WO2013039215A1 - Matière de protection contre les rayons thermiques - Google Patents

Matière de protection contre les rayons thermiques Download PDF

Info

Publication number
WO2013039215A1
WO2013039215A1 PCT/JP2012/073662 JP2012073662W WO2013039215A1 WO 2013039215 A1 WO2013039215 A1 WO 2013039215A1 JP 2012073662 W JP2012073662 W JP 2012073662W WO 2013039215 A1 WO2013039215 A1 WO 2013039215A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
heat ray
ray shielding
containing layer
shielding material
Prior art date
Application number
PCT/JP2012/073662
Other languages
English (en)
Japanese (ja)
Inventor
清都　尚治
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Publication of WO2013039215A1 publication Critical patent/WO2013039215A1/fr

Links

Images

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/206—Filters comprising particles embedded in a solid matrix
    • 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

Definitions

  • the present invention relates to a heat ray shielding material. More specifically, the present invention relates to a heat ray shielding material having good visible light permeability and heat shielding performance and good adhesion between a metal particle-containing layer and a polymer film as a substrate.
  • heat ray shielding materials for automobiles and building windows have been developed as an energy-saving measure for reducing carbon dioxide. From the viewpoint of the heat ray shielding property (acquisition rate of solar heat), the heat ray reflection type without re-radiation is better than the heat ray absorption type with re-radiation of absorbed light into the room (about 1/3 of the absorbed solar energy).
  • Various proposals have been made.
  • a filter using Ag tabular grains has been proposed as an infrared shielding filter (see Patent Document 1).
  • the infrared shielding filter described in Patent Document 1 is intended to be used in a plasma display panel (PDP), and the Ag tabular grains are not controlled in their arrangement, and therefore mainly have wavelengths in the infrared region. It functioned as a light infrared absorber and did not function as a material that actively reflects heat rays. Therefore, when an infrared shielding filter composed of such Ag tabular grains is used for heat shielding of direct sunlight, the infrared absorbing filter itself is warmed, and the room temperature rises due to the heat, so that it functions as an infrared shielding material. Was insufficient.
  • the dispersion liquid containing Ag tabular grain was apply
  • Patent Document 2 describes a wavelength selective film using granular silver.
  • an Ag layer in which granular silver particles are distributed is formed by sputtering and heat treatment of Ag. According to FIG. 3 of the same document, the shape of the granular silver particles is often indefinite. Further, Patent Document 2 did not describe a crosscut test.
  • Patent Document 3 there are 60% by number or more of hexagonal or circular tabular metal particles, and the main plane of the hexagonal or circular tabular metal particles is one surface of the metal particle-containing layer.
  • a heat ray shielding material having a plane orientation in an average range of 0 ° to ⁇ 30 ° is disclosed.
  • Patent Document 3 did not describe a crosscut test.
  • the infrared shielding filter described in Patent Document 1 is an infrared absorption type, the infrared absorber is warmed when used for heat insulation of sunlight, causing a temperature rise in the room. was there.
  • the glass breaks (becomes hot) due to a difference in temperature rise between a place where sunlight hits and a place where sunlight does not hit.
  • Patent Document 2 has a problem in that when infrared rays are shielded with granular silver, the half-width of the spectrum is large and the infrared rays cannot be shielded sharply, so that the infrared rays on the short wave side where the energy of sunlight is large cannot be sufficiently shielded. .
  • silver tabular grains are randomly arranged as in Patent Document 1, they are only absorbed, but when they are regularly arranged like the heat ray shielding material described in Patent Document 3, they are reflected, which is advantageous as an infrared shielding film. It was a thing.
  • the patent document 3 did not examine the cross-cut test as described above, the present inventor created the coating film of the example of the document and performed the cross-cut test. It has been found that there is a problem that the tabular grain-containing layer peels off in the cross-cut test.
  • Patent Document 4 describes an infrared shielding film having good cross-cut adhesion.
  • antimony trioxide tin oxide particles are used as metal particles, and the shape and arrangement of the metal particles are not described in the specification.
  • the method described in Patent Document 4 has a problem in that when used for shielding sunlight like the method of Patent Document 2 described above, infrared rays are not reflected, so that the window becomes hot and is heated.
  • the object of the present invention is to solve the conventional problems. That is, the problem to be solved by the present invention is that the visible light transmittance and the heat shielding performance (solar reflectance) are good, and the heat ray shielding has good adhesion between the metal particle-containing layer and the polymer film as the substrate. To provide materials.
  • the metal particle-containing layer is oriented in the range of °, the metal particle-containing layer contains a polymer, and the adhesion between the metal particle-containing layer and the polymer film Heat ray shielding material characterized by 2 or less points.
  • the polymer contained in the metal particle-containing layer preferably contains a polyester resin.
  • the main polymer of the polymer contained in the metal particle-containing layer is preferably a polyester resin.
  • the content of the polyester resin with respect to the metal particles contained in the metal particle-containing layer is preferably 1 to 10,000 mass%.
  • the thickness of the metal particle-containing layer is preferably 10 to 160 nm.
  • the polymer film is preferably a PET film.
  • the hexagonal to circular plate-like metal particles have an average particle diameter of 70 nm to 500 nm, and the hexagonal to circular shape.
  • the aspect ratio (average particle diameter / average particle thickness) of the shaped tabular metal particles is preferably 8 to 40.
  • the hexagonal or circular flat metal particles include at least silver.
  • the heat ray shielding material according to any one of [1] to [8] preferably has a visible light transmittance of 70% or more.
  • the heat ray shielding material according to any one of [1] to [9] preferably reflects infrared light.
  • a heat ray shielding material having good visible light permeability and heat shielding performance (solar reflectance) and good cross-cut adhesion between a metal particle-containing layer and a polymer film as a substrate. be able to.
  • FIG. 1 is a schematic view showing an example of the heat ray shielding material of the present invention.
  • FIG. 2 is a schematic view showing another example of the heat ray shielding material of the present invention.
  • FIG. 3A is a schematic view showing another example of the heat ray shielding material of the present invention.
  • FIG. 3B is a schematic view showing another example of the heat ray shielding material of the present invention.
  • FIG. 4A is a schematic perspective view showing an example of the shape of tabular grains contained in the heat ray shielding material of the present invention, and shows circular tabular metal particles.
  • FIG. 4B is a schematic perspective view showing an example of the shape of tabular grains contained in the heat ray shielding material of the present invention, and shows hexagonal tabular metal particles.
  • FIG. 1 is a schematic view showing an example of the heat ray shielding material of the present invention.
