WO2012157655A1 - Matériau de protection contre les rayons thermiques, structure stratifiée et verre feuilleté - Google Patents

Matériau de protection contre les rayons thermiques, structure stratifiée et verre feuilleté Download PDF

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Publication number
WO2012157655A1
WO2012157655A1 PCT/JP2012/062449 JP2012062449W WO2012157655A1 WO 2012157655 A1 WO2012157655 A1 WO 2012157655A1 JP 2012062449 W JP2012062449 W JP 2012062449W WO 2012157655 A1 WO2012157655 A1 WO 2012157655A1
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Prior art keywords
heat ray
shielding material
ray shielding
layer
metal particles
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PCT/JP2012/062449
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English (en)
Japanese (ja)
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鎌田　晃
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富士フイルム株式会社
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Publication of WO2012157655A1 publication Critical patent/WO2012157655A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10614—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer comprising particles for purposes other than dyeing
    • B32B17/10633—Infrared radiation absorbing or reflecting agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10788—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing ethylene vinylacetate

Definitions

  • the present invention relates to a heat ray shielding material, a laminated structure using such a heat ray shielding material, and laminated glass, which achieves high light transmittance in the visible light region while improving infrared reflectance over a wide band.
  • heat ray shielding materials for automobile and building windows have been developed as one of the energy-saving measures to reduce carbon dioxide.
  • About heat ray shielding imparting material from the viewpoint of heat ray shielding properties (acquisition rate of solar heat), re-radiation of absorbed light into the room (about 1/3 of the absorbed solar energy is emitted into the room)
  • a heat ray reflective type that does not re-emit in the first place is preferable to a certain heat ray absorbing type. Therefore, various proposals have been made for heat ray reflective heat ray shielding imparting materials.
  • a metal Ag thin film is generally used as a heat ray reflecting material because of its high reflectance, but it reflects not only visible light and heat rays but also radio waves, so that it has visible light permeability and radio wave permeability.
  • Low-E glass for example, manufactured by Asahi Glass Co., Ltd.
  • Ag and ZnO multilayer film is widely used in buildings in order to increase visible light transmittance, but Low-E glass is made of metal Ag on the glass surface. Since the thin film was formed, there existed a subject that radio wave permeability was low.
  • an infrared reflective layer in which 5 to 200 layers of at least two transparent thin layers having different refractive indexes are alternately laminated and a dispersion film of conductive fine particles such as tin-doped indium oxide (ITO), such as a polymer multilayer extruded film
  • a dispersion film of conductive fine particles such as tin-doped indium oxide (ITO)
  • ITO tin-doped indium oxide
  • infrared shielding after 1,100 nm is supplemented with an infrared absorbing layer containing ITO or the like.
  • ITO infrared absorbing layer
  • the infrared shielding filter is attached to a window glass, the temperature rises differently in places where it is not exposed to sunlight, so the glass breaks due to the difference in the expansion coefficient of the film, so-called thermal cracking phenomenon There was a problem that happened. Therefore, there is a demand for a heat ray shielding material having improved infrared reflectance over the entire band and having high light transmittance in the visible light region, and a laminated structure and laminated glass using the heat ray shielding material. It is.
  • the present invention aims to solve the above-mentioned problems and achieve the following objects. That is, the present invention provides a heat ray shielding material, a laminated structure using such a heat ray shielding material, and a laminated glass that achieves high light transmittance in the visible light region while improving infrared reflectance over a wide band.
  • the purpose is to provide.
  • Means for solving the above problems are as follows. That is, ⁇ 1> a metal particle-containing layer containing at least one metal particle; An infrared reflective layer in which 5 to 200 layers of at least two transparent thin layers having different refractive indexes are alternately laminated, and a heat ray shielding material,
  • the metal particles include hexagonal or circular and flat metal particles, A heat ray shielding material, wherein the ratio of flat metal particles to the total number of metal particles contained in the metal particle-containing layer is 60% by number or more.
  • the transparent thin layer is the heat ray shielding material according to ⁇ 1>, which is a layer containing a polymer.
  • ⁇ 3> The heat ray according to any one of ⁇ 1> to ⁇ 2>, wherein the infrared reflective layer is obtained by executing at least one of alternating thin layer extrusion, alternating coating, and alternating thin layer lamination, from the transparent thin layer. It is a shielding material.
  • ⁇ 4> The heat ray shielding material according to any one of ⁇ 1> to ⁇ 3>, wherein the difference between the maximum wavelength of the reflection spectrum of the infrared reflection layer and the maximum wavelength of the reflection spectrum of the metal particle-containing layer is 100 nm or more. is there.
  • the maximum wavelength of the reflection spectrum of the infrared reflection layer is 700 nm to 1,500 nm, the maximum wavelength of the reflection spectrum of the metal particle-containing layer is 900 nm to 2,000 nm, and the shielding coefficient is 0.7 or less.
  • the heat ray shielding material according to any one of ⁇ 1> to ⁇ 5>, wherein the ratio is 50% by number or more.
  • the main plane has a plane orientation in the range of 0 ° to ⁇ 30 ° with respect to one surface of the metal particle-containing layer.
  • the main plane has a plane orientation in the range of 0 ° to ⁇ 30 ° with respect to one surface of the metal particle-containing layer.
  • ⁇ 9> The heat ray shielding material according to any one of ⁇ 1> to ⁇ 8>, wherein a coefficient of variation in particle size distribution of the flat metal particles is 30% or less.
