WO2013039215A1 - Heat-ray shielding material - Google Patents
Heat-ray shielding material Download PDFInfo
- 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
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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.
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Abstract
This heat-ray shielding material has a polymer film as a base material, and a metal particle-containing layer that is disposed on at least one surface of the polymer film and that contains at least one type of metal particle. The metal particles comprise at least 60% by number of hexagonal or circular-shaped planar metal particles. The main plane of the hexagonal or circular-shaped planar metal particles is oriented at an average of 0°-±30° to one of the surfaces of the metal particle-containing layer, and the metal particle-containing layer includes a polymer. The adhesion between the metal particle-containing layer and the polymer film scores 2 points or less in a cross-cut Cellotape® peeling test as defined in JIS K5600-5-6. The heat-ray shielding material exhibits excellent visible light transmittance and heat shielding performance (solar reflectance), and the cross-cut adhesion between the metal particle-containing layer and the polymer film, which is the base material, is excellent.
Description
本発明は、熱線遮蔽材に関する。より詳しくは、可視光透過性および遮熱性能が良好であり、金属粒子含有層と基材であるポリマーフィルムとの密着性が良好な熱線遮蔽材に関する。
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.
近年、二酸化炭素削減のための省エネルギー施策の一つとして、自動車や建物の窓に対する熱線遮蔽性付与材料が開発されている。熱線遮蔽性（日射熱取得率）の観点からは、吸収した光の室内への再放射（吸収した日射エネルギーの約１／３量）がある熱線吸収型より、再放射がない熱線反射型が望ましく、様々な提案がなされている。
In recent years, 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.
赤外線遮蔽フィルタとして、Ａｇ平板粒子を用いたフィルタが提案されている（特許文献１参照）。しかし、特許文献１に記載の赤外線遮蔽フィルタはプラズマディスプレイパネル（ＰＤＰ）に用いることを意図したものであり、かかるＡｇ平板粒子は、その配列制御がなされていないことから、主に赤外域の波長光赤外線吸収体として機能し、積極的に熱線を反射する材料として機能するものではなかった。したがって、かかるＡｇ平板粒子からなる赤外線遮蔽フィルタを直射日光の遮熱に使用すると、この赤外線吸収フィルタ自体が暖まることになり、その熱で室温が上昇してしまうために、赤外線遮蔽材としての機能は不十分であった。また、特許文献１の実施例ではＡｇ平板粒子を含む分散液をガラス上に塗布して乾燥させて赤外線遮蔽フィルタを形成しているものの、クロスカット試験についての記載がなかった。
A filter using Ag tabular grains has been proposed as an infrared shielding filter (see Patent Document 1). However, 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. Moreover, in the Example of patent document 1, although the dispersion liquid containing Ag tabular grain was apply | coated on glass and it was made to dry and the infrared rays shielding filter was formed, there was no description about the crosscut test.
特許文献２には粒状の銀を用いた波長選択膜が記載されている。特許文献２ではＡｇのスパッタリングおよび熱処理によって粒状の銀粒子が分布したＡｇ層を形成しており、同文献の図３によれば粒状の銀粒子の形状は不定型のものが多かった。また、特許文献２にはクロスカット試験についての記載がなかった。
Patent Document 2 describes a wavelength selective film using granular silver. In Patent Document 2, 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.
一方、特許文献３には、六角形状乃至円形状の平板状金属粒子を６０個数％以上有し、前記六角形状乃至円形状の平板状金属粒子の主平面が前記金属粒子含有層の一方の表面に対して平均０°～±３０°の範囲で面配向している熱線遮蔽材が開示されている。しかしながら、特許文献３にはクロスカット試験についての記載がなかった。
On the other hand, in 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. In contrast, a heat ray shielding material having a plane orientation in an average range of 0 ° to ± 30 ° is disclosed. However, Patent Document 3 did not describe a crosscut test.
本発明者の検討によれば、特許文献１に記載の赤外線遮蔽フィルターは赤外線吸収型のため、太陽光の遮熱に使用すると赤外線吸収体が暖まってしまい、室内の温度上昇を起こしてしまう問題があった。また、窓ガラスに貼り合わせたとき、太陽光が当たる場所と当たらない場所で温度上昇が異なる影響でガラスが割れる（熱われ）などが起こる問題があった。
特許文献２は粒状の銀で赤外線を遮蔽すると、スペクトルの半値巾が大きく、赤外線をシャープに遮蔽することができないため、太陽光のエネルギーが多い短波側の赤外線を十分に遮蔽できない問題があった。
特許文献１のように銀平板粒子をランダムに並べると吸収しかしないのに対し、特許文献３に記載の熱線遮蔽材のように規則配列させると反射するようになり、赤外線遮蔽フィルムとして有利になるものであった。ここで、特許文献３には上記のとおりクロスカット試験について検討されていなかったため、本発明者が同文献の実施例の塗布膜を作成してクロスカット試験を行った結果、基材フィルムと銀平板粒子含有層とがクロスカット試験で剥離してしまう問題があることがわかった。 According to the study of the present inventor, since the infrared shielding filter described inPatent 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. In addition, when pasted on a window glass, there is a problem that 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. .
When silver tabular grains are randomly arranged as inPatent 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. Here, since 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.
特許文献２は粒状の銀で赤外線を遮蔽すると、スペクトルの半値巾が大きく、赤外線をシャープに遮蔽することができないため、太陽光のエネルギーが多い短波側の赤外線を十分に遮蔽できない問題があった。
特許文献１のように銀平板粒子をランダムに並べると吸収しかしないのに対し、特許文献３に記載の熱線遮蔽材のように規則配列させると反射するようになり、赤外線遮蔽フィルムとして有利になるものであった。ここで、特許文献３には上記のとおりクロスカット試験について検討されていなかったため、本発明者が同文献の実施例の塗布膜を作成してクロスカット試験を行った結果、基材フィルムと銀平板粒子含有層とがクロスカット試験で剥離してしまう問題があることがわかった。 According to the study of the present inventor, since the infrared shielding filter described in
When silver tabular grains are randomly arranged as in
これに対し、特許文献４にはクロスカット密着力が良好である赤外線遮蔽フィルムが記載されている。同文献の実施例では金属粒子として三酸化アンチモン酸化スズ粒子を使用しており、また明細書中に金属粒子の形状や配列についての記載はなかった。また、特許文献４に記載の方式では、上記の特許文献２の方式と同様に太陽光の遮蔽に使用すると赤外線を反射しないため窓が熱くなり、熱われなどが起こる問題があった。
In contrast, Patent Document 4 describes an infrared shielding film having good cross-cut adhesion. In the examples of the same document, 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. Further, 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.
本発明は、従来における前記諸問題を解決することを目的とする。すなわち、本発明が解決しようとする課題は、可視光透過性および遮熱性能（日射反射率）が良好であり、金属粒子含有層と基材であるポリマーフィルムとの密着性が良好な熱線遮蔽材を提供することにある。
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.
本発明者は、前記課題を解決すべく、金属粒子含有層における金属平板粒子の存在状態を鋭意検討した結果、金属平板粒子の形状や、その面配向があまりにランダムであると熱線遮蔽性能に劣ることがわかった。また、特許文献３の構成では、金属粒子含有層と基材であるポリマーフィルムとのクロスカット密着性が不十分であり、ポリマーフィルムが剥がれてしまうことがあることを見出すに至った。
そこで、特許文献３の構成において、金属平板粒子層にバインダーとしてポリマーを存在させることにより、可視光透過性および遮熱性能（日射反射率）が良好であり、金属粒子含有層と基材であるポリマーフィルムとのクロスカット密着性が良好な熱線遮蔽材を提供できることを見出すに至った。 As a result of earnestly examining the existence state of the tabular metal grains in the metal particle-containing layer in order to solve the above-mentioned problems, the present inventors have poor heat ray shielding performance when the shape of the tabular metal grains and the plane orientation thereof are too random. I understood it. Moreover, in the structure ofpatent document 3, it came to discover that the crosscut adhesiveness of the metal particle content layer and the polymer film which is a base material is inadequate, and a polymer film may peel off.
Then, in the structure ofpatent document 3, by making a polymer exist as a binder in a metal tabular grain layer, visible light permeability and heat insulation performance (sunlight reflectance) are favorable, and it is a metal particle content layer and a base material. It came to discover that the heat ray shielding material with favorable crosscut adhesiveness with a polymer film can be provided.
そこで、特許文献３の構成において、金属平板粒子層にバインダーとしてポリマーを存在させることにより、可視光透過性および遮熱性能（日射反射率）が良好であり、金属粒子含有層と基材であるポリマーフィルムとのクロスカット密着性が良好な熱線遮蔽材を提供できることを見出すに至った。 As a result of earnestly examining the existence state of the tabular metal grains in the metal particle-containing layer in order to solve the above-mentioned problems, the present inventors have poor heat ray shielding performance when the shape of the tabular metal grains and the plane orientation thereof are too random. I understood it. Moreover, in the structure of
Then, in the structure of
本発明は、本発明者による前記知見に基づくものであり、前記課題を解決するための手段としては、以下のとおりである。
［１］ 基材であるポリマーフィルムと、該ポリマーフィルムの少なくとも一方の面上に配置され、かつ、少なくとも１種の金属粒子を含有する金属粒子含有層を有し、前記金属粒子が、六角形状乃至円形状の平板状金属粒子を６０個数％以上有し、前記六角形状乃至円形状の平板状金属粒子の主平面が、前記金属粒子含有層の一方の表面に対して平均０°～±３０°の範囲で面配向し、前記金属粒子含有層がポリマーを含み、前記金属粒子含有層と前記ポリマーフィルムの密着がＪＩＳ Ｋ５６００－５－６に定められたクロスカットセロテープ（登録商標）剥離試験で2点以下であることを特徴とする熱線遮蔽材。
［２］ ［１］に記載の熱線遮蔽材は、前記金属粒子含有層に含まれるポリマーがポリエステル樹脂を含むことが好ましい。
［３］ ［１］または［２］に記載の熱線遮蔽材は、前記金属粒子含有層に含まれる前記ポリマーの主ポリマーが、ポリエステル樹脂であることが好ましい。
［４］ ［２］または［３］に記載の熱線遮蔽材は、前記金属粒子含有層に含まれる前記金属粒子に対する前記ポリエステル樹脂の含有量が１～１００００質量％であることが好ましい。
［５］ ［１］～［４］のいずれか一項に記載の熱線遮蔽材は、前記金属粒子含有層の膜厚が、１０～１６０ｎｍであることが好ましい。
［６］ ［１］～［５］のいずれか一項に記載の熱線遮蔽材は、前記ポリマーフィルムがＰＥＴフィルムであることが好ましい。
［７］ ［１］～［６］のいずれか一項に記載の熱線遮蔽材は、前記六角形状乃至円形状の平板状金属粒子の平均粒子径が７０ｎｍ～５００ｎｍであり、前記六角形状乃至円形状の平板状金属粒子のアスペクト比（平均粒子径／平均粒子厚み）が８～４０であることが好ましい。
［８］ ［１］～［７］のいずれか一項に記載の熱線遮蔽材は、前記六角形状乃至円形状の平板状金属粒子が、少なくとも銀を含むことが好ましい。
［９］ ［１］～［８］のいずれか一項に記載の熱線遮蔽材は、可視光透過率が７０％以上であることが好ましい。
［１０］ ［１］～［９］のいずれか一項に記載の熱線遮蔽材は、赤外光を反射することが好ましい。 This invention is based on the said knowledge by this inventor, As means for solving the said subject, it is as follows.