  • FIG. 2 is a schematic view showing another example of the heat ray shielding material of the present invention.
  • FIG. 3A is a
  • FIG. 5A is a schematic cross-sectional view showing an example of the existence state of a metal particle-containing layer containing metal tabular grains in the heat ray shielding material of the present invention.
  • FIG. 5B is a schematic cross-sectional view showing another example of the existence state of the metal particle-containing layer containing the metal tabular grains in the heat ray shielding material of the present invention.
  • FIG. 5C is a schematic cross-sectional view showing another example of the existence state of the metal particle-containing layer containing the metal tabular grains in the heat ray shielding material of the present invention.
  • FIG. 5A is a schematic cross-sectional view showing an example of the existence state of a metal particle-containing layer containing metal tabular grains in the heat ray shielding material of the present invention.
  • FIG. 5B is a schematic cross-sectional view showing another example of the existence state of the metal particle-containing layer containing the metal tabular grains in the heat ray shielding material of the present invention.
  • FIG. 5C is a schematic cross
  • FIG. 5D is a schematic cross-sectional view showing the existence state of a metal particle-containing layer containing metal tabular grains in the heat ray shielding material of the present invention, and is a metal particle-containing layer containing metal tabular grains (parallel to the plane of the substrate). ) And the main plane of the tabular metal particles (the plane that determines the equivalent circle diameter D).
  • FIG. 5E is a schematic cross-sectional view showing the existence state of the metal particle-containing layer containing the metal tabular grains in the heat ray shielding material of the present invention, and the metal tabular grains in the depth direction of the heat ray shielding material of the metal particle-containing layer.
  • 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 heat ray shielding material of the present invention has a polymer film as a base material and a metal particle-containing layer disposed on at least one surface of the polymer film and containing at least one metal particle,
  • the particles have at least 60% by number of hexagonal or circular tabular metal particles, and the main plane of the hexagonal or circular tabular metal particles is an average with respect to one surface of the metal particle-containing layer.
  • a cross-cut cello tape (registered) that is oriented in the range of 0 ° to ⁇ 30 °, the metal particle-containing layer contains a polymer, and the adhesion between the metal particle-containing layer and the polymer film is defined in JIS K5600-5-6 (Trademark) Characteristic of 2 points or less in peel test.
  • the heat ray shielding material of the present invention has a metal particle-containing layer containing at least one kind of metal particles, and, if necessary, other layers such as an adhesive layer, an ultraviolet absorbing layer, a base material, and a metal oxide particle-containing layer. An embodiment having a layer is also preferred.
  • the layer structure of the heat ray shielding material 10 has a metal particle-containing layer 2 containing at least one kind of metal particles, and the metal tabular grains 3 are unevenly distributed on the surface thereof. Can be mentioned.
  • the aspect which has the metal particle containing layer 2, the overcoat layer 4 on this metal particle containing layer, and the metal tabular grain 3 is unevenly distributed on the surface is mentioned.
  • the substrate 1 has a metal particle-containing layer 2 on the substrate, and an adhesive layer 11 on the metal particle-containing layer, and a hard coat layer on the back surface of the substrate 1
  • the aspect which has 5 is mentioned suitably.
  • the base material 1 the metal particle-containing layer 2 on the base material, the overcoat layer 4 on the metal particle-containing layer, and the adhesive layer 11 on the overcoat layer.
  • the aspect which has and has the hard-coat layer 5 in the back surface of the base material 1 is mentioned suitably.
  • the metal particle-containing layer is a layer containing at least one kind of metal particle, and the metal particle has 60% by number or more of hexagonal or circular plate-like metal particles, and the hexagonal or circular shape.
  • the main plane of the flat metal particles is plane-oriented in an average range of 0 ° to ⁇ 30 ° with respect to one surface of the metal particle-containing layer, and is appropriately selected according to the purpose. be able to.
  • the thickness of the metal particle-containing layer is d
  • 80% by number or more of the hexagonal or circular tabular metal particles are d / 2 from the surface of the metal particle-containing layer. It is preferable that it exists in the range.
  • the heat ray shielding material of the present invention is not limited to the following production method, but a specific polymer (preferably latex) is used when producing the metal particle-containing layer. By adding it, the metal tabular grains can be segregated on one surface of the metal particle-containing layer.
  • Metal particles have 60% by number or more of hexagonal or circular tabular metal particles, and the main plane of the hexagonal or circular tabular metal particles is on one surface of the metal particle-containing layer. On the other hand, there is no particular limitation as long as the plane orientation is in the range of 0 ° to ⁇ 30 ° on average, and it can be appropriately selected according to the purpose.
  • the thickness of the metal particle-containing layer is d
  • 80% by number or more of the hexagonal or circular tabular metal particles are present in the range of d / 2 from the surface of the metal particle-containing layer. More preferably, 80% by number or more of the hexagonal or circular plate-like metal particles are present in a range of d / 3 from the surface of the metal particle-containing layer.
  • the metal particle-containing layer hexagonal to circular plate-like metal particles are present as one surface of the metal particle-containing layer (the surface of the substrate when the heat ray shielding material of the present invention has a substrate).
  • the plane orientation is in the range of 0 ° to ⁇ 30 ° on the average.
  • one surface of the said metal particle content layer is a flat plane.
  • the metal particle-containing layer of the heat ray shielding material of the present invention has a base material as a temporary support, it is preferably substantially horizontal with the surface of the base material.
  • the said heat ray shielding material may have the said temporary support body, and does not need to have it.
  • the material of the metal particles is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of high heat ray (near infrared) reflectance, silver, gold, aluminum, copper, rhodium, nickel, Platinum or the like is preferable.
  • the metal tabular grain is not particularly limited as long as it is a grain composed of two main planes (see FIGS. 4A and 4B), and can be appropriately selected according to the purpose.
  • hexagonal shape, circular shape, triangular shape Examples include shape.
  • a polygonal shape or a circular shape having a hexagonal shape or more is more preferable, and a hexagonal shape or a circular shape is particularly preferable.
  • the circular shape means 0 per side of a metal tabular grain having a length of 50% or more of the average equivalent circle diameter of a tabular metal grain (synonymous with tabular metal grain) described later. Say the shape that is.
  • the circular tabular metal grains are not particularly limited as long as they have no corners and round shapes when observed from above the main plane with a transmission electron microscope (TEM), depending on the purpose. It can be selected appropriately.
  • 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 the metal tabular grains described later is 6 per one metal tabular grain. The same applies to other polygons.