  • the average particle size of the flat metal particles is 70 nm to 500 nm
  • the flat metal particles include at least silver.
  • ⁇ 12> The heat ray shielding material according to any one of ⁇ 1> to ⁇ 11>, wherein the visible light transmittance of the heat ray shielding material is 70% or more.
  • ⁇ 13> The heat ray shielding material according to any one of ⁇ 1> to ⁇ 12>, further including an adhesive layer.
  • ⁇ 14> A laminated structure comprising the heat ray shielding material according to any one of ⁇ 1> to ⁇ 13> and any one of glass and plastic.
  • ⁇ 15> At least one heat ray shielding material according to any one of ⁇ 1> to ⁇ 12>, at least two intermediate layers that sandwich the heat ray shielding material, and at least two glasses that sandwich the intermediate layer It is the laminated glass characterized by including.
  • ⁇ 16> The laminated glass according to ⁇ 15>, wherein the intermediate layer contains at least one of polyvinyl butyral and an ethylene vinyl copolymer.
  • the present invention it is possible to solve the problems of the prior art, achieve the above-mentioned object, improve the infrared reflectance over a wide band, and simultaneously achieve high light transmittance in the visible light region,
  • a laminated structure and a laminated glass using the heat ray shielding material can be provided.
  • FIG. 1A is a schematic perspective view showing an example of the shape of flat metal particles contained in the heat ray shielding material of the present invention, and shows circular and flat metal particles.
  • FIG. 1B is a schematic perspective view showing an example of the shape of flat metal particles contained in the heat ray shielding material of the present invention, and shows hexagonal flat metal particles.
  • FIG. 2A is a schematic cross-sectional view showing the existence state of a metal particle-containing layer containing flat metal particles in the heat ray shielding material of the present invention, and shows the most ideal existence state.
  • FIG. 1A is a schematic perspective view showing an example of the shape of flat metal particles contained in the heat ray shielding material of the present invention, and shows circular and flat metal particles.
  • FIG. 1B is a schematic perspective view showing an example of the shape of flat metal particles contained in the heat ray shielding material of the present invention, and shows hexagonal flat metal particles.
  • FIG. 2A is a schematic cross-sectional view showing the existence state of a metal particle-containing layer
  • FIG. 2B is a schematic cross-sectional view showing the existence state of the metal particle-containing layer containing flat metal particles in the heat ray shielding material of the present invention, and one surface of the metal particle-containing layer and the flat metal particles The figure explaining the angle ((theta)) which makes with a plane is shown.
  • FIG. 2C is a schematic cross-sectional view showing the existence state of a metal particle-containing layer containing flat metal particles in the heat ray shielding material of the present invention, and the presence of the metal particle-containing layer in the depth direction of the heat ray shielding material. It is a figure which shows an area
  • FIG. 3 is a graph showing a transmission spectrum, a reflection spectrum, and an absorption spectrum in the heat ray shielding material of Comparative Example 4.
  • FIG. 4 is a graph showing a reflection spectrum in the heat ray shielding material of Comparative Example 1.
  • the heat ray shielding material of the present invention has a metal particle-containing layer containing at least one kind of metal particles, and an infrared reflecting layer in which 5 to 200 layers of at least two kinds of transparent thin layers having different refractive indexes are alternately laminated. Furthermore, it has other layers, such as a pressure-sensitive adhesive layer, appropriately selected as necessary.
  • a metal particle content layer is a layer containing at least 1 sort (s) of metal particle, there will be no restriction
  • the metal particles are not particularly limited as long as they contain flat metal particles, and can be appropriately selected according to the purpose.
  • flat metal particles granular, cubic, hexahedral
  • Examples include a face shape and a rod shape.
  • the presence state of the metal particles may be unevenly distributed in one plane facing a substantially horizontal direction with respect to one surface of the metal particle-containing layer (the surface of the infrared reflecting layer), or randomly.
  • the form unevenly distributed in one plane facing the substantially horizontal direction is not particularly limited and can be appropriately selected according to the purpose.
  • one surface of the metal particle-containing layer is a surface in contact with the infrared reflective layer, and is a flat plane similarly to the surface of the infrared reflective layer.
  • the material of the metal particles is not particularly limited and can be appropriately selected according to the purpose. However, silver, gold, aluminum, copper, rhodium, nickel, platinum are preferred because of the high heat ray (near infrared) reflectance. Etc. are preferable.
  • the flat metal particles are not particularly limited as long as they are particles composed of two main planes (see FIGS. 1A and 1B), and can be appropriately selected according to the purpose.
  • a hexagonal shape, a circular shape examples include a triangle shape.
  • a hexagonal shape and a circular shape are particularly preferable in terms of high visible light transmittance.
  • the circular shape is not particularly limited as long as it has no corners and round shape when the flat metal particles are observed from above the main plane with a transmission electron microscope (TEM), and is appropriately selected according to the purpose. be able to.
  • TEM transmission electron microscope
  • the hexagonal shape is not particularly limited as long as it is a hexagonal shape when the flat metal particles are observed from above the main plane with a transmission electron microscope (TEM), and can be appropriately selected according to the purpose.
  • the hexagonal corners may be sharp or dull, but the corners are preferably dull in that the absorption in the visible light region can be reduced.
  • corner According to the objective, it can select suitably.
  • a material of a flat metal particle The same thing as a metal particle can be suitably selected according to the objective.