[1] A polymer film that is a base material, and a metal particle-containing layer that is disposed on at least one surface of the polymer film and contains at least one metal particle, and the metal particles are hexagonal Or 60% by number or more of flat plate-like metal particles having a circular shape, and the main plane of the hexagonal or circular plate-like metal particles has an average of 0 ° to ± 30 with respect to one surface of the metal particle-containing layer. In the cross-cut cello tape (registered trademark) peel test defined in JIS K5600-5-6, 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.
[2] In the heat ray shielding material according to [1], the polymer contained in the metal particle-containing layer preferably contains a polyester resin.
[3] In the heat ray shielding material according to [1] or [2], the main polymer of the polymer contained in the metal particle-containing layer is preferably a polyester resin.
[4] In the heat ray shielding material according to [2] or [3], 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%.
[5] In the heat ray shielding material according to any one of [1] to [4], the thickness of the metal particle-containing layer is preferably 10 to 160 nm.
[6] In the heat ray shielding material according to any one of [1] to [5], the polymer film is preferably a PET film.
[7] In the heat ray shielding material according to any one of [1] to [6], 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.
[8] In the heat ray shielding material according to any one of [1] to [7], it is preferable that the hexagonal or circular flat metal particles include at least silver.
[9] The heat ray shielding material according to any one of [1] to [8] preferably has a visible light transmittance of 70% or more.
[10] The heat ray shielding material according to any one of [1] to [9] preferably reflects infrared light.
［１］ 基材であるポリマーフィルムと、該ポリマーフィルムの少なくとも一方の面上に配置され、かつ、少なくとも１種の金属粒子を含有する金属粒子含有層を有し、前記金属粒子が、六角形状乃至円形状の平板状金属粒子を６０個数％以上有し、前記六角形状乃至円形状の平板状金属粒子の主平面が、前記金属粒子含有層の一方の表面に対して平均０°～±３０°の範囲で面配向し、前記金属粒子含有層がポリマーを含み、前記金属粒子含有層と前記ポリマーフィルムの密着がＪＩＳ Ｋ５６００－５－６に定められたクロスカットセロテープ（登録商標）剥離試験で2点以下であることを特徴とする熱線遮蔽材。
［２］ ［１］に記載の熱線遮蔽材は、前記金属粒子含有層に含まれるポリマーがポリエステル樹脂を含むことが好ましい。
［３］ ［１］または［２］に記載の熱線遮蔽材は、前記金属粒子含有層に含まれる前記ポリマーの主ポリマーが、ポリエステル樹脂であることが好ましい。
［４］ ［２］または［３］に記載の熱線遮蔽材は、前記金属粒子含有層に含まれる前記金属粒子に対する前記ポリエステル樹脂の含有量が１～１００００質量％であることが好ましい。
［５］ ［１］～［４］のいずれか一項に記載の熱線遮蔽材は、前記金属粒子含有層の膜厚が、１０～１６０ｎｍであることが好ましい。
［６］ ［１］～［５］のいずれか一項に記載の熱線遮蔽材は、前記ポリマーフィルムがＰＥＴフィルムであることが好ましい。
［７］ ［１］～［６］のいずれか一項に記載の熱線遮蔽材は、前記六角形状乃至円形状の平板状金属粒子の平均粒子径が７０ｎｍ～５００ｎｍであり、前記六角形状乃至円形状の平板状金属粒子のアスペクト比（平均粒子径／平均粒子厚み）が８～４０であることが好ましい。
［８］ ［１］～［７］のいずれか一項に記載の熱線遮蔽材は、前記六角形状乃至円形状の平板状金属粒子が、少なくとも銀を含むことが好ましい。
［９］ ［１］～［８］のいずれか一項に記載の熱線遮蔽材は、可視光透過率が７０％以上であることが好ましい。
［１０］ ［１］～［９］のいずれか一項に記載の熱線遮蔽材は、赤外光を反射することが好ましい。 This invention is based on the said knowledge by this inventor, As means for solving the said subject, it is as follows.
[1] A polymer film that is a base material, and a metal particle-containing layer that is disposed on at least one surface of the polymer film and contains at least one metal particle, and the metal particles are hexagonal Or 60% by number or more of flat plate-like metal particles having a circular shape, and the main plane of the hexagonal or circular plate-like metal particles has an average of 0 ° to ± 30 with respect to one surface of the metal particle-containing layer. In the cross-cut cello tape (registered trademark) peel test defined in JIS K5600-5-6, 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.
[2] In the heat ray shielding material according to [1], the polymer contained in the metal particle-containing layer preferably contains a polyester resin.
[3] In the heat ray shielding material according to [1] or [2], the main polymer of the polymer contained in the metal particle-containing layer is preferably a polyester resin.
[4] In the heat ray shielding material according to [2] or [3], 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%.
[5] In the heat ray shielding material according to any one of [1] to [4], the thickness of the metal particle-containing layer is preferably 10 to 160 nm.
[6] In the heat ray shielding material according to any one of [1] to [5], the polymer film is preferably a PET film.
[7] In the heat ray shielding material according to any one of [1] to [6], 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.
[8] In the heat ray shielding material according to any one of [1] to [7], it is preferable that the hexagonal or circular flat metal particles include at least silver.
[9] The heat ray shielding material according to any one of [1] to [8] preferably has a visible light transmittance of 70% or more.
[10] The heat ray shielding material according to any one of [1] to [9] preferably reflects infrared light.
本発明によれば、可視光透過性および遮熱性能（日射反射率）が良好であり、金属粒子含有層と基材であるポリマーフィルムとのクロスカット密着性が良好な熱線遮蔽材を提供することができる。
According to the present invention, there is provided 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.
以下、本発明の熱線遮蔽材について詳細に説明する。
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。なお、本明細書において「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値および上限値として含む範囲を意味する。 Hereinafter, the heat ray shielding material of the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, 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.
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。なお、本明細書において「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値および上限値として含む範囲を意味する。 Hereinafter, the heat ray shielding material of the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, 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.
（熱線遮蔽材）
本発明の熱線遮蔽材は、基材であるポリマーフィルムと、該ポリマーフィルムの少なくとも一方の面上に配置され、かつ、少なくとも１種の金属粒子を含有する金属粒子含有層を有し、前記金属粒子が、六角形状乃至円形状の平板状金属粒子を６０個数％以上有し、前記六角形状乃至円形状の平板状金属粒子の主平面が、前記金属粒子含有層の一方の表面に対して平均０°～±３０°の範囲で面配向し、前記金属粒子含有層がポリマーを含み、前記金属粒子含有層と前記ポリマーフィルムの密着がＪＩＳ Ｋ５６００－５－６に定められたクロスカットセロテープ（登録商標）剥離試験で2点以下であることを特徴とする。
本発明の熱線遮蔽材は、少なくとも１種の金属粒子を含有する金属粒子含有層を有し、必要に応じて、粘着層、紫外線吸収層、基材、金属酸化物粒子含有層などのその他の層を有する態様も好ましい。 (Heat ray shielding material)
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.
本発明の熱線遮蔽材は、基材であるポリマーフィルムと、該ポリマーフィルムの少なくとも一方の面上に配置され、かつ、少なくとも１種の金属粒子を含有する金属粒子含有層を有し、前記金属粒子が、六角形状乃至円形状の平板状金属粒子を６０個数％以上有し、前記六角形状乃至円形状の平板状金属粒子の主平面が、前記金属粒子含有層の一方の表面に対して平均０°～±３０°の範囲で面配向し、前記金属粒子含有層がポリマーを含み、前記金属粒子含有層と前記ポリマーフィルムの密着がＪＩＳ Ｋ５６００－５－６に定められたクロスカットセロテープ（登録商標）剥離試験で2点以下であることを特徴とする。
本発明の熱線遮蔽材は、少なくとも１種の金属粒子を含有する金属粒子含有層を有し、必要に応じて、粘着層、紫外線吸収層、基材、金属酸化物粒子含有層などのその他の層を有する態様も好ましい。 (Heat ray shielding material)
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.
前記熱線遮蔽材１０の層構成としては、図１に示すように、少なくとも１種の金属粒子を含有する金属粒子含有層２を有し、その表面に金属平板粒子３が偏在している態様が挙げられる。また、図２に示すように、金属粒子含有層２と、該金属粒子含有層上にオーバーコート層４とを有し、その表面に金属平板粒子３が偏在している態様が挙げられる。
また、図３Ａに示すように、基材１と、該基材上に金属粒子含有層２と、該金属粒子含有層上に粘着層１１とを有し、基材１の裏面にハードコート層５を有する態様が好適に挙げられる。
また、図３Ｂに示すように、基材１と、該基材上に金属粒子含有層２と、該金属粒子含有層上にオーバーコート層４と、該オーバーコート層上に粘着層１１とを有し、基材１の裏面にハードコート層５を有する態様が好適に挙げられる。 As shown in FIG. 1, the layer structure of the heatray 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. Moreover, as shown in FIG. 2, 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.
Further, as shown in FIG. 3A, thesubstrate 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.
3B, thebase 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.
また、図３Ａに示すように、基材１と、該基材上に金属粒子含有層２と、該金属粒子含有層上に粘着層１１とを有し、基材１の裏面にハードコート層５を有する態様が好適に挙げられる。
また、図３Ｂに示すように、基材１と、該基材上に金属粒子含有層２と、該金属粒子含有層上にオーバーコート層４と、該オーバーコート層上に粘着層１１とを有し、基材１の裏面にハードコート層５を有する態様が好適に挙げられる。 As shown in FIG. 1, the layer structure of the heat
Further, as shown in FIG. 3A, the
3B, the
＜１．金属粒子含有層＞
前記金属粒子含有層は、少なくとも１種の金属粒子を含有する層であり、前記金属粒子が、六角形状乃至円形状の平板状金属粒子を６０個数％以上有し、前記六角形状乃至円形状の平板状金属粒子の主平面が、前記金属粒子含有層の一方の表面に対して平均０°～±３０°の範囲で面配向していれば、特に制限はなく、目的に応じて適宜選択することができる。
前記金属粒子含有層は、前記金属粒子含有層の厚みをｄとしたとき、前記六角形状乃至円形状の平板状金属粒子の８０個数％以上が、前記金属粒子含有層の表面からｄ／２の範囲に存在していることが好ましい。いかなる理論に拘泥するものでもなく、また、本発明の熱線遮蔽材は以下の製造方法に限定されるものではないが、前記金属粒子含有層を製造するときに特定のポリマー（好ましくはラテックス）を添加することなどにより、金属平板粒子を前記金属粒子含有層の一方の表面に偏析させることができる。 <1. Metal particle content layer>
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. There is no particular limitation as long as 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.
In the metal particle-containing layer, when 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. It is not limited to any theory, and 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.
前記金属粒子含有層は、少なくとも１種の金属粒子を含有する層であり、前記金属粒子が、六角形状乃至円形状の平板状金属粒子を６０個数％以上有し、前記六角形状乃至円形状の平板状金属粒子の主平面が、前記金属粒子含有層の一方の表面に対して平均０°～±３０°の範囲で面配向していれば、特に制限はなく、目的に応じて適宜選択することができる。
前記金属粒子含有層は、前記金属粒子含有層の厚みをｄとしたとき、前記六角形状乃至円形状の平板状金属粒子の８０個数％以上が、前記金属粒子含有層の表面からｄ／２の範囲に存在していることが好ましい。いかなる理論に拘泥するものでもなく、また、本発明の熱線遮蔽材は以下の製造方法に限定されるものではないが、前記金属粒子含有層を製造するときに特定のポリマー（好ましくはラテックス）を添加することなどにより、金属平板粒子を前記金属粒子含有層の一方の表面に偏析させることができる。 <1. Metal particle content layer>
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. There is no particular limitation as long as 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.