  • the hexagonal metal tabular grain is not particularly limited as long as it is a hexagonal shape when the metal tabular grain is observed from above the main plane with a transmission electron microscope (TEM), and is 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 metal tabular grain preferably contains at least silver.
  • hexagonal or circular plate-like metal particles are 60% by number or more, preferably 65% by number or more, and 70 by number with respect to the total number of metal particles. % Or more is more preferable. When the proportion of the metal tabular grains is less than 60% by number, the visible light transmittance may be lowered.
  • the hexagonal or circular plate-like metal particles have a main plane on one surface of the metal particle-containing layer (when the heat ray shielding material has a substrate, the surface of the substrate).
  • it is plane-oriented in an average range of 0 ° to ⁇ 30 °, preferably plane-oriented in an average range of 0 ° to ⁇ 20 °, and plane-oriented in an average range of 0 ° to ⁇ 5 °. It is particularly preferable.
  • the presence state of the metal tabular grains is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably arranged as shown in FIGS. 5B and 5C described later.
  • FIGS. 5A to 5E are schematic cross-sectional views showing the existence state of the metal particle-containing layer containing the metal tabular grains in the heat ray shielding material of the present invention.
  • 5A, FIG. 5B, and FIG. 5C show the presence state of the metal tabular grain 3 in the metal particle-containing layer 2.
  • FIG. 5D is a diagram illustrating an angle ( ⁇ ⁇ ) formed by the plane of the substrate 1 and the plane of the metal tabular grain 3.
  • FIG. 5E shows the existence region in the depth direction of the heat ray shielding material of the metal particle-containing layer 2.
  • the angle ( ⁇ ⁇ ) formed by the surface of the substrate 1 and the main plane of the metal tabular grain 3 or an extension line of the main plane 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. 5D is small when the cross section of the heat ray shielding material is observed. In particular, FIG. A state where the flat surface is in contact, that is, a state where ⁇ is 0 ° is shown. When the angle of the plane orientation of the main plane of the metal tabular grain 3 with respect to the surface of the substrate 1, that is, ⁇ in FIG. Infrared light region) reflectivity is reduced.
  • the evaluation of whether or not the main plane of the metal tabular grain is plane-oriented with respect to one surface of the metal particle-containing layer (the surface of the substrate when the heat ray shielding material has a substrate).
  • an appropriate cross section is prepared, and a metal particle-containing layer (a base material when the heat ray shielding material has a base material) and a flat metal particle are observed in this section. It may be a method of evaluating.
  • a microtome or a focused ion beam is used to prepare a cross-section 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
  • covers a metal tabular grain in a heat ray shielding material does not swell with water, you may produce the said cross-section sample or cross-section slice sample.
  • the main surface of the metal tabular grain is one of the surfaces of the metal particle-containing layer in the sample (or the base material surface when the heat ray shielding material has a base material).
  • the plane is plane-oriented, and it can be appropriately selected according to the purpose.
  • observation using an FE-SEM, TEM, optical microscope, or the like can be given. It is done.
  • observation may be performed by FE-SEM, and in the case of the cross section sample, observation may be performed by TEM.
  • the average particle diameter (average equivalent circle diameter) of the metal tabular grains 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 100 nm to 400 nm. When the average particle diameter (average equivalent circle diameter) is less than 70 nm, the contribution of absorption of the metal tabular grains becomes larger than the reflection, so that sufficient heat ray reflectivity may not be obtained. (Scattering) may increase and the transparency of the substrate may be impaired.
  • the average particle diameter means an average value of main plane diameters (maximum lengths) of 200 tabular grains arbitrarily selected from images obtained by observing grains with a TEM. To do. Two or more kinds of metal particles having different average particle diameters (average circle equivalent diameters) can be contained in the metal particle-containing layer. In this case, the peak of the average particle diameter (average circle equivalent diameter) of the metal particles is 2 It may have two or more, that is, two average particle diameters (average circle equivalent diameter).
  • the coefficient of variation in the particle size distribution of the metal tabular grains is preferably 30% or less, and more preferably 20% or less. When the coefficient of variation 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 metal tabular grains is, for example, plotting the distribution range of the particle diameters of the 200 metal tabular grains used for calculating the average value obtained as described above, and calculating the standard deviation of the particle size distribution. 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 metal tabular grain is not particularly limited and may be appropriately selected depending on the intended purpose. However, since the reflectance in the infrared region with a wavelength of 800 nm to 1,800 nm is high, it is 8 to 40 is preferable, and 10 to 35 is 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 circle equivalent diameter) of the tabular metal grains by the average grain thickness of the tabular metal grains.
  • the average grain thickness corresponds to the distance between the main planes of the metal tabular grain, and is, for example, as shown in FIGS. 4A and 4B and can be measured by an atomic force microscope (AFM).
  • the method for measuring the average particle thickness by the AFM is not particularly limited and can be appropriately selected depending on the purpose.For example, a particle dispersion containing metal tabular particles is dropped onto a glass substrate and dried. For example, a method of measuring the thickness of one particle may be used.
  • the thickness of the metal tabular grain is preferably 5 to 20 nm.
  • the heat ray shielding material of the present invention it is preferable that 80% by number or more of the hexagonal or circular plate-like metal particles are present in a range of d / 2 from the surface of the metal particle-containing layer, More preferably, it exists in the range, and more preferably 60% by number or more of the hexagonal or circular plate-like metal particles are exposed on one surface of the metal particle-containing layer.
  • the presence of the metal tabular grains in the range of d / 2 from the surface of the metal particle-containing layer means that at least a part of the metal tabular grains is included in the range of d / 2 from the surface of the metal particle-containing layer. . That is, the metal tabular grain described in FIG.
  • FIG. 5C in which a part of the metal tabular grain protrudes from the surface of the metal particle-containing layer is also in the range of d / 2 from the surface of the metal particle-containing layer.
  • Treat as. FIG. 5C means that only a part of each metal tabular grain in the thickness direction is buried in the metal particle-containing layer, and each metal tabular grain is not stacked on the surface of the metal particle-containing layer. Absent.
  • that the metal tabular grain is exposed on one surface of the metal particle-containing layer means that a part of one surface of the metal tabular grain protrudes from the surface of the metal particle-containing layer.