  • the flat metal particles preferably contain at least silver.
  • the hexagonal or disc-shaped flat metal particles are 60% by number or more, preferably 65% by number or more, based on the total number of metal particles. A number% or more is more preferable. If the proportion of the flat metal particles is less than 60% by number, the visible light transmittance may be lowered.
  • the flat metal particles have a plane orientation in the range of 0 ° to ⁇ 30 ° with respect to one surface of the metal particle-containing layer (or the surface of the infrared reflecting layer). It is preferable that the plane orientation is in the range of 0 ° to ⁇ 20 °.
  • the ratio of the flat metal particles whose main plane is plane-oriented in the range of 0 ° to ⁇ 30 ° with respect to one surface of the metal particle-containing layer with respect to the total number of flat metal particles. Is preferably 50% by number or more, more preferably 80% by number or more, and still more preferably 90% by number or more.
  • the presence state of the flat metal particles is not particularly limited and may be appropriately selected depending on the purpose. However, it is preferable that the flat metal particles are arranged on the infrared reflecting layer as shown in FIG.
  • FIG. 2A to FIG. 2C are schematic cross-sectional views showing the presence state of the metal particle-containing layer containing flat metal particles in the heat ray shielding material of the present invention.
  • FIG. 2A shows the most ideal existence state of the plate-like metal particles 3 in the metal particle-containing layer 2.
  • FIG. 2B is a diagram for explaining an angle ( ⁇ ⁇ ) formed by the plane of the infrared reflecting layer 1 and the plane of the flat metal particle 3.
  • FIG. 2C shows the existence region in the depth direction of the heat ray shielding material of the metal particle-containing layer 2.
  • the angle ( ⁇ ⁇ ) formed between the surface of the infrared reflective layer 1 and the main plane or extension of the main plane of the flat metal particles 3 corresponds to a predetermined range in the plane orientation. That is, the plane orientation means a state in which the inclination angle ( ⁇ ⁇ ) shown in FIG. 2B is small when the cross section of the heat ray shielding material is observed.
  • FIG. 2A shows the surface of the infrared reflecting layer 1 and the flat metal particles. 3 is in contact with the main plane, that is, a state where ⁇ is 0 °.
  • a predetermined wavelength of the heat ray shielding material for example, a visible light region long wavelength
  • the reflectance in the near infrared light region from the side is reduced.
  • the evaluation of whether or not the main plane of the flat metal particles is plane-oriented with respect to one surface of the metal particle-containing layer (or the surface of the infrared reflective layer) is not particularly limited and is appropriately selected according to the purpose.
  • a method may be used in which an appropriate cross section is prepared and the metal particle-containing layer and the flat metal particles in the slice are observed and evaluated.
  • a microtome and a focused ion beam are used to prepare a cross-sectional sample or a cross-section sample of the heat ray shielding material, and this is used for various microscopes (for example, a field emission scanning electron microscope (FE-SEM) etc.), and a method of evaluating from an image obtained by observation.
  • FE-SEM field emission scanning electron microscope
  • the binder that covers the flat metal particles swells with water
  • the sample frozen in liquid nitrogen is cut with a diamond cutter mounted on a microtome to obtain a cross-section sample or a cross-section sample. May be produced.
  • covers a flat metal particle in a heat ray shielding material does not swell with water, you may produce a cross-section sample thru
  • the main plane of the plate-like metal particles is plane-oriented with respect to one surface of the metal particle-containing layer (or the surface of the infrared reflective layer).
  • it can be appropriately selected according to the purpose, and examples thereof include observation using an FE-SEM, TEM, optical microscope, and the like.
  • observation may be performed by FE-SEM
  • observation may be performed by TEM.
  • TEM When evaluating by FE-SEM, it is preferable to have a spatial resolution with which the shape and inclination angle ( ⁇ ⁇ in FIG. 2B) of the flat metal particles can be clearly determined.
  • the average particle diameter (average equivalent circle diameter) of the flat metal particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 70 nm to 500 nm, and more preferably 80 nm to 400 nm.
  • the average particle diameter (average equivalent circle diameter) is less than 70 nm, the contribution of the absorption of the flat metal particles is larger than the reflection, so that sufficient heat ray reflectivity may not be obtained.
  • Haze (scattering) increases, and the transparency of the heat ray shielding material may be impaired.
  • the average particle diameter is an average value of main plane diameters (maximum lengths) of 200 flat metal particles arbitrarily selected from images obtained by observing particles with a TEM. Means. Two or more kinds of metal particles having different average particle diameters (average equivalent circle diameters) can be included in the metal particle-containing layer. In this case, two or more peaks of the average particle diameter (average equivalent circle diameter) of the metal particles are present. That is, you may have two average particle diameters (average circle equivalent diameter).
  • the coefficient of variation in the particle size distribution of the flat metal particles is preferably 30% or less, and more preferably 20% or less. When the variation coefficient exceeds 30%, the reflection wavelength region of the heat ray in the heat ray shielding material may become broad.
  • the coefficient of variation in the particle size distribution of the flat metal particles is plotted, for example, by plotting the particle size distribution range of the 200 flat metal particles used for calculating the average value obtained as described above. The standard deviation is obtained, and is a value (%) divided by 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 flat metal particles is not particularly limited and may be appropriately selected depending on the intended purpose. However, since the reflectance in the infrared light region having a wavelength of 900 nm to 2,000 nm is high, the aspect ratio is 10%. To 45 is preferable, and 20 to 35 is more preferable. When the aspect ratio is less than 10, the reflection wavelength becomes smaller than 900 nm, and when it exceeds 45, the reflection wavelength becomes longer than 2,000 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 the flat metal particles by the average particle thickness of the flat metal particles.