In the metal particle-containing layer, when 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. It is not limited to any theory, and 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.
－１－１．金属粒子－
前記金属粒子としては、六角形状乃至円形状の平板状金属粒子を６０個数％以上有し、前記六角形状乃至円形状の平板状金属粒子の主平面が、前記金属粒子含有層の一方の表面に対して平均０°～±３０°の範囲で面配向していれば特に制限はなく、目的に応じて適宜選択することができる。前記金属粒子含有層の厚みをｄとしたとき、前記六角形状乃至円形状の平板状金属粒子の８０個数％以上が前記金属粒子含有層の表面からｄ／２の範囲に存在していることが好ましく、前記六角形状乃至円形状の平板状金属粒子の８０個数％以上が、前記金属粒子含有層の表面からｄ／３の範囲に存在することがより好ましい。
前記金属粒子含有層において、六角形状乃至円形状の平板状金属粒子の存在形態としては、金属粒子含有層の一方の表面（本発明の熱線遮蔽材が基材を有する場合は、基材表面）に対して平均０°～±３０°の範囲で面配向している。
なお、前記金属粒子含有層の一方の表面は、フラットな平面であることが好ましい。本発明の熱線遮蔽材の前記金属粒子含有層が仮支持体としての基材を有する場合は、基材の表面とともに略水平面であることが好ましい。ここで、前記熱線遮蔽材は、前記仮支持体を有していてもよく、有していなくてもよい。
前記金属粒子の大きさとしては、特に制限はなく、目的に応じて適宜選択することができ、例えば、５００ｎｍ以下の平均粒子径を有するものであってもよい。
前記金属粒子の材料としては、特に制限はなく、目的に応じて適宜選択することができるが、熱線（近赤外線）の反射率が高い点から、銀、金、アルミニウム、銅、ロジウム、ニッケル、白金などが好ましい。 1-1. Metal particles
The 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. When 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.
In 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.
In addition, it is preferable that one surface of the said metal particle content layer is a flat plane. When 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. Here, the said heat ray shielding material may have the said temporary support body, and does not need to have it.
There is no restriction | limiting in particular as a magnitude | size of the said metal particle, According to the objective, it can select suitably, For example, you may have an average particle diameter of 500 nm or less.
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.
前記金属粒子としては、六角形状乃至円形状の平板状金属粒子を６０個数％以上有し、前記六角形状乃至円形状の平板状金属粒子の主平面が、前記金属粒子含有層の一方の表面に対して平均０°～±３０°の範囲で面配向していれば特に制限はなく、目的に応じて適宜選択することができる。前記金属粒子含有層の厚みをｄとしたとき、前記六角形状乃至円形状の平板状金属粒子の８０個数％以上が前記金属粒子含有層の表面からｄ／２の範囲に存在していることが好ましく、前記六角形状乃至円形状の平板状金属粒子の８０個数％以上が、前記金属粒子含有層の表面からｄ／３の範囲に存在することがより好ましい。
前記金属粒子含有層において、六角形状乃至円形状の平板状金属粒子の存在形態としては、金属粒子含有層の一方の表面（本発明の熱線遮蔽材が基材を有する場合は、基材表面）に対して平均０°～±３０°の範囲で面配向している。
なお、前記金属粒子含有層の一方の表面は、フラットな平面であることが好ましい。本発明の熱線遮蔽材の前記金属粒子含有層が仮支持体としての基材を有する場合は、基材の表面とともに略水平面であることが好ましい。ここで、前記熱線遮蔽材は、前記仮支持体を有していてもよく、有していなくてもよい。
前記金属粒子の大きさとしては、特に制限はなく、目的に応じて適宜選択することができ、例えば、５００ｎｍ以下の平均粒子径を有するものであってもよい。
前記金属粒子の材料としては、特に制限はなく、目的に応じて適宜選択することができるが、熱線（近赤外線）の反射率が高い点から、銀、金、アルミニウム、銅、ロジウム、ニッケル、白金などが好ましい。 1-1. Metal particles
The 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. When 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.
In 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.
In addition, it is preferable that one surface of the said metal particle content layer is a flat plane. When 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. Here, the said heat ray shielding material may have the said temporary support body, and does not need to have it.
There is no restriction | limiting in particular as a magnitude | size of the said metal particle, According to the objective, it can select suitably, For example, you may have an average particle diameter of 500 nm or less.
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.
－１－２．金属平板粒子－
前記金属平板粒子としては、２つの主平面からなる粒子（図４Ａ及び図４Ｂ参照）であれば特に制限はなく、目的に応じて適宜選択することができ、例えば、六角形状、円形状、三角形状などが挙げられる。これらの中でも、可視光透過率が高い点で、六角形状以上の多角形状～円形状であることがより好ましく、六角形状または円形状であることが特に好ましい。
本明細書中、円形状とは、後述する金属平板粒子（平板状金属粒子と同義）の平均円相当径の５０％以上の長さを有する辺の個数が１個の金属平板粒子当たり０個である形状のことを言う。前記円形状の金属平板粒子としては、透過型電子顕微鏡（ＴＥＭ）で金属平板粒子を主平面の上方から観察した際に、角が無く、丸い形状であれば特に制限はなく、目的に応じて適宜選択することができる。
本明細書中、六角形状とは、後述する金属平板粒子の平均円相当径の２０％以上の長さを有する辺の個数が１個の金属平板粒子当たり６個である形状のことを言う。なお、その他の多角形についても同様である。前記六角形状の金属平板粒子としては、透過型電子顕微鏡（ＴＥＭ）で金属平板粒子を主平面の上方から観察した際に、六角形状であれば特に制限はなく、目的に応じて適宜選択することができ、例えば、六角形状の角が鋭角のものでも、鈍っているものでもよいが、可視光域の吸収を軽減し得る点で、角が鈍っているものであることが好ましい。角の鈍りの程度としては、特に制限はなく、目的に応じて適宜選択することができる。
前記金属平板粒子の材料としては、特に制限はなく、前記金属粒子と同じものを目的に応じて適宜選択することができる。前記金属平板粒子は、少なくとも銀を含むことが好ましい。 -1-2. Tabular grain metal
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. For example, hexagonal shape, circular shape, triangular shape Examples include shape. Among these, in terms of high visible light transmittance, 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.
In the present specification, 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.
In the present specification, 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. For example, 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. There is no restriction | limiting in particular as a grade of the dullness of an angle, According to the objective, it can select suitably.
There is no restriction | limiting in particular as a material of the said metal tabular grain, The same thing as the said metal particle can be suitably selected according to the objective. The metal tabular grain preferably contains at least silver.
前記金属平板粒子としては、２つの主平面からなる粒子（図４Ａ及び図４Ｂ参照）であれば特に制限はなく、目的に応じて適宜選択することができ、例えば、六角形状、円形状、三角形状などが挙げられる。これらの中でも、可視光透過率が高い点で、六角形状以上の多角形状～円形状であることがより好ましく、六角形状または円形状であることが特に好ましい。
本明細書中、円形状とは、後述する金属平板粒子（平板状金属粒子と同義）の平均円相当径の５０％以上の長さを有する辺の個数が１個の金属平板粒子当たり０個である形状のことを言う。前記円形状の金属平板粒子としては、透過型電子顕微鏡（ＴＥＭ）で金属平板粒子を主平面の上方から観察した際に、角が無く、丸い形状であれば特に制限はなく、目的に応じて適宜選択することができる。
本明細書中、六角形状とは、後述する金属平板粒子の平均円相当径の２０％以上の長さを有する辺の個数が１個の金属平板粒子当たり６個である形状のことを言う。なお、その他の多角形についても同様である。前記六角形状の金属平板粒子としては、透過型電子顕微鏡（ＴＥＭ）で金属平板粒子を主平面の上方から観察した際に、六角形状であれば特に制限はなく、目的に応じて適宜選択することができ、例えば、六角形状の角が鋭角のものでも、鈍っているものでもよいが、可視光域の吸収を軽減し得る点で、角が鈍っているものであることが好ましい。角の鈍りの程度としては、特に制限はなく、目的に応じて適宜選択することができる。
前記金属平板粒子の材料としては、特に制限はなく、前記金属粒子と同じものを目的に応じて適宜選択することができる。前記金属平板粒子は、少なくとも銀を含むことが好ましい。 -1-2. Tabular grain metal
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. For example, hexagonal shape, circular shape, triangular shape Examples include shape. Among these, in terms of high visible light transmittance, 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.
In the present specification, 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.
In the present specification, 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. For example, 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. There is no restriction | limiting in particular as a grade of the dullness of an angle, According to the objective, it can select suitably.
There is no restriction | limiting in particular as a material of the said metal tabular grain, The same thing as the said metal particle can be suitably selected according to the objective. The metal tabular grain preferably contains at least silver.
前記金属粒子含有層に存在する金属粒子のうち、六角形状乃至円形状の平板状金属粒子は、金属粒子の全個数に対して、６０個数％以上であり、６５個数％以上が好ましく、７０個数％以上が更に好ましい。前記金属平板粒子の割合が、６０個数％未満であると、可視光線透過率が低くなってしまうことがある。
Of the metal particles present in the metal particle-containing layer, 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.
［１－２－１．面配向］
本発明の熱線遮蔽材において、前記六角形状乃至円形状の平板状金属粒子は、その主平面が金属粒子含有層の一方の表面（熱線遮蔽材が基材を有する場合は、基材表面）に対して、平均０°～±３０°の範囲で面配向しており、平均０°～±２０°の範囲で面配向していることが好ましく、平均０°～±５°の範囲で面配向していることが特に好ましい。
前記金属平板粒子の存在状態は、特に制限はなく、目的に応じて適宜選択することができるが、後述する図５Ｂ、図５Ｃのように並んでいることが好ましい。 [1-2-1. Planar orientation]
In the heat ray shielding material of the present invention, 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). On the other hand, 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.
本発明の熱線遮蔽材において、前記六角形状乃至円形状の平板状金属粒子は、その主平面が金属粒子含有層の一方の表面（熱線遮蔽材が基材を有する場合は、基材表面）に対して、平均０°～±３０°の範囲で面配向しており、平均０°～±２０°の範囲で面配向していることが好ましく、平均０°～±５°の範囲で面配向していることが特に好ましい。
前記金属平板粒子の存在状態は、特に制限はなく、目的に応じて適宜選択することができるが、後述する図５Ｂ、図５Ｃのように並んでいることが好ましい。 [1-2-1. Planar orientation]
In the heat ray shielding material of the present invention, 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). On the other hand, 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.
ここで、図５Ａ～図５Ｅは、本発明の熱線遮蔽材において、金属平板粒子を含む金属粒子含有層の存在状態を示した概略断面図である。図５Ａ、図５Ｂおよび図５Ｃは、金属粒子含有層２中における金属平板粒子３の存在状態を示す。図５Ｄは、基材１の平面と金属平板粒子３の平面とのなす角度（±θ）を説明する図である。図５Ｅは、金属粒子含有層２の熱線遮蔽材の深さ方向における存在領域を示すものである。
図５Ｄにおいて、基材１の表面と、金属平板粒子３の主平面または主平面の延長線とのなす角度（±θ）は、前記の面配向における所定の範囲に対応する。即ち、面配向とは、熱線遮蔽材の断面を観察した際、図５Ｄに示す傾角（±θ）が小さい状態をいい、特に、図５Ｂは、基材１の表面と金属平板粒子３の主平面とが接している状態、即ち、θが０°である状態を示す。基材１の表面に対する金属平板粒子３の主平面の面配向の角度、即ち図５Ｄにおけるθが±３０°を超えると、熱線遮蔽材の所定の波長（例えば、可視光域長波長側から近赤外光領域）の反射率が低下してしまう。 Here, 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 metaltabular grain 3 in the metal particle-containing layer 2. FIG. 5D is a diagram illustrating an angle (± θ) 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.