  • the distribution of the tabular metal particles in 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 plasmon resonance wavelength ⁇ of the metal constituting the metal tabular grain in the metal particle-containing layer is not particularly limited and can be appropriately selected according to the purpose. However, in terms of imparting heat ray reflection performance, 400 nm to 2, The thickness is preferably 500 nm, and more preferably 700 nm to 2,500 nm from the viewpoint of imparting visible light transmittance.
  • the heat ray shielding material of the present invention contains a polymer as a medium in the metal particle-containing layer.
  • the adhesion between the metal particle-containing layer and the polymer film should be easily controlled to be 2 points or less in the cross-cut cello tape (registered trademark) peel test defined in JIS K5600-5-6. Can do.
  • the cross-cut cello tape registered trademark
  • the polymer examples 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. And 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.
  • the heat ray shielding material of the present invention is a polyester resin.
  • the main polymer of the said polymer contained in the said metal-particle content layer means the polymer component which occupies 50 mass% or more of the polymer contained in the said metal-particle content layer.
  • the content of the polyester resin with respect to the metal particles contained in the metal particle-containing layer is preferably 1 to 10000% by mass, more preferably 10 to 1000% by mass, It is particularly preferably 20 to 500% by mass.
  • the refractive index n of the medium is preferably 1.4 to 1.7.
  • the thickness of the hexagonal or circular plate-like metal particles is a, 80% or more of the hexagonal or circular plate-like metal particles are a / in the thickness direction.
  • the hexagonal or circular plate-like metal particles are buried in the metal particle-containing layer at a certain ratio or more, whereby the rubbing resistance can be further increased. That is, the heat ray shielding material of the present invention is preferably in the mode of FIG. 5B rather than the mode of FIG. 5C.
  • the area ratio [(B / A) ⁇ 100], which is the ratio of the 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 base material from above or an image obtained by AFM (atomic force microscope) observation. .
  • the average inter-particle distance between the metal tabular grains adjacent in the horizontal direction in the metal particle-containing layer is preferably 1/10 or more of the average particle diameter of the metal tabular grains in terms of visible light transmittance and maximum heat ray reflectance. .
  • the horizontal average inter-grain distance of the metal tabular grains is less than 1/10 of the average grain diameter of the metal tabular grains, the maximum reflectance 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 inter-particle distance in the horizontal direction of the metal tabular grains means an average value of inter-particle distances between two adjacent grains.
  • the average inter-particle distance is random as follows: “When taking a two-dimensional autocorrelation of luminance values when binarizing an SEM image including 100 or more metal tabular grains, other than the origin. It has no significant local maximum.
  • the tabular metal grains are arranged in the form of a metal particle-containing layer containing tabular metal grains, as shown in FIGS. 5A to 5E.
  • the metal particle-containing layer may be composed of a single layer as shown in FIGS. 5A to 5E, or may be composed of a plurality of metal particle-containing layers. When comprised with a several metal particle content layer, it becomes possible to provide the shielding performance according to the wavelength range
  • the heat ray shielding material of the present invention has a thickness d of the outermost metal particle-containing layer at least in the outermost metal particle-containing layer. It is preferable that 80% by number or more of the hexagonal or circular tabular metal particles are present in the range of d ′ / 2 from the surface of the outermost metal particle-containing layer.
  • the thickness of the metal particle-containing layer is preferably 10 to 160 nm, and more preferably 20 to 80 nm.
  • the thickness d of the metal particle-containing layer is preferably a to 10a, more preferably 2a to 8a, where a is the thickness of the hexagonal or circular flat metal particles.
  • 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. Moreover, even when it has other layers, such as an overcoat layer mentioned later, on the said metal-particle content layer of a heat ray shielding material, the boundary of another layer and the said metal-particle content layer is determined by the same method. And the thickness d of the metal particle-containing layer can be determined.
  • the boundary between the metal particle-containing layer and the metal particle-containing layer is usually determined by an SEM observation image. And the thickness d of the metal particle-containing layer can be determined.
  • the method for synthesizing the metal tabular grain is not particularly limited as long as it can synthesize hexagonal or circular tabular metal particles, and can be appropriately selected according to the purpose.
  • a chemical reduction method examples thereof include liquid phase methods such as a photochemical reduction method and 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 to triangular tabular metal grains can be obtained by, for example, etching treatment with a dissolved species that dissolves silver such as nitric acid and sodium sulfite, and aging treatment by heating.
  • the flat metal particles having a hexagonal shape or a circular shape may be obtained.
  • a seed crystal may be previously fixed on the surface of a transparent substrate such as a film or glass, and then metal grains (for example, Ag) may be grown in a tabular form.
  • metal grains for example, Ag
  • the metal tabular grains 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 metal tabular grain may be coated with a high refractive index material having high visible light region transparency.
  • the 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 SiO 2 or polymer shell layer is appropriately formed, The 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 of deteriorating the matrix in which the metal tabular grains are dispersed. After forming a TiO x layer on the tabular grains, an SiO 2 layer may be appropriately formed.
  • the metal tabular grains may adsorb an antioxidant such as mercaptotetrazole or ascorbic acid in order to prevent oxidation of metals such as silver constituting the metal tabular grains.
  • an oxidation sacrificial layer such as Ni may be formed on the surface of the metal tabular grain for the purpose of preventing oxidation. Further, it may be covered with a metal oxide film such as SiO 2 for the purpose of blocking oxygen.
  • the metal tabular grain is, for example, a low molecular weight dispersant or a high molecular weight dispersant containing at least one of N elements such as quaternary ammonium salts and amines, S elements, and P elements.
  • a dispersant may be added.
  • the heat ray shielding material of the present invention has a polymer film as a base material, and the adhesion between the metal particle-containing layer and the polymer film is a cross-cut cello tape (registered trademark) peel test defined in JIS K5600-5-6. It is characterized by 2 points or less.
  • the heat ray shielding material has a base material on the surface opposite to the surface of the metal particle-containing layer on which 80% by number or more of the hexagonal or circular plate-like metal particles are unevenly distributed. preferable.
  • 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 heat ray shielding material. It can be appropriately selected according to the above.
  • the material of the base material used for the heat ray shielding material of the present invention is not particularly limited except that it is a polymer film, and can be appropriately selected from various transparent plastic films according to the situation.