  • the average particle thickness corresponds to the distance between the main planes of the flat metal particles, and is, for example, as shown in FIGS. 1A and 1B and can be measured by an atomic force microscope (AFM).
  • the method for measuring the average particle thickness by AFM is not particularly limited and can be appropriately selected depending on the purpose.For example, a particle dispersion containing flat metal particles is dropped onto a glass substrate and dried. For example, a method of measuring the thickness of one particle may be used.
  • the plasmon resonance wavelength of the metal constituting the flat metal particle 3 in the metal particle-containing layer 2 is ⁇
  • the refractive index of the medium in the metal particle-containing layer 2 is
  • the metal particle-containing layer 2 is preferably present in the range of 0 to ( ⁇ / n) / 4 in the depth direction from the horizontal plane of the heat ray shielding material.
  • the effect of increasing the amplitude of the reflected wave due to the phase of the reflected wave at the interface air interface between the upper and lower metal particle-containing layers of the heat ray shielding material is reduced, haze characteristics, The visible light transmittance and the maximum heat ray reflectance may decrease.
  • the plasmon resonance wavelength ⁇ of the metal constituting the flat metal particles in the metal particle-containing layer is not particularly limited and can be appropriately selected according to the purpose, but is 400 nm to 2 in terms of imparting heat ray reflection performance. , 500 nm is preferable, and from the viewpoint of imparting visible light transmittance, 700 nm to 2,500 nm is more preferable.
  • a medium in a metal particle content layer there is no restriction
  • the refractive index n of the medium is preferably 1.4 to 1.7.
  • the area of the plate-like metal particles relative to the area A of the heat ray shielding material when the heat ray shielding material is viewed from above (the total projected area A of the metal particle containing layer when viewed from the direction perpendicular to the metal particle containing layer)
  • the area ratio [(B / A) ⁇ 100] which is the ratio of the total value B, is preferably 15% or more, and more preferably 20% or more.
  • the area ratio can be measured, for example, by performing image processing on an image obtained by SEM observation of the heat ray shielding material from above or an image obtained by AFM (atomic force microscope) observation.
  • the average inter-particle distance between the flat metal particles adjacent in the horizontal direction in the metal particle-containing layer is 1/10 of the average particle diameter of the flat metal particles in terms of the visible light transmittance and the maximum reflectance of the heat ray.
  • the above is preferable.
  • the average interparticle distance in the horizontal direction of the flat metal particles is less than 1/10 of the average particle diameter of the flat metal particles, the maximum reflectivity of the heat rays is lowered.
  • the average interparticle distance in the horizontal direction is preferably non-uniform (random) in terms of visible light transmittance. If it is not random, that is, if it is uniform, absorption of visible light occurs, and the transmittance may decrease.
  • the average interparticle distance in the horizontal direction of the flat metal particles means the average value of the interparticle distance between two adjacent particles.
  • the average distance between the particles means that “other than the origin when taking a two-dimensional autocorrelation of luminance values when binarizing an SEM image including 100 or more tabular metal particles. Does not have a significant local maximum. "
  • the flat metal particles are arranged in the form of a metal particle-containing layer containing flat metal particles, as shown in FIGS. 2A to 2C.
  • the metal particle-containing layer may be composed of a single layer as shown in FIGS. 2A to 2C, or may be composed of a plurality of metal particle-containing layers.
  • the thickness of the metal particle-containing layer is not particularly limited and may be appropriately selected depending on the intended purpose. However, in consideration of actual coating and drying load, 0.01 to 1 ⁇ m is preferable, and 0.02 to 0. 5 ⁇ m is more preferable.
  • the thickness of each layer of the metal particle-containing layer can be measured, for example, from an image obtained by SEM observation of a cross-sectional sample of the heat ray shielding material.
  • the method for synthesizing the flat metal particles is not particularly limited as long as it can synthesize a hexagonal shape or a circular shape, and can be appropriately selected according to the purpose.
  • a chemical reduction method, a photochemical reduction method examples thereof include a liquid phase method such as an 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 or triangular plate-like metal particles After synthesizing hexagonal or triangular plate-like metal particles, for example, by performing etching treatment with a dissolved species that dissolves silver such as nitric acid or sodium sulfite, aging treatment by heating, etc., hexagonal or triangular plate
  • the corners of the metal particles may be blunted to obtain substantially hexagonal or substantially circular flat metal particles.
  • metal particles for example, Ag
  • a transparent substrate such as a film or glass
  • the flat metal particles 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 plate-like metal particles 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. Furthermore, a metal oxide layer may be formed on the shell layer.
  • TiO x is used as a 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 flat metal particles are dispersed may be deteriorated. After forming the TiO x layer on the flat metal particles, an SiO 2 layer may be appropriately formed.
  • the flat metal particles adsorb an antioxidant such as mercaptotetrazole and ascorbic acid in order to prevent oxidation of metals such as silver constituting the flat metal particles. May be. Further, for the purpose of preventing oxidation, an antioxidant layer such as Ni may be formed on the surface of the flat metal particles. Further, it may be covered with a metal oxide film such as SiO 2 for the purpose of blocking oxygen.