In FIG. 5D, the angle (± θ) formed by the surface of thesubstrate 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 (± θ) 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 θ 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, θ in FIG. Infrared light region) reflectivity is reduced.
図５Ｄにおいて、基材１の表面と、金属平板粒子３の主平面または主平面の延長線とのなす角度（±θ）は、前記の面配向における所定の範囲に対応する。即ち、面配向とは、熱線遮蔽材の断面を観察した際、図５Ｄに示す傾角（±θ）が小さい状態をいい、特に、図５Ｂは、基材１の表面と金属平板粒子３の主平面とが接している状態、即ち、θが０°である状態を示す。基材１の表面に対する金属平板粒子３の主平面の面配向の角度、即ち図５Ｄにおけるθが±３０°を超えると、熱線遮蔽材の所定の波長（例えば、可視光域長波長側から近赤外光領域）の反射率が低下してしまう。 Here, 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
In FIG. 5D, the angle (± θ) formed by the surface of the
前記金属粒子含有層の一方の表面（熱線遮蔽材が基材を有する場合は、基材表面）に対して金属平板粒子の主平面が面配向しているかどうかの評価としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、適当な断面切片を作製し、この切片における金属粒子含有層（熱線遮蔽材が基材を有する場合は、基材）及び金属平板粒子を観察して評価する方法であってもよい。具体的には、熱線遮蔽材を、ミクロトーム、集束イオンビーム（ＦＩＢ）を用いて熱線遮蔽材の断面サンプルまたは断面切片サンプルを作製し、これを、各種顕微鏡（例えば、電界放射型走査電子顕微鏡（ＦＥ－ＳＥＭ）等）を用いて観察して得た画像から評価する方法などが挙げられる。
There is no particular limitation on 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). , Can be selected appropriately according to the purpose. For example, 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. Specifically, as a heat ray shielding material, a microtome or a focused ion beam (FIB) 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.
前記熱線遮蔽材において、金属平板粒子を被覆するバインダーが水で膨潤する場合は、液体窒素で凍結した状態の試料を、ミクロトームに装着されたダイヤモンドカッター切断することで、前記断面サンプルまたは断面切片サンプルを作製してもよい。また、熱線遮蔽材において金属平板粒子を被覆するバインダーが水で膨潤しない場合は、前記断面サンプルまたは断面切片サンプルを作製してもよい。
In the heat ray shielding material, when the binder covering the metal tabular grain swells with water, the sample frozen in liquid nitrogen is cut with a diamond cutter attached to a microtome, so that the cross section sample or cross section sample May be produced. Moreover, when the binder which coat | 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.
前記の通り作製した断面サンプルまたは断面切片サンプルの観察としては、サンプルにおいて金属粒子含有層の一方の表面（熱線遮蔽材が基材を有する場合は、基材表面）に対して金属平板粒子の主平面が面配向しているかどうかを確認し得るものであれば、特に制限はなく、目的に応じて適宜選択することができ、例えば、ＦＥ－ＳＥＭ、ＴＥＭ、光学顕微鏡などを用いた観察が挙げられる。前記断面サンプルの場合は、ＦＥ－ＳＥＭにより、前記断面切片サンプルの場合は、ＴＥＭにより観察を行ってもよい。ＦＥ－ＳＥＭで評価する場合は、金属平板粒子の形状と傾角（図５Ｄの±θ）が明瞭に判断できる空間分解能を有することが好ましい。
As the observation of the cross-section sample or cross-section sample prepared as described above, 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). There is no particular limitation as long as it can confirm whether or not the plane is plane-oriented, and it can be appropriately selected according to the purpose. For example, observation using an FE-SEM, TEM, optical microscope, or the like can be given. It is done. In the case of the cross section sample, observation may be performed by FE-SEM, and in the case of the cross section sample, observation may be performed by TEM. When evaluating by FE-SEM, it is preferable to have a spatial resolution with which the shape and tilt angle (± θ in FIG. 5D) of the metal tabular grains can be clearly determined.
［１－２－２．平均粒子径（平均円相当径）及び平均粒子径（平均円相当径）の粒度分布］
前記金属平板粒子の平均粒子径（平均円相当径）としては、特に制限はなく、目的に応じて適宜選択することができるが、７０ｎｍ～５００ｎｍが好ましく、１００ｎｍ～４００ｎｍがより好ましい。前記平均粒子径（平均円相当径）が、７０ｎｍ未満であると、金属平板粒子の吸収の寄与が反射より大きくなるため十分な熱線反射能が得られなくなることがあり、５００ｎｍを超えると、ヘイズ（散乱）が大きくなり、基材の透明性が損なわれてしまうことがある。
ここで、前記平均粒子径（平均円相当径）とは、ＴＥＭで粒子を観察して得た像から任意に選んだ２００個の平板粒子の主平面直径（最大長さ）の平均値を意味する。
前記金属粒子含有層中に平均粒子径（平均円相当径）が異なる２種以上の金属粒子を含有することができ、この場合、金属粒子の平均粒子径（平均円相当径）のピークが２つ以上、即ち２つの平均粒子径（平均円相当径）を有していてもよい。 [1-2-2. Average particle diameter (average equivalent circle diameter) and average particle diameter (average equivalent circle diameter) particle size distribution]
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.
Here, the average particle diameter (average equivalent circle 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).
前記金属平板粒子の平均粒子径（平均円相当径）としては、特に制限はなく、目的に応じて適宜選択することができるが、７０ｎｍ～５００ｎｍが好ましく、１００ｎｍ～４００ｎｍがより好ましい。前記平均粒子径（平均円相当径）が、７０ｎｍ未満であると、金属平板粒子の吸収の寄与が反射より大きくなるため十分な熱線反射能が得られなくなることがあり、５００ｎｍを超えると、ヘイズ（散乱）が大きくなり、基材の透明性が損なわれてしまうことがある。
ここで、前記平均粒子径（平均円相当径）とは、ＴＥＭで粒子を観察して得た像から任意に選んだ２００個の平板粒子の主平面直径（最大長さ）の平均値を意味する。
前記金属粒子含有層中に平均粒子径（平均円相当径）が異なる２種以上の金属粒子を含有することができ、この場合、金属粒子の平均粒子径（平均円相当径）のピークが２つ以上、即ち２つの平均粒子径（平均円相当径）を有していてもよい。 [1-2-2. Average particle diameter (average equivalent circle diameter) and average particle diameter (average equivalent circle diameter) particle size distribution]
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.
Here, the average particle diameter (average equivalent circle 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).
本発明の熱線遮蔽材において、金属平板粒子の粒度分布における変動係数としては、３０％以下が好ましく、２０％以下がより好ましい。前記変動係数が、３０％を超えると、熱線遮蔽材における熱線の反射波長域がブロードになってしまうことがある。
ここで、前記金属平板粒子の粒度分布における変動係数は、例えば前記の通り得た平均値の算出に用いた２００個の金属平板粒子の粒子径の分布範囲をプロットし、粒度分布の標準偏差を求め、前記の通り得た主平面直径（最大長さ）の平均値（平均粒子径（平均円相当径））で割った値（％）である。 In the heat ray shielding material of the present invention, 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.
Here, 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.
ここで、前記金属平板粒子の粒度分布における変動係数は、例えば前記の通り得た平均値の算出に用いた２００個の金属平板粒子の粒子径の分布範囲をプロットし、粒度分布の標準偏差を求め、前記の通り得た主平面直径（最大長さ）の平均値（平均粒子径（平均円相当径））で割った値（％）である。 In the heat ray shielding material of the present invention, 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.
Here, 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.
［１－２－３．アスペクト比］
前記金属平板粒子のアスペクト比としては、特に制限はなく、目的に応じて適宜選択することができるが、波長８００ｎｍ～１，８００ｎｍの赤外光領域での反射率が高くなる点から、８～４０が好ましく、１０～３５がより好ましい。前記アスペクト比が８未満であると反射波長が８００ｎｍより小さくなり、４０を超えると、反射波長が１，８００ｎｍより長くなり、十分な熱線反射能が得られないことがある。
前記アスペクト比は、金属平板粒子の平均粒子径（平均円相当径）を金属平板粒子の平均粒子厚みで除算した値を意味する。平均粒子厚みは、金属平板粒子の主平面間距離に相当し、例えば、図４Ａ及び図４Ｂに示す通りであり、原子間力顕微鏡（ＡＦＭ）により測定することができる。
前記ＡＦＭによる平均粒子厚みの測定方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ガラス基板に金属平板粒子を含有する粒子分散液を滴下し、乾燥させて、粒子１個の厚みを測定する方法などが挙げられる。
なお、前記金属平板粒子の厚みは５～２０ｎｍであることが好ましい。 [1-2-3. aspect ratio]
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.
前記金属平板粒子のアスペクト比としては、特に制限はなく、目的に応じて適宜選択することができるが、波長８００ｎｍ～１，８００ｎｍの赤外光領域での反射率が高くなる点から、８～４０が好ましく、１０～３５がより好ましい。前記アスペクト比が８未満であると反射波長が８００ｎｍより小さくなり、４０を超えると、反射波長が１，８００ｎｍより長くなり、十分な熱線反射能が得られないことがある。
前記アスペクト比は、金属平板粒子の平均粒子径（平均円相当径）を金属平板粒子の平均粒子厚みで除算した値を意味する。平均粒子厚みは、金属平板粒子の主平面間距離に相当し、例えば、図４Ａ及び図４Ｂに示す通りであり、原子間力顕微鏡（ＡＦＭ）により測定することができる。
前記ＡＦＭによる平均粒子厚みの測定方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ガラス基板に金属平板粒子を含有する粒子分散液を滴下し、乾燥させて、粒子１個の厚みを測定する方法などが挙げられる。
なお、前記金属平板粒子の厚みは５～２０ｎｍであることが好ましい。 [1-2-3. aspect ratio]
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.
［１－２－４．金属平板粒子の存在範囲］
本発明の熱線遮蔽材では、前記六角形状乃至円形状の平板状金属粒子の８０個数％以上が、前記金属粒子含有層の表面からｄ／２の範囲に存在することが好ましく、ｄ／３の範囲に存在することがより好ましく、前記六角形状乃至円形状の平板状金属粒子の６０個数％以上が前記金属粒子含有層の一方の表面に露出していることが更に好ましい。金属平板粒子が金属粒子含有層の表面からｄ／２の範囲に存在するとは、金属平板粒子の少なくとも一部が金属粒子含有層の表面からｄ／２の範囲に含まれていることを意味する。すなわち、金属平板粒子の一部が、金属粒子含有層の表面よりも突出している図５Ｃに記載される金属平板粒子も、金属粒子含有層の表面からｄ／２の範囲に存在する金属平板粒子として扱う。なお、図５Ｃは、各金属平板粒子の厚み方向のごく一部が金属粒子含有層に埋没してことを意味し、各金属平板粒子が金属粒子含有層の表面上に積まれているわけではない。
また、金属平板粒子が前記金属粒子含有層の一方の表面に露出しているとは、金属平板粒子の一方の表面の一部が、金属粒子含有層の表面よりも突出していることを意味する。
ここで、前記金属粒子含有層中の金属平板粒子存在分布は、例えば、熱線遮蔽材の断面試料をＳＥＭ観察した画像より測定することができる。 [1-2-4. Range of tabular metal grains]
In 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. 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.