  • 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 heat ray shielding material 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 functional film includes 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 heat ray shielding material of the present invention in order to prevent oxidation and sulfidation of the metal tabular grains due to mass transfer and to provide scratch resistance, the heat ray shielding material of the present invention comprises the hexagonal or circular tabular metal particles. You may have the overcoat layer closely_contact
  • the heat ray shielding material of the present invention particularly when the metal tabular grains are unevenly distributed on the surface of the metal particle-containing layer, prevents contamination of the production process due to peeling of the metal tabular grains, prevents the disorder of the arrangement of the metal tabular grains at the time of coating another layer, etc. Therefore, it may have an overcoat layer.
  • 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.For example, 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 depending on the purpose, and may be an adhesive layer, or a layer (for example, an overcoat) between the adhesive layer and the metal particle-containing layer. Layer). In any case, the ultraviolet absorber is preferably added to a layer disposed on the side irradiated with sunlight with respect to the metal particle-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 binder absorbs heat rays, the reflection effect of the metal tabular grains is weakened. Therefore, the ultraviolet absorbing layer formed between the heat ray source and the metal tabular grains 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 thickness of the ultraviolet absorbing layer is preferably 0.01 ⁇ m to 1,000 ⁇ m, more preferably 0.02 ⁇ m to 500 ⁇ m.
  • the absorption of ultraviolet rays may be insufficient, and when it exceeds 1,000 ⁇ m, the visible light transmittance may decrease.
  • the content of the ultraviolet absorbing layer varies depending on the ultraviolet absorbing layer to be used and cannot be generally defined, but it is preferable to appropriately select a content that gives a desired ultraviolet transmittance in the heat ray shielding material of the present invention.
  • the ultraviolet transmittance is preferably 5% or less, and more preferably 2% or less. When the ultraviolet transmittance exceeds 5%, the color of the metal tabular grain layer may change due to ultraviolet rays of sunlight.
  • the heat ray shielding material of the present invention preferably contains at least one kind of metal oxide particles in order to absorb long wave infrared rays from the viewpoint of balance between heat ray shielding and production cost.
  • the layer containing the metal oxide particles is a surface of the metal particle-containing layer on which the hexagonal or circular plate-like metal particles of the metal particle-containing layer are exposed. It is preferable to have it on the opposite surface side.
  • the hard coat layer 5 preferably contains metal oxide particles.
  • the hard coat layer 5 may be laminated with the metal particle-containing layer 2 via the substrate 1.
  • the metal particle-containing layer 2 when the heat ray shielding material of the present invention is disposed so that the metal particle-containing layer 2 is on the incident direction side of the heat rays such as sunlight, the metal particle-containing layer 2 can After reflecting the part (or all), the hard coat layer 5 absorbs a part of the heat rays, and the heat ray shielding is caused by the heat rays that are not absorbed by the metal oxide-containing layer and pass through the heat ray shielding material.
  • the amount of heat directly received inside the material and the amount of heat absorbed by the metal oxide-containing layer of the heat ray shielding material and indirectly transmitted to the inside of the heat ray shielding material can be reduced.
  • a tin dope indium oxide (henceforth "ITO")
  • a tin dope antimony oxide (henceforth).
  • ATO tin dope antimony oxide
  • ITO, ATO, and zinc oxide are more preferable, and infrared rays having a wavelength of 1,200 nm or more are preferably 90 in that they have excellent heat ray absorption ability and can produce a heat ray shielding material having a wide range of heat ray absorption ability when combined with metal tabular grains.
  • ITO is preferable in that it has a visible light transmittance of 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.
  • limiting in particular as 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.
  • Method for forming metal particle-containing layer The method for forming the metal particle-containing layer of the present invention is not particularly limited and may be appropriately selected depending on the purpose.
  • a dispersion having the metal tabular particles on the surface of the lower layer such as the substrate. May be applied by a dip coater, a die coater, a slit coater, a bar coater, a gravure coater, or the like, or may be subjected to surface orientation by a method such as an LB film method, a self-organization method, or spray coating.
  • the composition of the metal particle-containing layer used in the examples described later, and by adding latex or the like, more than 80% by number of the hexagonal or circular plate metal particles are It is preferable to be in a range of d / 2 from the surface of the metal particle-containing layer. More preferably, 80% by number or more of the hexagonal or circular plate-like metal particles are present in a range of d / 3 from the surface of the metal particle-containing layer.
  • the amount of the latex added is not particularly limited. For example, it is preferably added in an amount of 1 to 10,000% by mass, more preferably 10 to 1000% by mass, and more preferably 20 to 500% by mass based on the tabular metal particles. It is particularly preferred.
  • a pressure roller such as a calender roller or a lami roller.
  • the overcoat layer is preferably formed by coating.
  • the coating method at this time is not particularly limited, and a known method can be used.
  • a dispersion containing the ultraviolet absorber can be used as a dip coater, a die coater, a slit coater, a bar coater, a gravure coater, or the like. The method of apply
  • coating by etc. is mentioned.
  • the hard coat layer is preferably formed by coating.
  • the coating method at this time is not particularly limited, and a known method can be used.
  • a dispersion containing the ultraviolet absorber can be used as a dip coater, a die coater, a slit coater, a bar coater, a gravure coater, or the like. The method of apply
  • coating by etc. is mentioned.
  • the adhesive layer is preferably formed by coating.
  • it can be laminated on the surface of the lower layer such as the substrate, the metal particle-containing layer, or the 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 automotive glass or building glass, the outside may be difficult to see.
  • the ultraviolet ray transmittance of the heat ray shielding material of the present invention is preferably 5% or less, more preferably 2% or less.
  • the haze of the heat ray shielding material 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.
  • Adhesive layer lamination by dry lamination When the functionality is imparted to the existing window glass using the heat ray shielding material film of the present invention, an adhesive is laminated and attached to the indoor side of the glass. In that case, it is better to laminate the adhesive layer on the silver nanodisk particle layer and paste it from the surface to the window glass, because the reflective layer facing the sunlight side will prevent heat generation as much as possible. It is.
  • a coating solution containing a pressure-sensitive adhesive can be applied directly to the surface, but various additives, plasticizers and solvents used in the pressure-sensitive adhesive However, in some cases, the arrangement of the silver nanodisk layer may be disturbed, or the silver nanodisk itself may be altered.