  • the flat metal particles are, for example, quaternary ammonium salts, low molecular weight dispersants containing at least one of N elements such as amines, S elements, and P elements, and high molecular weight dispersants.
  • a dispersant may be added.
  • the infrared reflecting layer is not particularly limited as long as at least two kinds of transparent thin layers having different refractive indexes are alternately laminated, and can be appropriately selected according to the purpose.
  • the infrared reflective layer is preferably an infrared reflective layer (organic multilayer film) in which 20 to 200 layers of at least two polymers having different refractive indexes are alternately laminated, and are alternately laminated, alternately laminated extruded, alternately coated, and alternately thin. More preferably, it is at least one of layer laminates.
  • the transparent thin layer has a visible light transmittance of 70% or more and has a thickness of 50 nm to 300 nm, and may be a thin layer made of a polymer.
  • the thickness of the transparent thin layer is not particularly limited as long as it is 50 nm to 300 nm, and can be appropriately selected according to the purpose, but is preferably 70 nm to 200 nm.
  • thickness of the transparent thin layer which consists of a different material it may mutually differ between different materials, and may be the same.
  • thickness of the transparent thin layer which consists of 1 type of material it may mutually differ between several transparent thin layers, and may be the same.
  • the refractive indexes are different from each other means that at least two kinds of transparent thin layers have different refractive indexes of 0.01 or more, and when the transparent thin layer is a thin layer made of a polymer, 0.02 or more. It is preferable.
  • the polymer is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the method for alternately laminating the polymers is not particularly limited, and a known method can be appropriately selected according to the purpose. For example, a lamination extrusion method, a roll coating method, a flow coating method, a dipping method, or the like can be applied. And a method of laminating a thin polymer layer.
  • the infrared reflective layer is made up of a unit laminate by alternately laminating 10 to 40 layers of polymer thin layers having different thicknesses t1 and t2 having different refractive indices, and changing the thicknesses t1 and t2. It is preferable to have 2 to 6 unit laminates from the viewpoint that the reflection wavelength range can be widened.
  • the thickness of the infrared reflective layer that is, the total thickness of the plurality of transparent thin layers is not particularly limited and can be appropriately selected according to the purpose.
  • the infrared reflective layer has at least two kinds of refractive indexes different from each other.
  • the polymer is an infrared reflective layer (organic multilayer film) in which 20 to 200 layers are alternately laminated
  • the thickness is preferably 30 to 200 ⁇ m, more preferably 50 to 100 ⁇ m.
  • the maximum wavelength of the reflection spectrum of the infrared reflection layer is preferably 700 nm to 1,500 nm, the maximum wavelength of the reflection spectrum of the metal particle-containing layer is preferably 900 nm to 2,000 nm, and the shielding coefficient is preferably 0.7 or less. Moreover, it is preferable that the difference between the maximum wavelength of the reflection spectrum of the infrared reflection layer and the maximum wavelength of the reflection spectrum of the metal particle-containing layer is 100 nm or more. Further, the shielding coefficient is more preferably 0.65 or less, and particularly preferably 0.6 or less.
  • the heat ray shielding material of the present invention preferably further has an adhesive layer.
  • 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.
  • you may add an antistatic agent, a lubricant, an antiblocking agent, etc. to the adhesion layer.
  • the thickness of the adhesive layer is preferably 0.1 ⁇ m to 10 ⁇ m.
  • ⁇ Protective layer In the heat ray shielding material of the present invention, it is preferable to have a protective layer in order to improve adhesion to the infrared reflective layer or to protect it from mechanical strength.
  • a protective layer There is no restriction
  • the binder is not particularly limited and may be appropriately selected depending on the intended purpose.
  • cellulose polyvinyl chloride, and polyvinyl pyrrolidone.
  • a method for forming the protective layer an appropriate organic solvent is selected as a solution, applied to the surface of the metal particle-containing layer, and then dried to form a thin film, or depending on the resin, a water-soluble emulsion is prepared.
  • a method of forming a thin film by coating the surface of the metal particle-containing layer as an aqueous solution and then heat drying to fuse the emulsion particles.
  • the method for forming the metal particle-containing layer is not particularly limited and can be appropriately selected depending on the purpose.
  • a dispersion having flat metal particles on the surface of a lower layer such as an infrared reflective layer
  • examples thereof include a method of coating by a dip coater, a die coater, a slit coater, a bar coater, a gravure coater, and the like, and a method of surface orientation by a method such as an LB film method, a self-organization method, and spray coating.
  • the method for forming the metal particle-containing layer includes a method in which plane orientation is performed using electrostatic interaction in order to improve the adsorptivity to the infrared reflective layer surface and plane orientation of the flat metal particles.
  • plane orientation is performed using electrostatic interaction in order to improve the adsorptivity to the infrared reflective layer surface and plane orientation of the flat metal particles.
  • a method for example, when the surface of the flat metal particle is negatively charged (for example, dispersed in a negatively charged medium such as citric acid), the surface of the infrared reflective layer is positively
  • a method of aligning the surface by electrostatically enhancing the surface orientation by charging for example, modifying the surface of the infrared reflecting layer with an amino group or the like).
  • the surface of the flat metal particles is hydrophilic
  • a hydrophilic / hydrophobic sea-island structure is formed on the surface of the infrared reflecting layer by using a block copolymer, microcontact stamp method, etc., and the hydrophilic / hydrophobic interaction is utilized.
  • the plane orientation and the interparticle distance of the flat metal particles may be controlled.