Moreover, 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. .
Here, 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.
本発明の熱線遮蔽材では、前記六角形状乃至円形状の平板状金属粒子の８０個数％以上が、前記金属粒子含有層の表面からｄ／２の範囲に存在することが好ましく、ｄ／３の範囲に存在することがより好ましく、前記六角形状乃至円形状の平板状金属粒子の６０個数％以上が前記金属粒子含有層の一方の表面に露出していることが更に好ましい。金属平板粒子が金属粒子含有層の表面からｄ／２の範囲に存在するとは、金属平板粒子の少なくとも一部が金属粒子含有層の表面からｄ／２の範囲に含まれていることを意味する。すなわち、金属平板粒子の一部が、金属粒子含有層の表面よりも突出している図５Ｃに記載される金属平板粒子も、金属粒子含有層の表面からｄ／２の範囲に存在する金属平板粒子として扱う。なお、図５Ｃは、各金属平板粒子の厚み方向のごく一部が金属粒子含有層に埋没してことを意味し、各金属平板粒子が金属粒子含有層の表面上に積まれているわけではない。
また、金属平板粒子が前記金属粒子含有層の一方の表面に露出しているとは、金属平板粒子の一方の表面の一部が、金属粒子含有層の表面よりも突出していることを意味する。
ここで、前記金属粒子含有層中の金属平板粒子存在分布は、例えば、熱線遮蔽材の断面試料をＳＥＭ観察した画像より測定することができる。 [1-2-4. Range of tabular metal grains]
In 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. 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.
Moreover, 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. .
Here, 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.
前記金属粒子含有層における金属平板粒子を構成する金属のプラズモン共鳴波長λは、特に制限はなく、目的に応じて適宜選択することができるが、熱線反射性能を付与する点で、４００ｎｍ～２，５００ｎｍであることが好ましく、可視光透過率を付与する点から、７００ｎｍ～２，５００ｎｍであることがより好ましい。
The plasmon resonance wavelength λ 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.
［１－２－５．金属粒子含有層の媒質］
本発明の熱線遮蔽材は、前記金属粒子含有層における媒質としてポリマーを含む。このような構成により、前記金属粒子含有層と前記ポリマーフィルムの密着がＪＩＳ Ｋ５６００－５－６に定められたクロスカットセロテープ（登録商標）剥離試験で2点以下であるように制御しやすくすることができる。
前記ポリマーとしては、特に制限はなく、目的に応じて適宜選択することができる。前記ポリマーとしては、例えば、ポリビニルアセタール樹脂、ポリビニルアルコール樹脂、ポリビニルブチラール樹脂、ポリアクリレート樹脂、ポリメチルメタクリレート樹脂、ポリカーボネート樹脂、ポリ塩化ビニル樹脂、（飽和）ポリエステル樹脂、ポリウレタン樹脂、ゼラチンやセルロース等の天然高分子等の高分子などが挙げられる。その中でも、本発明では、前記ポリマーの主ポリマーがポリビニルアルコール樹脂、ポリビニルブチラール樹脂、ポリ塩化ビニル樹脂、（飽和）ポリエステル樹脂、ポリウレタン樹脂であることが好ましく、ポリエステル樹脂およびポリウレタン樹脂であることが前記六角形状乃至円形状の平板状金属粒子の８０個数％以上を前記金属粒子含有層の表面からｄ／２の範囲に存在させやすい観点からより好ましく、ポリエステル樹脂であることが本発明の熱線遮蔽材のクロスカット密着性をより改善する観点から特に好ましい。
また、本明細書中、前記金属粒子含有層に含まれる前記ポリマーの主ポリマーとは、前記金属粒子含有層に含まれるポリマーの５０質量％以上を占めるポリマー成分のことを言う。
本発明の熱線遮蔽材は、前記金属粒子含有層に含まれる前記金属粒子に対する前記ポリエステル樹脂の含有量が１～１００００質量％であることが好ましく、１０～１０００質量％であることがより好ましく、２０～５００質量％であることが特に好ましい。
前記媒質の屈折率ｎは、１．４～１．７であることが好ましい。
本発明の熱線遮蔽材は、前記六角形状乃至円形状の平板状金属粒子の厚みをａとしたとき、前記六角形状乃至円形状の平板状金属粒子の８０個数％以上が、厚み方向のａ／１０以上を前記ポリマーに覆われていることが好ましく、厚み方向のａ／１０～１０ａを前記ポリマーに覆われていることがより好ましく、ａ／８～４ａを前記ポリマーに覆われていることが特に好ましい。このように前記六角形状乃至円形状の平板状金属粒子が前記金属粒子含有層に一定割合以上埋没していることにより、よりこすり耐性を高めることができる。すなわち、本発明の熱線遮蔽材は、図５Ｃの態様よりも、図５Ｂの態様の方が好ましい。 [1-2-5. Medium of metal particle containing layer]
The heat ray shielding material of the present invention contains a polymer as a medium in the metal particle-containing layer. With such a configuration, 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.
There is no restriction | limiting in particular as said polymer, According to the objective, it can select suitably. Examples of the polymer include polyvinyl acetal resin, polyvinyl alcohol resin, polyvinyl butyral resin, polyacrylate resin, polymethyl methacrylate resin, polycarbonate resin, polyvinyl chloride resin, (saturated) polyester resin, polyurethane resin, gelatin resin and cellulose. And polymers such as natural polymers. Among them, in the present invention, the main polymer of the polymer is preferably a polyvinyl alcohol resin, a polyvinyl butyral resin, a polyvinyl chloride resin, a (saturated) polyester resin, a polyurethane resin, and preferably the polyester resin and the polyurethane resin. More preferably, 80% by number or more of hexagonal or circular plate-like metal particles are present in the range of d / 2 from the surface of the metal particle-containing layer, and the heat ray shielding material of the present invention is a polyester resin. This is particularly preferable from the viewpoint of further improving the cross-cut adhesion.
Moreover, in this specification, 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.
In the heat ray shielding material of the present invention, 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.
In the heat ray shielding material of the present invention, when 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. It is preferable that 10 or more is covered with the polymer, a / 10 to 10a in the thickness direction is more preferably covered with the polymer, and a / 8 to 4a is covered with the polymer. Particularly preferred. As described above, 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.
本発明の熱線遮蔽材は、前記金属粒子含有層における媒質としてポリマーを含む。このような構成により、前記金属粒子含有層と前記ポリマーフィルムの密着がＪＩＳ Ｋ５６００－５－６に定められたクロスカットセロテープ（登録商標）剥離試験で2点以下であるように制御しやすくすることができる。
前記ポリマーとしては、特に制限はなく、目的に応じて適宜選択することができる。前記ポリマーとしては、例えば、ポリビニルアセタール樹脂、ポリビニルアルコール樹脂、ポリビニルブチラール樹脂、ポリアクリレート樹脂、ポリメチルメタクリレート樹脂、ポリカーボネート樹脂、ポリ塩化ビニル樹脂、（飽和）ポリエステル樹脂、ポリウレタン樹脂、ゼラチンやセルロース等の天然高分子等の高分子などが挙げられる。その中でも、本発明では、前記ポリマーの主ポリマーがポリビニルアルコール樹脂、ポリビニルブチラール樹脂、ポリ塩化ビニル樹脂、（飽和）ポリエステル樹脂、ポリウレタン樹脂であることが好ましく、ポリエステル樹脂およびポリウレタン樹脂であることが前記六角形状乃至円形状の平板状金属粒子の８０個数％以上を前記金属粒子含有層の表面からｄ／２の範囲に存在させやすい観点からより好ましく、ポリエステル樹脂であることが本発明の熱線遮蔽材のクロスカット密着性をより改善する観点から特に好ましい。
また、本明細書中、前記金属粒子含有層に含まれる前記ポリマーの主ポリマーとは、前記金属粒子含有層に含まれるポリマーの５０質量％以上を占めるポリマー成分のことを言う。
本発明の熱線遮蔽材は、前記金属粒子含有層に含まれる前記金属粒子に対する前記ポリエステル樹脂の含有量が１～１００００質量％であることが好ましく、１０～１０００質量％であることがより好ましく、２０～５００質量％であることが特に好ましい。
前記媒質の屈折率ｎは、１．４～１．７であることが好ましい。
本発明の熱線遮蔽材は、前記六角形状乃至円形状の平板状金属粒子の厚みをａとしたとき、前記六角形状乃至円形状の平板状金属粒子の８０個数％以上が、厚み方向のａ／１０以上を前記ポリマーに覆われていることが好ましく、厚み方向のａ／１０～１０ａを前記ポリマーに覆われていることがより好ましく、ａ／８～４ａを前記ポリマーに覆われていることが特に好ましい。このように前記六角形状乃至円形状の平板状金属粒子が前記金属粒子含有層に一定割合以上埋没していることにより、よりこすり耐性を高めることができる。すなわち、本発明の熱線遮蔽材は、図５Ｃの態様よりも、図５Ｂの態様の方が好ましい。 [1-2-5. Medium of metal particle containing layer]
The heat ray shielding material of the present invention contains a polymer as a medium in the metal particle-containing layer. With such a configuration, 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.
There is no restriction | limiting in particular as said polymer, According to the objective, it can select suitably. Examples of the polymer include polyvinyl acetal resin, polyvinyl alcohol resin, polyvinyl butyral resin, polyacrylate resin, polymethyl methacrylate resin, polycarbonate resin, polyvinyl chloride resin, (saturated) polyester resin, polyurethane resin, gelatin resin and cellulose. And polymers such as natural polymers. Among them, in the present invention, the main polymer of the polymer is preferably a polyvinyl alcohol resin, a polyvinyl butyral resin, a polyvinyl chloride resin, a (saturated) polyester resin, a polyurethane resin, and preferably the polyester resin and the polyurethane resin. More preferably, 80% by number or more of hexagonal or circular plate-like metal particles are present in the range of d / 2 from the surface of the metal particle-containing layer, and the heat ray shielding material of the present invention is a polyester resin. This is particularly preferable from the viewpoint of further improving the cross-cut adhesion.
Moreover, in this specification, 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.
In the heat ray shielding material of the present invention, 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.
In the heat ray shielding material of the present invention, when 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. It is preferable that 10 or more is covered with the polymer, a / 10 to 10a in the thickness direction is more preferably covered with the polymer, and a / 8 to 4a is covered with the polymer. Particularly preferred. As described above, 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.
［１－２－６．金属平板粒子の面積率］
前記熱線遮蔽材を上から見た時の基材の面積Ａ（金属粒子含有層に対して垂直方向から見たときの前記金属粒子含有層の全投影面積Ａ）に対する金属平板粒子の面積の合計値Ｂの割合である面積率〔（Ｂ／Ａ）×１００〕としては、１５％以上が好ましく、２０％以上がより好ましい。前記面積率が、１５％未満であると、熱線の最大反射率が低下してしまい、遮熱効果が十分に得られないことがある。
ここで、前記面積率は、例えば熱線遮蔽材基材を上からＳＥＭ観察で得られた画像や、ＡＦＭ（原子間力顕微鏡）観察で得られた画像を画像処理することにより測定することができる。 [1-2-6. Area ratio of metal tabular grains]
The total area of the metal tabular grains relative to the area A of the base material when 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 value B, is preferably 15% or more, and more preferably 20% or more. When the area ratio is less than 15%, the maximum reflectance of the heat ray is lowered, and the heat shielding effect may not be sufficiently obtained.