  • a film is prepared by previously applying and drying an adhesive on a release film, and the adhesive surface of the film and the silver nanodisk layer surface of the film of the present invention are prepared. It is effective to laminate in a dry state.
  • the heat ray shielding material of this invention manufactured as mentioned above is glass or plastics for vehicles, such as a motor vehicle. And a method of bonding to glass or plastic for building materials.
  • the heat ray shielding material of the present invention is not particularly limited as long as it is an embodiment used for selectively reflecting or absorbing heat rays (near infrared rays), and may be appropriately selected according to the purpose. Examples include films and laminated structures, building material films and laminated structures, agricultural films, and the like. Among these, in terms of energy saving effect, a vehicle film and a laminated structure, a building material film and a laminated structure are preferable.
  • heat rays mean near infrared rays (780 nm to 1,800 nm) contained in sunlight by about 50%.
  • a white precipitate mixed solution of silver sulfite obtained 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 was added. The mixture was stirred until the silver was sufficiently reduced, and 72 mL of 0.17 M NaOH aqueous solution was added. Thus, a tabular silver particle dispersion A was obtained.
  • silver tabular grain dispersion liquid A it was confirmed that silver hexagonal tabular grains having an average equivalent circular diameter of 240 nm (hereinafter referred to as Ag hexagonal tabular grains) were formed. Further, when the thickness of the hexagonal tabular grains was measured with an atomic force microscope (Nanocute II, manufactured by Seiko Instruments Inc.), it was found that tabular grains having an average of 8 nm and an aspect ratio of 17.5 were generated. . The results are shown in Table 1.
  • the shape uniformity of Ag tabular grains is the shape of 200 grains arbitrarily extracted from the observed SEM image, hexagonal or circular tabular metal grains are A, an irregular shape such as a teardrop shape, and a substantially hexagonal shape. Image analysis was carried out by assuming that polygonal particles of less than B were B, and the ratio (number%) of the number of particles corresponding to A was obtained.
  • 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 of the tabular grains A (average equivalent circle diameter), and the standard deviation of the particle size distribution is the average particle diameter ( The coefficient of variation (%) of the particle size distribution of the tabular grains A divided by the average equivalent circle diameter was determined.
  • the obtained dispersion liquid containing tabular metal particles is dropped on a glass substrate and dried, and the thickness of one tabular metal particle corresponding to A is measured by an atomic force microscope (AFM) (Nanocute II, manufactured by Seiko Instruments Inc.). ).
  • the measurement conditions using the AFM were a self-detecting sensor, DFM mode, a measurement range of 5 ⁇ m, a scanning speed of 180 seconds / frame, and a data point of 256 ⁇ 256.
  • the average value of the obtained data was defined as the average grain thickness of the tabular grain A.
  • Example 1 -Preparation of coating solution 1- A coating solution 1 having the composition shown below was prepared.
  • Surfactant B Aronactee CL-95 (Sanyo Chemical Industries, Ltd., solid content: 1% by mass) 15.5 parts by mass: Silver tabular grain dispersion B1 of Production Example 1 200 parts by mass, water: 800 parts by mass
  • Example 1 -Formation of metal particle containing layer-
  • a PET film Cosmo Shine A4300, manufactured by Toyobo Co., Ltd., thickness: 75 ⁇ m
  • the coating liquid 1 is applied using a wire bar so that the average thickness after drying is 0.08 ⁇ m (80 nm). did. 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 obtained.
  • the average thickness of the metal particle-containing layer after drying is as follows: the thickness of the PET film before applying the coating solution 1 using a laser microscope (VK-8510, manufactured by Keyence Corporation); It can be calculated by measuring the difference from the thickness after heating, drying and solidification as the thickness and averaging the thickness of these 10 points.
  • the heat ray shielding material was cleaved with a razor in a frozen state with liquid nitrogen, and a vertical section sample of the heat ray shielding material was produced. This vertical section sample was observed with a scanning electron microscope (SEM), and the inclination angle (corresponding to ⁇ ⁇ in FIG. 5D) of the 100 metal tabular grains with respect to the horizontal plane was calculated as an average value.
  • SEM scanning electron microscope
  • 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.
  • Example 2 In Example 1, except that the amount of the polyester latex aqueous dispersion added to the coating liquid 1 was changed to 3.2 parts by mass and the average thickness after drying was 0.009 ⁇ m (9 nm). In the same manner as described above, a thermal battle shielding material of Example 2 was prepared.
  • Example 3 In Example 1, the amount of the polyester latex aqueous dispersion added to the coating liquid 1 was changed to 7.0 parts by weight, and the coating was performed so that the average thickness after drying was 0.02 ⁇ m (20 nm). In the same manner as described above, a thermal battle shielding material of Example 3 was prepared.
  • Example 4 In Example 1, the amount of the polyester latex aqueous dispersion added to the coating liquid 1 was changed to 52.9 parts by mass, and the coating was applied so that the average thickness after drying was 0.15 ⁇ m (150 nm). In the same manner as described above, a thermal battle shielding material of Example 4 was prepared.
  • Example 5 Example 1 except that the amount of the polyester latex aqueous dispersion added to the coating solution 1 was changed to 63.5 parts by mass in Example 1 and the average thickness after drying was 0.18 ⁇ m (180 nm). In the same manner as described above, a thermal battle shielding material of Example 5 was prepared.
  • Example 1 Comparative Example 1
  • surfactant A, surfactant B and polyester latex aqueous dispersion of coating solution 1 were not added. Instead, surfactant C was added to coating solution 1 (W-1 below: solid content 2% by mass).
  • the heat ray shielding material of the comparative example 1 was produced like Example 1 except having added 200 mass of.
  • the metal particle content layer of the heat ray shielding material of the comparative example 1 did not contain a polymer, and the film thickness d was 100 nm.
  • Example 2 In Example 1, except that 100 parts by mass of gelatin having a number average molecular weight of 200,000 or more was further added to the coating solution 1, a comparison was made in that the film thickness d of the metal particle-containing layer was 80 nm in the same manner as in Example 1. The heat ray shielding material of Example 2 was produced. It has been found that the addition of gelatin disturbs the arrangement of the metal particles and deteriorates the plane orientation (see Table 2 described later).
  • the heat ray shielding material of the present invention has high visible light transmittance and high solar reflectance, is excellent in heat shielding performance, and has high cross-cut adhesion between the metal particle-containing layer and the polymer film as the base material. Since the arrangement can be maintained, it can be suitably used as various members that are required to prevent the transmission of heat rays, such as films for automobiles, buses, etc., laminated structures, films for building materials, laminated structures, etc. It is.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Optical Filters (AREA)
  • Laminated Bodies (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