  • a pressure roller such as a calender roller or a laminating roller.
  • the adhesive layer is preferably formed by coating.
  • it can be laminated on the surface of a lower layer such as an infrared reflecting layer, a metal particle-containing layer, or an ultraviolet absorbing layer.
  • a lower layer such as an infrared reflecting layer, a metal particle-containing layer, or an ultraviolet absorbing layer.
  • the coating method at this time A well-known method can be used.
  • the solar radiation reflectance of the heat ray shielding material of the present invention preferably has a maximum value in the range of 600 nm to 2,000 nm (preferably 800 nm to 1,800 nm) from the viewpoint that the efficiency of the heat ray reflectance can be increased.
  • the visible light transmittance of the heat ray shielding material of the present invention is preferably 60% or more, and more preferably 70% or more. When the visible light transmittance is less than 60%, for example, when used as glass for automobiles or glass for buildings, the outside may be difficult to see.
  • the haze of the heat ray shielding material of the present invention is preferably 20% or less. If the haze exceeds 20%, it may be unfavorable in terms of safety, for example, when it is used as automotive glass or building glass, it becomes difficult to see the outside.
  • a film is prepared by previously applying and drying an adhesive on a release film, and the adhesive surface of the film and the metal particles of the heat ray shielding material of the present invention are used. It is effective to laminate in a dry state by laminating the surface of the containing layer.
  • the bonding structure of the present invention is formed by bonding the heat ray shielding material of the present invention and either glass or plastic.
  • the heat ray shielding material of this invention which has the contact bonding layer manufactured as mentioned above is glass for vehicles, such as a motor vehicle. Or a method of bonding to glass or plastic for building materials or plastic.
  • the laminated glass of the present invention includes at least one heat ray shielding material of the present invention, at least two intermediate layers, and at least two glasses, and the intermediate layer sandwiching the heat ray shielding material is at least two glasses. Hold it.
  • the intermediate layer preferably contains at least one of polyvinyl butyral and ethylene vinyl copolymer.
  • the heat ray shielding material of this invention is laminated
  • autoclaving under conditions of 130 ° C., 13 atm, and 1 hour may be used.
  • the glass is not particularly limited and can be appropriately selected according to the purpose.For example, it has good smoothness, little distortion of the fluoroscopic image, little distortion due to wind and external force with a certain degree of rigidity, and in the visible light region. Examples thereof include soda lime glass called a transparent type or a clear type, which is excellent in permeation and has a reduced coloring component such as metal oxide by a float method obtained at a relatively low cost.
  • the heat ray shielding material, the laminated structure and the laminated glass of the present invention are not particularly limited as long as they are used for selectively reflecting or absorbing heat rays (near infrared rays), and are appropriately selected according to the purpose.
  • a film for vehicles, a laminated structure or laminated glass, a film for building materials, a laminated structure or laminated glass, an agricultural film, and the like can be given.
  • the film for vehicles, the laminated structure and the laminated glass, the film for building material, the laminated structure and the laminated glass are preferable from the viewpoint of energy saving effect.
  • heat rays mean near infrared rays (780 nm to 1,800 nm) contained in sunlight by about 50%.
  • Infrared reflective layer 1 (organic multilayer film) [Infrared reflective layer 1] was produced by alternately laminating two types of thin polymer layers having different refractive indexes by the following procedure.
  • Polymethylmethacrylate (PMMA) was used for the low refractive polymer thin layer
  • PET polyethylene terephthalate
  • a low refractive index layer formed using PMMA is called a PMMA layer
  • a high refractive index layer formed using PET is called a PET layer.
  • the PMMA layer was formed by applying a solution obtained by dissolving PMMA in 2-methoxyethyl acetate by a roll coating method.
  • the refractive index was 1.49.
  • the PET layer was formed by applying PET pellets while melting them with an extruder.
  • the refractive index of the PET layer was 1.65.
  • 20 layers of 0.144 ⁇ m PMMA layers and 0.159 ⁇ m PET layers are alternately laminated, and further, 10 layers of 0.165 ⁇ m PMMA layers and 0.183 ⁇ m PET layers are alternately laminated, and 15 layers of 0.187 ⁇ m PMMA layers and 0.207 ⁇ m PET layers are alternately stacked, and further 15 layers of 0.158 ⁇ m PMMA layers and 0.175 ⁇ m PET layers are alternately stacked. 15 layers of 0.172 ⁇ m PMMA layers and 0.191 ⁇ m PET layers were alternately laminated to produce [Infrared reflective layer 1]. There are 150 polymer thin layers in total.
  • [Infrared reflective layer 2] comprises the following three polymer components: component A comprises a styrene-methyl methacrylate copolymer (P-359, Richardson's copolymer) having a refractive index of 1.57 and a density of 1.08.
  • component B is a methyl methacrylate-styrene copolymer (RPC-440, manufactured by Richardson Polymer Corporation) having a refractive index of 1.53 and a density of 1.13; and
  • Component C Is polymethylmethacrylate (VS-100, manufactured by Rohm and Haas) having a refractive index of 1.49 and a density of 1.20.
  • a protective layer of polycarbonate was provided on both sides of [Infrared reflective layer 2], which was sufficient to eliminate surface instability and to provide mechanical properties.
  • This three-component film was coextruded to obtain a 165-layer film having ABCB repeating units.
  • the three component feed block has 42 feed slots for component A, 82 feed slots for component B, and 41 feed slots for component C.