Here, 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. .
前記熱線遮蔽材を上から見た時の基材の面積Ａ（金属粒子含有層に対して垂直方向から見たときの前記金属粒子含有層の全投影面積Ａ）に対する金属平板粒子の面積の合計値Ｂの割合である面積率〔（Ｂ／Ａ）×１００〕としては、１５％以上が好ましく、２０％以上がより好ましい。前記面積率が、１５％未満であると、熱線の最大反射率が低下してしまい、遮熱効果が十分に得られないことがある。
ここで、前記面積率は、例えば熱線遮蔽材基材を上からＳＥＭ観察で得られた画像や、ＡＦＭ（原子間力顕微鏡）観察で得られた画像を画像処理することにより測定することができる。 [1-2-6. Area ratio of metal tabular grains]
The total area of the metal tabular grains relative to the area A of the base material when 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 value B, is preferably 15% or more, and more preferably 20% or more. When the area ratio is less than 15%, the maximum reflectance of the heat ray is lowered, and the heat shielding effect may not be sufficiently obtained.
Here, 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. .
［１－２－７．金属平板粒子の平均粒子間距離］
前記金属粒子含有層における水平方向に隣接する金属平板粒子の平均粒子間距離としては、可視光線透過率及び熱線の最大反射率の点から、金属平板粒子の平均粒子径の１／１０以上が好ましい。
前記金属平板粒子の水平方向の平均粒子間距離が、前記金属平板粒子の平均粒子径の１／１０未満となると、熱線の最大反射率が低下してしまう。また、水平方向の平均粒子間距離は、可視光線透過率の点で、不均一（ランダム）であることが好ましい。ランダムでない場合、即ち、均一であると、可視光線の吸収が起こり、透過率が低下してしまうことがある。 [1-2-7. Average distance between tabular grains]
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. .
When 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. Further, 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.
前記金属粒子含有層における水平方向に隣接する金属平板粒子の平均粒子間距離としては、可視光線透過率及び熱線の最大反射率の点から、金属平板粒子の平均粒子径の１／１０以上が好ましい。
前記金属平板粒子の水平方向の平均粒子間距離が、前記金属平板粒子の平均粒子径の１／１０未満となると、熱線の最大反射率が低下してしまう。また、水平方向の平均粒子間距離は、可視光線透過率の点で、不均一（ランダム）であることが好ましい。ランダムでない場合、即ち、均一であると、可視光線の吸収が起こり、透過率が低下してしまうことがある。 [1-2-7. Average distance between tabular grains]
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. .
When 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. Further, 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.
ここで、前記金属平板粒子の水平方向の平均粒子間距離とは、隣り合う２つの粒子の粒子間距離の平均値を意味する。また、前記平均粒子間距離がランダムであるとは、「１００個以上の金属平板粒子が含まれるＳＥＭ画像を二値化した際の輝度値の２次元自己相関を取ったときに、原点以外に有意な極大点を持たない」ことを意味する。
Here, 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. In addition, 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.
［１－２－８．金属粒子含有層の層構成］
本発明の熱線遮蔽材において、金属平板粒子は、図５Ａ～図５Ｅに示すように、金属平板粒子を含む金属粒子含有層の形態で配置される。
前記金属粒子含有層としては、図５Ａ～図５Ｅに示すように単層で構成されてもよく、複数の金属粒子含有層で構成されてもよい。複数の金属粒子含有層で構成される場合、遮熱性能を付与したい波長帯域に応じた遮蔽性能を付与することが可能となる。なお、前記金属粒子含有層が複数の金属粒子含有層で構成される場合、本発明の熱線遮蔽材は、少なくとも最表面の金属粒子含有層において、該最表面の金属粒子含有層の厚みをｄ’としたとき、前記六角形状乃至円形状の平板状金属粒子の８０個数％以上が、該最表面の金属粒子含有層の表面からｄ’／２の範囲に存在することが好ましい。 [1-2-8. Layer structure of metal particle-containing layer]
In the heat ray shielding material of the present invention, 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 | band which wants to provide heat insulation performance. When the metal particle-containing layer is composed of a plurality of metal particle-containing layers, 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.
本発明の熱線遮蔽材において、金属平板粒子は、図５Ａ～図５Ｅに示すように、金属平板粒子を含む金属粒子含有層の形態で配置される。
前記金属粒子含有層としては、図５Ａ～図５Ｅに示すように単層で構成されてもよく、複数の金属粒子含有層で構成されてもよい。複数の金属粒子含有層で構成される場合、遮熱性能を付与したい波長帯域に応じた遮蔽性能を付与することが可能となる。なお、前記金属粒子含有層が複数の金属粒子含有層で構成される場合、本発明の熱線遮蔽材は、少なくとも最表面の金属粒子含有層において、該最表面の金属粒子含有層の厚みをｄ’としたとき、前記六角形状乃至円形状の平板状金属粒子の８０個数％以上が、該最表面の金属粒子含有層の表面からｄ’／２の範囲に存在することが好ましい。 [1-2-8. Layer structure of metal particle-containing layer]
In the heat ray shielding material of the present invention, 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 | band which wants to provide heat insulation performance. When the metal particle-containing layer is composed of a plurality of metal particle-containing layers, 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.
［１－２－９．金属粒子含有層の厚み］
前記金属粒子含有層の厚みは、１０～１６０ｎｍであることが好ましく、２０～８０ｎｍであることがより好ましい。前記金属粒子含有層の厚みｄは、前記六角形状乃至円形状の平板状金属粒子の厚みをａとしたとき、ａ～１０ａであることが好ましく、２ａ～８ａであることがより好ましい。 [1-2-9. Thickness of 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.
前記金属粒子含有層の厚みは、１０～１６０ｎｍであることが好ましく、２０～８０ｎｍであることがより好ましい。前記金属粒子含有層の厚みｄは、前記六角形状乃至円形状の平板状金属粒子の厚みをａとしたとき、ａ～１０ａであることが好ましく、２ａ～８ａであることがより好ましい。 [1-2-9. Thickness of 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.
ここで、前記金属粒子含有層の各層の厚みは、例えば、熱線遮蔽材の断面試料をＳＥＭ観察した画像より測定することができる。
また、熱線遮蔽材の前記金属粒子含有層の上に、例えば後述するオーバーコート層などの他の層を有する場合においても、他の層と前記金属粒子含有層の境界は同様の方法によって決定することができ、前記金属粒子含有層の厚みｄを決定することができる。なお、前記金属粒子含有層に含まれるポリマーと同じ種類のポリマーを用いて、前記金属粒子含有層の上にコーティングをする場合は通常はＳＥＭ観察した画像によって前記金属粒子含有層との境界を判別できることができ、前記金属粒子含有層の厚みｄを決定することができる。 Here, 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. When coating the metal particle-containing layer using the same type of polymer as the polymer contained in the metal particle-containing layer, 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.
また、熱線遮蔽材の前記金属粒子含有層の上に、例えば後述するオーバーコート層などの他の層を有する場合においても、他の層と前記金属粒子含有層の境界は同様の方法によって決定することができ、前記金属粒子含有層の厚みｄを決定することができる。なお、前記金属粒子含有層に含まれるポリマーと同じ種類のポリマーを用いて、前記金属粒子含有層の上にコーティングをする場合は通常はＳＥＭ観察した画像によって前記金属粒子含有層との境界を判別できることができ、前記金属粒子含有層の厚みｄを決定することができる。 Here, 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. When coating the metal particle-containing layer using the same type of polymer as the polymer contained in the metal particle-containing layer, 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.
［１－２－１０．金属平板粒子の合成方法］
前記金属平板粒子の合成方法としては、六角形状乃至円形状の平板状金属粒子を合成し得るものであれば特に制限はなく、目的に応じて適宜選択することができ、例えば、化学還元法、光化学還元法、電気化学還元法等の液相法などが挙げられる。これらの中でも、形状とサイズ制御性の点で、化学還元法、光化学還元法などの液相法が特に好ましい。六角形～三角形状の金属平板粒子を合成後、例えば、硝酸、亜硫酸ナトリウム等の銀を溶解する溶解種によるエッチング処理、加熱によるエージング処理などを行うことにより、六角形～三角形状の金属平板粒子の角を鈍らせて、六角形状乃至円形状の平板状金属粒子を得てもよい。 [1-2-10. Method for synthesizing tabular metal grains]
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. For example, a chemical reduction method, Examples thereof include liquid phase methods such as a photochemical reduction method and an electrochemical reduction method. Among these, 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. After synthesizing hexagonal to triangular metal tabular grains, 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.
前記金属平板粒子の合成方法としては、六角形状乃至円形状の平板状金属粒子を合成し得るものであれば特に制限はなく、目的に応じて適宜選択することができ、例えば、化学還元法、光化学還元法、電気化学還元法等の液相法などが挙げられる。これらの中でも、形状とサイズ制御性の点で、化学還元法、光化学還元法などの液相法が特に好ましい。六角形～三角形状の金属平板粒子を合成後、例えば、硝酸、亜硫酸ナトリウム等の銀を溶解する溶解種によるエッチング処理、加熱によるエージング処理などを行うことにより、六角形～三角形状の金属平板粒子の角を鈍らせて、六角形状乃至円形状の平板状金属粒子を得てもよい。 [1-2-10. Method for synthesizing tabular metal grains]
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. For example, a chemical reduction method, Examples thereof include liquid phase methods such as a photochemical reduction method and an electrochemical reduction method. Among these, 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. After synthesizing hexagonal to triangular metal tabular grains, 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.
前記金属平板粒子の合成方法としては、前記の他、予めフィルム、ガラスなどの透明基材の表面に種晶を固定後、平板状に金属粒子（例えばＡｇ）を結晶成長させてもよい。
As a method for synthesizing the metal tabular grains, in addition to the above, 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.
本発明の熱線遮蔽材において、金属平板粒子は、所望の特性を付与するために、更なる処理を施してもよい。前記更なる処理としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、高屈折率シェル層の形成、分散剤、酸化防止剤等の各種添加剤を添加することなどが挙げられる。
In the heat ray shielding material of the present invention, 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. For example, 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.
－１－２－１０－１．高屈折率シェル層の形成－
前記金属平板粒子は、可視光域透明性を更に高めるために、可視光域透明性が高い高屈折率材料で被覆されてもよい。
前記高屈折率材料としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ＴｉＯｘ、ＢａＴｉＯ３、ＺｎＯ、ＳｎＯ２、ＺｒＯ２、ＮｂＯｘなどが挙げられる。 -1-2-10-1. Formation of high refractive index shell layer
In order to further improve the visible light region transparency, the metal tabular grain may be coated with a high refractive index material having high visible light region transparency.
As 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.
前記金属平板粒子は、可視光域透明性を更に高めるために、可視光域透明性が高い高屈折率材料で被覆されてもよい。
前記高屈折率材料としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ＴｉＯｘ、ＢａＴｉＯ３、ＺｎＯ、ＳｎＯ２、ＺｒＯ２、ＮｂＯｘなどが挙げられる。 -1-2-10-1. Formation of high refractive index shell layer
In order to further improve the visible light region transparency, the metal tabular grain may be coated with a high refractive index material having high visible light region transparency.
As 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.
前記被覆する方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、Ｌａｎｇｍｕｉｒ、２０００年、１６巻、ｐ．２７３１－２７３５に報告されているようにテトラブトキシチタンを加水分解することにより銀の金属平板粒子の表面にＴｉＯｘ層を形成する方法であってもよい。
There is no restriction | limiting in particular as said coating method, According to the objective, it can select suitably, For example, Langmuir, 2000, 16 volumes, p. As reported in 2731-2735, a method of forming a TiO x layer on the surface of silver metal tabular grains by hydrolyzing tetrabutoxy titanium may be used.