La présente invention porte sur une matière de protection contre les rayons thermiques qui a un film polymère en tant que matière de base, et une couche à teneur en particules métalliques qui est disposée sur au moins une surface du film polymère et qui contient au moins un type de particules métalliques. Les particules métalliques comprennent au moins 60 % en nombre de particules métalliques planes de forme hexagonale ou circulaire. Le plan principal des particules métalliques planes de forme hexagonale ou circulaire est orienté à une moyenne de 0°- ±30° vers l'une des surfaces de la couche à teneur en particules métalliques, et la couche à teneur en particules métalliques comprend un polymère. L'adhérence entre la couche à teneur en particules métalliques et le film polymère marque 2 points ou moins dans un test de pelage de Cellotape® de quadrillage tel que défini dans JIS K5600-5-6. La matière de protection contre les rayons thermiques présente une excellente transmittance de la lumière visible et des performances de protection contre la chaleur (réflectance solaire), et l'adhérence de quadrillage entre la couche à teneur en particules métalliques et le film polymère, qui est la matière de base, est excellente.
PCT/JP2012/073662 2011-09-15 2012-09-14 Matière de protection contre les rayons thermiques WO2013039215A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011202385 2011-09-15
JP2011-202385 2011-09-15

Publications (1)

Publication Number Publication Date
WO2013039215A1 true WO2013039215A1 (fr) 2013-03-21