  • Three separate extruders feedblock each polymer component at a rate of 8.5 kg / hr for component A, 9.0 kg / hr for component B, and 9.8 kg / hr for component C. Supplied to.
  • As a protective layer 6.8 kg / hr polycarbonate was coextruded on both surfaces of the film.
  • the drop rate of the film was adjusted to show a strong primary reflectivity at 1,400 nm with a film thickness of about 204 ⁇ m (0.9 mil).
  • an [infrared reflective layer 2] in which the layer thickness of component A was 148.6 nm, the layer thickness of component B was 76.3 nm, and the layer thickness of component C was 156.6 nm was obtained. Therefore, the optical thickness ratio fA of the first component A is 1/3, the optical thickness ratio fB of the second component B is 1/6, and the optical thickness ratio fC of the third component C is The refractive index of each component satisfies the relationship of the following formula.
  • the optical thickness ratio f i is defined by the following equation.
  • ni the refractive index of the polymer i
  • di the layer thickness of the polymer i.
  • [Infrared reflective layer 2] was found to exhibit strong primary reflection at a wavelength ( ⁇ I) of 1,400 nm in the near-infrared spectral region.
  • ⁇ I wavelength of 1,400 nm in the near-infrared spectral region.
  • secondary, tertiary and quaternary reflections were suppressed. Therefore, secondary reflection at a wavelength of 700 nm ( ⁇ I / 2) in the red region of visible light, tertiary reflection at a wavelength of 467 nm ( ⁇ I / 3) in the blue region of visible light, and 350 nm in the ultraviolet region. All fourth-order reflections at a wavelength of ( ⁇ I / 4) were suppressed.
  • Second growth step of tabular silver particles-- After stirring the said solution for 30 minutes, 71.1 mL of 0.35M potassium hydroquinonesulfonate aqueous solution was added, and 200 g of 7 mass% gelatin aqueous solution was added. To this solution was added a white precipitate mixture formed by mixing 107 mL of a 0.25 M aqueous sodium sulfite solution and 107 mL of a 0.47 M aqueous silver nitrate solution. This was stirred for 300 minutes, and flat silver particle dispersion liquid a1 was obtained.
  • silver hexagonal silver tabular grains having an average equivalent circle diameter of 310 nm (hereinafter referred to as Ag hexagonal tabular grains) are generated. confirmed. Further, when the thickness of the Ag hexagonal tabular grains was measured with an atomic force microscope (Nanocute II, manufactured by Seiko Instruments Inc.), the average hexagonal tabular grains having an aspect ratio of 23.8 and 13 nm were formed. I understood.
  • tabular silver particles were evaluated as follows. The results are shown in Tables 1 and 2.
  • ⁇ Evaluation of metal particles >> -Ratio of flat metal particles, average particle diameter (average equivalent circle diameter), coefficient of variation-
  • the shape uniformity of tabular silver particles is the shape of 200 particles arbitrarily extracted from the observed SEM image, A is a hexagonal shape or circular shape, and the shape is an irregular shape such as a teardrop shape.
  • B was subjected to image analysis, and the ratio (number%) of the number of particles corresponding to A was determined.
  • the particle diameter of 100 particles corresponding to A is measured with a digital caliper, the average value is defined as the average particle diameter (average equivalent circle diameter), and the standard deviation of the particle size distribution is the average particle diameter (average equivalent circle diameter). ) To obtain the coefficient of variation (%).
  • AFM atomic force microscope
  • a coating solution 1 having the composition shown below was prepared.
  • Composition of coating solution 1 Polyester latex aqueous dispersion: Finetex ES-650 (Manufactured by DIC, solid content concentration 30% by mass) 28.2 parts by mass
  • Surfactant A Rapisol A-90 (Nippon Yushi Co., Ltd., solid content concentration 1% by mass) 12.5 parts by mass
  • Surfactant B Aronactee CL-95 (Sanyo Chemical Industries, Ltd., solid content concentration 1% by mass) 15.5 parts by weight
  • Example 1 On one surface of [Infrared reflective layer 1], coating solution 1 was applied using a wire bar so that the average thickness after drying was 0.08 ⁇ m. Then, it heated at 150 degreeC for 10 minute (s), dried and solidified, the metal particle content layer was formed, and the heat ray shielding material of Example 1 was produced.
  • the average thickness can be determined by peeling a part of the coating film with an adhesive tape and measuring the stepped portion between the base and the coating film with a stylus roughness meter (DEKTAK).
  • Example 1-1 Production of heat ray shielding material having adhesive layer
  • the adhesive layer was bonded together.
  • the pressure-sensitive adhesive PD-S1 manufactured by Panac Co., Ltd. was used, and the surface of the pressure-sensitive adhesive, from which one release sheet was peeled, was bonded to the surface of the heat ray shielding material by overlapping with the metal particle-containing layer surface.
  • a heat ray shielding material having the adhesive layer of Example 1-1 was produced.
  • Example 1-2 Production of bonded structure of heat ray shielding material
  • the obtained heat ray shielding material release sheet having the adhesive layer was peeled off and bonded to transparent glass (thickness: 3 mm) to produce a heat ray shielding material bonded structure of Example 1-2.
  • the transparent glass used is one that has been wiped off with isopropyl alcohol and left to stand.
  • a rubber roller is used and the surface pressure is 0.5 kg / cm 2 at 25 ° C. and 65% humidity. Crimped.
