-2020E (Nippon Shokubai Co., Ltd., solid content concentration 20% by mass) 0.51 parts by mass Surfactant A: F Ripar 8780P Ripar 870P (Lion Corporation, solid content 1% by mass) 0.96 parts by mass
  • Surfactant B Naroacty CL-95 (Manufactured by Sanyo Chemical Industries, Ltd., solid content 1 mass%) 1.18 parts by mass Silver nanoparticle dispersion B1 32.75 parts by mass 1- (m-methylureidophenyl) -5-mercaptotetrazole (Wako Pure Chemical ( Co., Ltd., solid
  • composition of coating liquid O1 for overcoat layer Colloidal silica fine particles: Snowtex XL (Average particle size 40 nm, manufactured by Nissan Chemical Industries, Ltd., solid content 10% by mass) 1.29 parts by mass of colloidal silica fine particles: Aerosil OX-50 (Average particle size 40 nm, manufactured by Nippon Aerosil Co., Ltd., (Preparing an aqueous dispersion having a solid content of 10% by mass) 0.29 parts by mass Acrylic polymer aqueous dispersion: AS563A (Daicel Finechem Co., Ltd., solid content 27.5% by mass) 0.49 parts by mass carnauba wax: cellosol 524 (manufactured by Chukyo Yushi Co., Ltd., solid content 3% by mass) 2.86 parts by weight cross-linking agent: Carbodilite V-02-L2 (Nisshinbo Chemical Co., Ltd., solid concentration 20% by mass) 1.71 parts by mass Surfactant A: Ripar 870
  • composition of coating liquid C3 for the metal oxide particle-containing layer UV-curable ITO coating PI-3 (Mitsubishi Materials Electronics Chemical Co., Ltd.) 25 parts by mass Toluene (Wako Pure Chemical Industries, Ltd.) 75 parts by mass
  • a coating solution C2 for a metal particle-containing layer was applied using a wire bar so that the average thickness after drying was 80 nm. Then, it heated at 130 degreeC for 1 minute, dried and solidified, and formed the metal particle content layer. Next, the overcoat layer coating solution O1 was applied using a wire bar so that the average thickness after drying was 350 nm. Then, it dried and solidified at 130 degreeC and formed the overcoat layer.
  • the coating liquid C3 for the metal oxide particle-containing layer is averaged after drying using a wire bar. It was applied so that the thickness was 1.5 ⁇ m.
  • the metal oxide particle-containing layer was cured by irradiating with ultraviolet rays using a high-pressure mercury lamp. The coating layer was irradiated with ultraviolet rays at 400 mJ / cm 2 .
  • the adhesive layer was provided with the method mentioned later with respect to the obtained heat ray shielding film.
  • the average thickness can be calculated by observing cross sections SEM and TEM of the heat ray shielding film. It selects suitably according to application
  • cross-section processing and cross-section observation were performed by FIB-TEM, and the average value obtained by measuring the thickness of the coating film at 10 points was defined as the film thickness.
  • cross-section processing can be performed by mechanical polishing, ion milling, microtome, or the like.
  • An adhesive was bonded to the surface of the overcoat layer of the obtained heat ray shielding film.
  • PD-S1 manufactured by Panac
  • the obtained heat ray shielding material was used as the heat ray shielding material of Example 7.
  • Example 8 A heat ray shielding material of Example 8 was obtained in the same manner as Example 7 except that 8.1 L of 0.5 mM silver nitrate aqueous solution was added with stirring at 1000 mL / min (addition time 8.1 minutes).
  • Example 9 A heat ray shielding material of Example 9 was produced in the same manner as Example 7 except that 8.1 L of 0.5 mM silver nitrate aqueous solution was added with stirring at 405 mL / min (addition time: 20 minutes).
  • Example 10 After adding the silver sulfite precipitate mixed solution, immediately after adding 0.2 M NaOH aqueous solution, the pH of the silver nanoparticle dispersion liquid was changed to 7.2. A shielding material was obtained.
  • Comparative Example 1 A heat ray shielding material of Comparative Example 1 was obtained in the same manner as in Example 1 except that 79.6 ml of 0.5 mM silver nitrate aqueous solution was added with stirring at 20 ml / min (addition time: 4.0 minutes).
  • Comparative Example 2 A heat ray shielding material of Comparative Example 2 was obtained in the same manner as in Example 1 except that 79.6 ml of 0.5 mM silver nitrate aqueous solution was added with stirring at 50 ml / min (addition time 1.6 minutes).
  • Comparative Example 3 A heat ray shielding material of Comparative Example 3 was obtained in the same manner as in Example 1 except that 79.6 ml of 0.5 mM silver nitrate aqueous solution was added with stirring at 100 ml / min (addition time 0.8 minutes).
  • Comparative Example 7 A heat ray shielding material of Comparative Example 7 was obtained in the same manner as in Example 7 except that 8.1 L of 0.5 mM aqueous silver nitrate solution was added with stirring at 2000 mL / min (addition time 4.1 minutes).
  • Comparative Example 8 A heat ray shielding material of Comparative Example 8 was obtained in the same manner as in Example 7 except that 8.1 L of 0.5 mM aqueous silver nitrate solution was added with stirring at 4000 mL / min (addition time: 2.0 minutes).
  • the visible light transmittance and the shielding coefficient of the heat ray shielding material can be changed depending on the coating amount when forming the metal particle-containing layer.
  • a large number of heat ray shielding materials were prepared by changing the coating amount of the coating liquid C1 for the metal particle-containing layer containing the metal tabular particle-containing liquid of each example and comparative example, The visible light transmittance and the shielding coefficient were calculated by the method.
  • Measuring method of visible light transmittance and shielding coefficient The transmission spectrum and reflection spectrum of the heat ray shielding material prepared in each example and comparative example were measured using an ultraviolet-visible-near infrared spectrometer (manufactured by JASCO Corporation, V-670, using an integrating sphere unit), and JIS R3106, JIS A5759. The visible light transmittance and shielding coefficient were calculated according to the above.
  • the heat ray shielding material of the present invention had a color tone of
  • the heat ray shielding material of each comparative example has a color tone in the L * a * b * color system of
  • the silver particle-containing film of the present invention is excellent in color tone, for example, when a landscape is observed through the silver particle-containing film when pasted on a window or the like as a film for a vehicle or a building material such as a car or a bus. Natural (grayscale) color tone is obtained and eye strain is low. Since the silver particle-containing film of the present invention has the above-mentioned characteristics, it is attached to a window or the like as various members that are required to prevent transmission of heat rays, for example, as a film for a vehicle such as an automobile or a bus or a film for a building material. It can be suitably used as a heat ray shielding material.