また、前記金属平板粒子に直接高屈折率金属酸化物層シェルを形成することが困難な場合は、前記の通り金属平板粒子を合成した後、適宜ＳｉＯ２やポリマーのシェル層を形成し、更に、このシェル層上に前記金属酸化物層を形成してもよい。ＴｉＯｘを高屈折率金属酸化物層の材料として用いる場合には、ＴｉＯｘが光触媒活性を有することから、金属平板粒子を分散するマトリクスを劣化させてしまう懸念があるため、目的に応じて金属平板粒子にＴｉＯｘ層を形成した後、適宜ＳｉＯ２層を形成してもよい。
In addition, when it is difficult to form a high refractive index metal oxide layer shell directly on the metal tabular grain, after synthesizing the metal tabular grain as described above, an SiO 2 or polymer shell layer is appropriately formed, The metal oxide layer may be formed on the shell layer. When 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.
－１－２－１０－２．各種添加物の添加－
本発明の熱線遮蔽材において、金属平板粒子は、該金属平板粒子を構成する銀などの金属の酸化を防止するために、メルカプトテトラゾール、アスコルビン酸等の酸化防止剤を吸着していてもよい。また、酸化防止を目的として、Ｎｉ等の酸化犠牲層が金属平板粒子の表面に形成されていてもよい。また、酸素を遮断することを目的として、ＳｉＯ２などの金属酸化物膜で被覆されていてもよい。 -1-2-10-2. Addition of various additives-
In the heat ray shielding material of the present invention, 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. Further, 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.
本発明の熱線遮蔽材において、金属平板粒子は、該金属平板粒子を構成する銀などの金属の酸化を防止するために、メルカプトテトラゾール、アスコルビン酸等の酸化防止剤を吸着していてもよい。また、酸化防止を目的として、Ｎｉ等の酸化犠牲層が金属平板粒子の表面に形成されていてもよい。また、酸素を遮断することを目的として、ＳｉＯ２などの金属酸化物膜で被覆されていてもよい。 -1-2-10-2. Addition of various additives-
In the heat ray shielding material of the present invention, 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. Further, 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.
前記金属平板粒子は、分散性付与を目的として、例えば、４級アンモニウム塩、アミン類等のＮ元素、Ｓ元素、及びＰ元素の少なくともいずれかを含む低分子量分散剤、高分子量分散剤などの分散剤を添加してもよい。
For the purpose of imparting dispersibility, 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.
＜２．基材＞
本発明の熱線遮蔽材は、基材であるポリマーフィルムを有し、前記金属粒子含有層と前記ポリマーフィルムの密着がＪＩＳ Ｋ５６００－５－６に定められたクロスカットセロテープ（登録商標）剥離試験で2点以下であることを特徴とする。
前記熱線遮蔽材は、前記六角形状乃至円形状の平板状金属粒子の８０個数％以上が偏在している方の前記金属粒子含有層の表面とは反対側の表面に、基材を有することが好ましい。 <2. Base material>
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.
本発明の熱線遮蔽材は、基材であるポリマーフィルムを有し、前記金属粒子含有層と前記ポリマーフィルムの密着がＪＩＳ Ｋ５６００－５－６に定められたクロスカットセロテープ（登録商標）剥離試験で2点以下であることを特徴とする。
前記熱線遮蔽材は、前記六角形状乃至円形状の平板状金属粒子の８０個数％以上が偏在している方の前記金属粒子含有層の表面とは反対側の表面に、基材を有することが好ましい。 <2. Base material>
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.
前記基材としては、光学的に透明な基材であれば特に制限はなく、目的に応じて適宜選択することができ、例えば、可視光線透過率が７０％以上のもの、好ましくは８０％以上のもの、近赤外線域の透過率が高いものなどが挙げられる。
前記基材としては、ポリマーフィルムであること以外はその形状、構造、大きさ、材料などについては、特に制限はなく、目的に応じて適宜選択することができる。前記形状としては、例えば、平板状などが挙げられ、前記構造としては、単層構造であってもよいし、積層構造であってもよく、前記大きさとしては、前記熱線遮蔽材の大きさなどに応じて適宜選択することができる。 The substrate is not particularly limited as long as it is an optically transparent substrate, and can be appropriately selected according to the purpose. For example, 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.
There is no restriction | limiting in particular about the shape, a structure, a magnitude | size, material, etc. as said base material except being a polymer film, According to the objective, it can select suitably. Examples of 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.
前記基材としては、ポリマーフィルムであること以外はその形状、構造、大きさ、材料などについては、特に制限はなく、目的に応じて適宜選択することができる。前記形状としては、例えば、平板状などが挙げられ、前記構造としては、単層構造であってもよいし、積層構造であってもよく、前記大きさとしては、前記熱線遮蔽材の大きさなどに応じて適宜選択することができる。 The substrate is not particularly limited as long as it is an optically transparent substrate, and can be appropriately selected according to the purpose. For example, 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.
There is no restriction | limiting in particular about the shape, a structure, a magnitude | size, material, etc. as said base material except being a polymer film, According to the objective, it can select suitably. Examples of 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.
本発明の熱線遮蔽材に用いられる前記基材の材料としては、ポリマーフィルムであること以外は特に制限はなく、様々な透明プラスチックフィルムの中から、状況に応じて適宜選択することができる。この透明プラスチックフィルムとしては、例えば、ポリエチレン、ポリプロピレン、ポリ４－メチルペンテン－１、ポリブテン－１等のポリオレフィン系樹脂；ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル系樹脂；ポリカーボネート系樹脂；ポリ塩化ビニル系樹脂；ポリフェニレンサルファイド系樹脂；ポリエーテルサルフォン系樹脂；ポリエチレンサルファイド系樹脂；ポリフェニレンエーテル系樹脂；スチレン系樹脂；アクリル系樹脂；ポリアミド系樹脂；ポリイミド系樹脂；セルロースアセテート等のセルロース系樹脂などからなるフィルム；又はこれらの積層フィルムが挙げられる。これらの中で、特にポリエチレンテレフタレートフィルムが好適である。
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. Examples of 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. Resin; Polyphenylene sulfide resin; Polyethersulfone resin; Polyethylene sulfide resin; Polyphenylene ether resin; Styrene resin; Acrylic resin; Polyamide resin; Polyimide resin; Cellulose resin such as cellulose acetate Film; or a laminated film thereof. Among these, a polyethylene terephthalate film is particularly preferable.
この基材フィルムの厚みとしては、特に制限はなく、日射遮蔽フィルムの使用目的に応じて適宜選択することができ、通常は１０μｍ～５００μｍ程度であり、１２μｍ～３００μｍが好ましく、１６μｍ～１２５μｍがより好ましい。
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 μm to 500 μm, preferably 12 μm to 300 μm, more preferably 16 μm to 125 μm. preferable.
＜３．その他の層＞
＜＜３－１．粘着層＞＞
本発明の熱線遮蔽材は、粘着層を有することが好ましい。前記粘着層は、紫外線吸収剤を含むことができる。
前記粘着層の形成に利用可能な材料としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ポリビニルブチラール（ＰＶＢ）樹脂、アクリル樹脂、スチレン／アクリル樹脂、ウレタン樹脂、ポリエステル樹脂、シリコーン樹脂などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。これらの材料からなる粘着層は、塗布により形成することができる。
さらに、前記粘着層には帯電防止剤、滑剤、ブロッキング防止剤などを添加してもよい。
前記粘着層の厚みとしては、０．１μｍ～３０μｍが好ましい。 <3. Other layers>
<< 3-1. Adhesive layer >>
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. For example, polyvinyl butyral (PVB) resin, acrylic resin, styrene / acrylic resin, urethane resin, polyester Examples thereof include resins and silicone resins. These may be used individually by 1 type and may use 2 or more types together. An adhesive layer made of these materials can be formed by coating.
Furthermore, 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 μm to 30 μm.
＜＜３－１．粘着層＞＞
本発明の熱線遮蔽材は、粘着層を有することが好ましい。前記粘着層は、紫外線吸収剤を含むことができる。
前記粘着層の形成に利用可能な材料としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ポリビニルブチラール（ＰＶＢ）樹脂、アクリル樹脂、スチレン／アクリル樹脂、ウレタン樹脂、ポリエステル樹脂、シリコーン樹脂などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。これらの材料からなる粘着層は、塗布により形成することができる。
さらに、前記粘着層には帯電防止剤、滑剤、ブロッキング防止剤などを添加してもよい。
前記粘着層の厚みとしては、０．１μｍ～３０μｍが好ましい。 <3. Other layers>
<< 3-1. Adhesive layer >>
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. For example, polyvinyl butyral (PVB) resin, acrylic resin, styrene / acrylic resin, urethane resin, polyester Examples thereof include resins and silicone resins. These may be used individually by 1 type and may use 2 or more types together. An adhesive layer made of these materials can be formed by coating.
Furthermore, 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 μm to 30 μm.
＜＜３－２．ハードコート層＞＞
耐擦傷性を付加するために、機能性フィルムがハードコート性を有するハードコート層を含むことも好適である。ハードコート層には金属酸化物粒子を含むことができる。
前記ハードコート層としては、特に制限はなく、目的に応じて適宜その種類も形成方法も選択することができ、例えば、アクリル系樹脂、シリコーン系樹脂、メラミン系樹脂、ウレタン系樹脂、アルキド系樹脂、フッ素系樹脂等の熱硬化型又は光硬化型樹脂などが挙げられる。前記ハードコート層の厚みとしては、特に制限はなく、目的に応じて適宜選択することができるが、１μｍ～５０μｍが好ましい。前記ハードコート層上に更に反射防止層及び／又は防眩層を形成すると、耐擦傷性に加え、反射防止性及び／又は防眩性を有する機能性フィルムが得られ好適である。また、前記ハードコート層に前記金属酸化物粒子を含有してもよい。 << 3-2. Hard coat layer >>
In order to add scratch resistance, it is also preferable that the functional film includes a hard coat layer having hard coat properties. The hard coat layer can contain metal oxide particles.
There is no restriction | limiting in particular as said hard-coat layer, 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 μm to 50 μm. When an antireflection layer and / or an antiglare layer are further formed on the hard coat layer, a functional film having antireflection properties and / or antiglare properties in addition to scratch resistance is preferably obtained. The hard coat layer may contain the metal oxide particles.
耐擦傷性を付加するために、機能性フィルムがハードコート性を有するハードコート層を含むことも好適である。ハードコート層には金属酸化物粒子を含むことができる。
前記ハードコート層としては、特に制限はなく、目的に応じて適宜その種類も形成方法も選択することができ、例えば、アクリル系樹脂、シリコーン系樹脂、メラミン系樹脂、ウレタン系樹脂、アルキド系樹脂、フッ素系樹脂等の熱硬化型又は光硬化型樹脂などが挙げられる。前記ハードコート層の厚みとしては、特に制限はなく、目的に応じて適宜選択することができるが、１μｍ～５０μｍが好ましい。前記ハードコート層上に更に反射防止層及び／又は防眩層を形成すると、耐擦傷性に加え、反射防止性及び／又は防眩性を有する機能性フィルムが得られ好適である。また、前記ハードコート層に前記金属酸化物粒子を含有してもよい。 << 3-2. Hard coat layer >>
In order to add scratch resistance, it is also preferable that the functional film includes a hard coat layer having hard coat properties. The hard coat layer can contain metal oxide particles.