  • Example 1-3 Production of laminated glass
  • the heat ray shielding material of Example 1 was sandwiched from both sides with a polyvinyl butyral film (thickness 0.38 mm, S-LECT B, manufactured by Sekisui Chemical Co., Ltd.), and further sandwiched between 2 mm thick glass plates from both sides of the laminate (each The size in the plane direction was 50 mm square). In that state, it was temporarily pressure-bonded through a roll laminator having a metal roll heated at 60 ° C. The temporarily pressure-bonded sample was put in an autoclave and subjected to main pressure bonding by autoclaving under conditions of 130 ° C., 13 atm and 1 hour to obtain a laminated glass of Example 1-3.
  • the reflection spectrum and transmission spectrum of each produced heat ray shielding material were measured using an ultraviolet-visible near-infrared spectrometer (manufactured by JASCO Corporation, V-670).
  • an absolute reflectance measurement unit ARV-474, manufactured by JASCO Corporation was used, and the incident light passed through a 45 ° polarizing plate and was regarded as incident light that can be regarded as non-polarized light.
  • the shielding coefficient was calculated
  • the shielding coefficient (0 to 1) is small.
  • Example 2 In Example 1, instead of [Infrared reflective layer 1], [Infrared reflective layer 2] was used, except that the coating liquid 1 was applied on one surface of [Infrared reflective layer 2].
  • the heat ray shielding material of Example 2 the heat ray shielding material having the adhesive layer of Example 2-1, the bonded structure of the heat ray shielding material of Example 2-2, and the combination of Example 2-3 Glass was produced.
  • Example 1 In Example 1, except that the coating liquid 1 was not applied, the heat ray shielding material of Comparative Example 1, the heat ray shielding material having the adhesive layer of Comparative Example 1-1, and Comparative Example 1 were the same as Example 1. -2 heat ray shielding material laminated structure and Comparative Example 1-3 laminated glass were produced.
  • Example 2 In Example 1, the heat ray shielding material of Comparative Example 2 was used in the same manner as in Example 1 except that instead of the coating liquid 1, an ITO hard coat coating liquid (EI-1 manufactured by Mitsubishi Materials Corporation) was applied. A heat ray shielding material having an adhesive layer of Comparative Example 2-1, a laminated structure of the heat ray shielding material of Comparative Example 2-2, and a laminated glass of Comparative Example 2-3 were produced.
  • the ITO particles have a transmittance of 1,400 nm to 2,200 nm of 10% or less and a visible transmittance of 90%.
  • Example 3 (Comparative Example 3)
  • the heat ray shielding material of Comparative Example 3 the heat ray shielding material having the adhesive layer of Comparative Example 3-1, and Comparative Example 3 were the same as Example 2 except that the coating liquid 1 was not applied.
  • Example 4 In Example 1, instead of [Infrared reflective layer 1], a transparent PET film having a thickness of 100 ⁇ m was used, and the coating liquid 1 was applied on one surface of the PET film, as in Example 1.
  • the heat ray shielding material of Comparative Example 4 the heat ray shielding material having the adhesive layer of Comparative Example 4-1, the laminated structure of the heat ray shielding material of Comparative Example 4-2, and the laminated glass of Comparative Example 4-3 Produced.
  • Example 2 The characteristics of the heat ray shielding materials of Example 2 and Comparative Examples 1 to 4 were evaluated in the same manner as in Example 1. The results are shown in Table 3. Moreover, the spectrum of the comparative example 4 (only a metal particle content layer) is shown in FIG. 3, and the reflection spectrum of the comparative example 1 (only [infrared reflective layer 1]) is shown in FIG.
  • the heat ray shielding material of the present invention can improve the reflectance of infrared rays over a wide band and can achieve both high light transmittance in the visible light region.
  • the heat ray shielding material of the present invention can improve the reflectance of infrared rays over a wide band and can achieve both high light transmittance in the visible light region, for example, films for vehicles such as automobiles and buses, bonded structures, As a laminated glass, a building material film, a laminated structure, a laminated glass, etc., it can be suitably used as various members that are required to prevent the transmission of heat rays.

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Abstract

La présente invention a trait à un matériau de protection contre les rayons thermiques qui améliore le pouvoir réfléchissant des rayons infrarouges à travers une large région tout en offrant une haute transparence dans la région du rayonnement visible. La présente invention a également trait à une structure stratifiée et à un verre feuilleté qui utilisent ce matériau de protection contre les rayons thermiques. Ce matériau de protection contre les rayons thermiques est doté d'une couche contenant des particules métalliques qui contient au moins un type de particule métallique et d'une couche réfléchissant les rayons infrarouges qui est obtenue en empilant de façon alternée 5 à 200 couches d'au moins deux types de couches minces transparentes dotées d'indices de réfraction mutuellement différents, lesquelles particules métalliques se présentent sous une forme hexagonale ou ronde, et des particules métalliques plates représentent 60 % ou plus des particules.
PCT/JP2012/062449 2011-05-17 2012-05-16 Matériau de protection contre les rayons thermiques, structure stratifiée et verre feuilleté WO2012157655A1 (fr)

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JP6732138B2 (ja) * 2017-09-25 2020-07-29 富士フイルム株式会社 赤外吸収材料、赤外センサー、波長選択光源及び放射冷却システム
JP7041424B2 (ja) * 2017-09-27 2022-03-24 國雄 吉田 薄膜の形成方法及び光学素子

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