Family

ID=47883431

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/073662 WO2013039215A1 (fr) 2011-09-15 2012-09-14 Matière de protection contre les rayons thermiques

Country Status (2)

Country Link
JP (1) JP2013077007A (fr)
WO (1) WO2013039215A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9091812B2 (en) 2009-11-06 2015-07-28 Sharp Laboratories Of America, Inc. Energy-efficient transparent solar film
WO2014178180A1 (fr) * 2013-04-29 2014-11-06 Sharp Kabushiki Kaisha Film solaire transparent à haut rendement énergétique, procédé de fabrication d'un matériau d'absorption optique à film solaire et fenêtre à haut rendement énergétique
JP6375272B2 (ja) * 2015-07-31 2018-08-15 富士フイルム株式会社 遮熱材料、断熱材料、及び窓ガラス
LU100018B1 (en) * 2017-01-11 2018-08-14 Luxembourg Inst Science & Tech List Infrared reflective and electrical conductive composite film and manufacturing method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005095097A1 (fr) * 2004-03-31 2005-10-13 Toray Industries, Inc. Film stratifie
JP2009139925A (ja) * 2007-11-16 2009-06-25 Epson Toyocom Corp 光学多層膜フィルタ、光学多層膜フィルタの製造方法および電子機器装置
JP2011118347A (ja) * 2009-11-06 2011-06-16 Fujifilm Corp 熱線遮蔽材

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005095097A1 (fr) * 2004-03-31 2005-10-13 Toray Industries, Inc. Film stratifie
JP2009139925A (ja) * 2007-11-16 2009-06-25 Epson Toyocom Corp 光学多層膜フィルタ、光学多層膜フィルタの製造方法および電子機器装置
JP2011118347A (ja) * 2009-11-06 2011-06-16 Fujifilm Corp 熱線遮蔽材

Also Published As

Publication number Publication date
JP2013077007A (ja) 2013-04-25

Similar Documents

Publication Publication Date Title
WO2013137373A1 (fr) Film de protection contre les rayons infrarouges
WO2013035802A1 (fr) Matière de protection vis-à-vis du rayonnement thermique
JP5956291B2 (ja) 多層構造および貼合せ構造体
JP5833518B2 (ja) 熱線遮蔽材
JP5878059B2 (ja) 赤外線遮蔽フィルム
JP5771584B2 (ja) 熱線遮蔽材
JP5709707B2 (ja) 熱線遮蔽材
WO2012070477A1 (fr) Matériau de protection contre le rayonnement thermique
JP5878139B2 (ja) 熱線遮蔽材および貼合せ構造体
WO2013146447A1 (fr) Film contenant des particules d'argent et son procédé de fabrication, et matériau de protection contre les rayonnements thermiques
JP5703156B2 (ja) 熱線遮蔽材
JP5922919B2 (ja) 熱線遮蔽材および貼合せ構造体
JP5833516B2 (ja) 遠赤外線遮蔽材
WO2014038457A1 (fr) Film arrêtant les infrarouges
WO2012157655A1 (fr) Matériau de protection contre les rayons thermiques, structure stratifiée et verre feuilleté
WO2013039215A1 (fr) Matière de protection contre les rayons thermiques
JP5878050B2 (ja) 熱線遮蔽材
JP6012527B2 (ja) 熱線遮蔽材、合わせガラス用中間膜および合わせガラス
JP2013210573A (ja) 熱線遮蔽材

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12831897

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12831897

Country of ref document: EP

Kind code of ref document: A1