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PCT/JP2013/057753 2012-03-27 2013-03-19 Film contenant des particules d'argent et son procédé de fabrication, et matériau de protection contre les rayonnements thermiques Ceased WO2013146447A1 (fr)

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JP2015172687A (ja) * 2014-03-12 2015-10-01 凸版印刷株式会社 光学材料及び光学フィルター
WO2018061678A1 (fr) * 2016-09-29 2018-04-05 富士フイルム株式会社 Structure antireflet

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JP6012527B2 (ja) * 2013-03-27 2016-10-25 富士フイルム株式会社 熱線遮蔽材、合わせガラス用中間膜および合わせガラス
JP6569201B2 (ja) * 2014-09-29 2019-09-04 大日本印刷株式会社 採光具
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JP7125742B2 (ja) * 2018-09-03 2022-08-25 国立大学法人 筑波大学 六角板状銀ナノ粒子の製造方法、六角板状銀ナノ粒子
CN112703434B (zh) 2018-09-14 2022-12-02 Ａｇｃ株式会社 电波透射性基板
JP7389443B2 (ja) * 2018-12-25 2023-11-30 国立研究開発法人産業技術総合研究所 赤外線反射薄膜及びこれを形成するためのインク、並びに赤外線反射薄膜を備える赤外線反射シール及び赤外線反射体、並びに該赤外線反射体を備えた建築物又は乗り物

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JP5970638B2 (ja) * 2014-01-23 2016-08-17 西松建設株式会社 銀ナノ粒子の製造方法
JP2015172687A (ja) * 2014-03-12 2015-10-01 凸版印刷株式会社 光学材料及び光学フィルター
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