There is no restriction | limiting in particular as said hard-coat layer, 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 μm to 50 μm. When an antireflection layer and / or an antiglare layer are further formed on the hard coat layer, a functional film having antireflection properties and / or antiglare properties in addition to scratch resistance is preferably obtained. The hard coat layer may contain the metal oxide particles.
＜＜３－３．オーバーコート層＞＞
本発明の熱線遮蔽材において、物質移動による金属平板粒子の酸化・硫化を防止し、耐擦傷性を付与するため、本発明の熱線遮蔽材は、前記六角形状乃至円形状の平板状金属粒子が露出している方の前記金属粒子含有層の表面に密接するオーバーコート層を有していてもよい。また、前記金属粒子含有層と後述の紫外線吸収層との間にオーバーコート層を有していてもよい。本発明の熱線遮蔽材は特に金属平板粒子が金属粒子含有層の表面に偏在する場合は、金属平板粒子の剥落による製造工程のコンタミ防止、別層塗布時の金属平板粒子配列乱れの防止、などのため、オーバーコート層を有していてもよい。
前記オーバーコート層には紫外線吸収剤を含んでもよい。
前記オーバーコート層としては、特に制限はなく、目的に応じて適宜選択することができるが、例えば、バインダー、マット剤、及び界面活性剤を含有し、更に必要に応じてその他の成分を含有してなる。
前記バインダーとしては、特に制限はなく、目的に応じて適宜選択することができ、例えば、アクリル系樹脂、シリコーン系樹脂、メラミン系樹脂、ウレタン系樹脂、アルキド系樹脂、フッ素系樹脂等の熱硬化型又は光硬化型樹脂などが挙げられる。
前記オーバーコート層の厚みとしては、０．０１μｍ～１，０００μｍが好ましく、０．０２μｍ～５００μｍがより好ましく、０．１～１０μｍが特に好ましく、０．２～５μｍがより特に好ましい。 << 3-3. Overcoat layer >>
In 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 | adhered to the surface of the said exposed metal particle content layer. Moreover, you may have an overcoat layer between the said metal particle content layer and the below-mentioned ultraviolet absorption layer. 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. For example, thermosetting of acrylic resin, silicone resin, melamine resin, urethane resin, alkyd resin, fluorine resin, etc. Mold or photo-curable resin.
The thickness of the overcoat layer is preferably 0.01 μm to 1,000 μm, more preferably 0.02 μm to 500 μm, particularly preferably 0.1 to 10 μm, and particularly preferably 0.2 to 5 μm.
本発明の熱線遮蔽材において、物質移動による金属平板粒子の酸化・硫化を防止し、耐擦傷性を付与するため、本発明の熱線遮蔽材は、前記六角形状乃至円形状の平板状金属粒子が露出している方の前記金属粒子含有層の表面に密接するオーバーコート層を有していてもよい。また、前記金属粒子含有層と後述の紫外線吸収層との間にオーバーコート層を有していてもよい。本発明の熱線遮蔽材は特に金属平板粒子が金属粒子含有層の表面に偏在する場合は、金属平板粒子の剥落による製造工程のコンタミ防止、別層塗布時の金属平板粒子配列乱れの防止、などのため、オーバーコート層を有していてもよい。
前記オーバーコート層には紫外線吸収剤を含んでもよい。
前記オーバーコート層としては、特に制限はなく、目的に応じて適宜選択することができるが、例えば、バインダー、マット剤、及び界面活性剤を含有し、更に必要に応じてその他の成分を含有してなる。
前記バインダーとしては、特に制限はなく、目的に応じて適宜選択することができ、例えば、アクリル系樹脂、シリコーン系樹脂、メラミン系樹脂、ウレタン系樹脂、アルキド系樹脂、フッ素系樹脂等の熱硬化型又は光硬化型樹脂などが挙げられる。
前記オーバーコート層の厚みとしては、０．０１μｍ～１，０００μｍが好ましく、０．０２μｍ～５００μｍがより好ましく、０．１～１０μｍが特に好ましく、０．２～５μｍがより特に好ましい。 << 3-3. Overcoat layer >>
In 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 | adhered to the surface of the said exposed metal particle content layer. Moreover, you may have an overcoat layer between the said metal particle content layer and the below-mentioned ultraviolet absorption layer. 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. For example, thermosetting of acrylic resin, silicone resin, melamine resin, urethane resin, alkyd resin, fluorine resin, etc. Mold or photo-curable resin.
The thickness of the overcoat layer is preferably 0.01 μm to 1,000 μm, more preferably 0.02 μm to 500 μm, particularly preferably 0.1 to 10 μm, and particularly preferably 0.2 to 5 μm.
＜＜３－４．紫外線吸収剤＞＞
前記紫外線吸収剤を含有する層は、目的に応じて適宜選択することができ、粘着層であってもよく、また、前記粘着層と前記金属粒子含有層との間の層（例えば、オーバーコート層など）であってもよい。いずれの場合も、前記紫外線吸収剤は、前記金属粒子含有層に対して、太陽光が照射される側に配置される層に添加されることが好ましい。 << 3-4. UV absorber >>
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.
前記紫外線吸収剤を含有する層は、目的に応じて適宜選択することができ、粘着層であってもよく、また、前記粘着層と前記金属粒子含有層との間の層（例えば、オーバーコート層など）であってもよい。いずれの場合も、前記紫外線吸収剤は、前記金属粒子含有層に対して、太陽光が照射される側に配置される層に添加されることが好ましい。 << 3-4. UV absorber >>
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.
前記紫外線吸収剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ベンゾフェノン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤、トリアジン系紫外線吸収剤、サリチレート系紫外線吸収剤、シアノアクリレート系紫外線吸収剤などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。
The ultraviolet absorber is not particularly limited and may be appropriately selected depending on the purpose. For example, 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.
前記ベンゾフェノン系紫外線吸収剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、２，４ドロキシ－４－メトキシ－５－スルホベンゾフェノンなどが挙げられる。
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.
前記ベンゾトリアゾール系紫外線吸収剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、２－（５－クロロ－２Ｈ－ベンゾトリアゾール－２－イル）－４－メチル－６－ｔｅｒｔ－ブチルフェノール（チヌビン３２６）、２－（２－ヒドロキシ－５－メチルフェニル）ベンゾトリアゾール、２－（２－ヒドロキシ－５－ターシャリーブチルフェニル）ベンゾトリアゾール、２－（２－ヒドロキシ－３－５－ジターシャリーブチルフェニル）－５－クロロベンゾトリアゾールなどが挙げられる。
The benzotriazole ultraviolet absorber is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 2- (5-chloro-2H-benzotriazol-2-yl) -4-methyl-6 -Tert-butylphenol (tinuvin 326), 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tertiarybutylphenyl) benzotriazole, 2- (2-hydroxy-3- 5-ditertiary butylphenyl) -5-chlorobenzotriazole and the like.
前記トリアジン系紫外線吸収剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、モノ（ヒドロキシフェニル）トリアジン化合物、ビス（ヒドロキシフェニル）トリアジン化合物、トリス（ヒドロキシフェニル）トリアジン化合物などが挙げられる。
前記モノ（ヒドロキシフェニル）トリアジン化合物としては、例えば、２－[４－[(２－ヒドロキシ－３－ドデシルオキシプロピル)オキシ]－２－ヒドロキシフェニル]－４,６－ビス(２,４－ジメチルフェニル)－１,３,５－トリアジン、２－[４－[(２－ヒドロキシ－３－トリデシルオキシプロピル)オキシ]－２－ヒドロキシフェニル]－４,６－ビス(２,４－ジメチルフェニル)－１,３,５－トリアジン、２－(２,４－ジヒドロキシフェニル)－４,６－ビス(２,４－ジメチルフェニル)－１,３,５－トリアジン、２－(２－ヒドロキシ－４－イソオクチルオキシフェニル)－４,６－ビス(２,４－ジメチルフェニル)－１,３,５－トリアジン、２－(２－ヒドロキシ－４－ドデシルオキシフェニル)－４,６－ビス(２,４－ジメチルフェニル)－１,３,５－トリアジンなどが挙げられる。前記ビス（ヒドロキシフェニル）トリアジン化合物としては、例えば、２,４－ビス(２－ヒドロキシ－４－プロピルオキシフェニル)－６－(２,４－ジメチルフェニル)－１,３,５－トリアジン、２,４－ビス(２－ヒドロキシ－３－メチル－４－プロピルオキシフェニル)－６－(４－メチルフェニル)－１,３,５－トリアジン、２,４－ビス(２－ヒドロキシ－３－メチル－４－ヘキシルオキシフェニル)－６－(２,４－ジメチルフェニル)－１,３,５－トリアジン、２－フェニル－４,６－ビス[２－ヒドロキシ－４－[３－(メトキシヘプタエトキシ)－２－ヒドロキシプロピルオキシ]フェニル]－１,３,５－トリアジンなどが挙げられる。前記トリス（ヒドロキシフェニル）トリアジン化合物としては、例えば、２,４－ビス(２－ヒドロキシ－４－ブトキシフェニル)－６－(２,４－ジブトキシフェニル)－１,３,５－トリアジン、２,４,６－トリス(２－ヒドロキシ－４－オクチルオキシフェニル)－１,３,５－トリアジン、２,４,６－トリス[２－ヒドロキシ－４－(３－ブトキシ－２－ヒドロキシプロピルオキシ)フェニル]－１,３,５－トリアジン、２,４－ビス[２－ヒドロキシ－４－[１－(イソオクチルオキシカルボニル)エトキシ]フェニル]－６－(２,４－ジヒドロキシフェニル)－１,３,５－トリアジン、２,４,６－トリス[２－ヒドロキシ－４－[１－(イソオクチルオキシカルボニル)エトキシ]フェニル]－１,３,５－トリアジン、２,４－ビス[２－ヒドロキシ－４－[１－(イソオクチルオキシカルボニル)エトキシ]フェニル]－６－[２,４－ビス[１－(イソオクチルオキシカルボニル)エトキシ]フェニル]－１,３,５－トリアジンなどが挙げられる。 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. Is mentioned. 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. Examples of the tris (hydroxyphenyl) triazine compound 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- [1- (isooctyloxy) Carbonyl) ethoxy] phenyl] -6- [2,4-bis [1- (iso-octyloxy) ethoxy] phenyl] -1,3,5-triazine.
前記モノ（ヒドロキシフェニル）トリアジン化合物としては、例えば、２－[４－[(２－ヒドロキシ－３－ドデシルオキシプロピル)オキシ]－２－ヒドロキシフェニル]－４,６－ビス(２,４－ジメチルフェニル)－１,３,５－トリアジン、２－[４－[(２－ヒドロキシ－３－トリデシルオキシプロピル)オキシ]－２－ヒドロキシフェニル]－４,６－ビス(２,４－ジメチルフェニル)－１,３,５－トリアジン、２－(２,４－ジヒドロキシフェニル)－４,６－ビス(２,４－ジメチルフェニル)－１,３,５－トリアジン、２－(２－ヒドロキシ－４－イソオクチルオキシフェニル)－４,６－ビス(２,４－ジメチルフェニル)－１,３,５－トリアジン、２－(２－ヒドロキシ－４－ドデシルオキシフェニル)－４,６－ビス(２,４－ジメチルフェニル)－１,３,５－トリアジンなどが挙げられる。前記ビス（ヒドロキシフェニル）トリアジン化合物としては、例えば、２,４－ビス(２－ヒドロキシ－４－プロピルオキシフェニル)－６－(２,４－ジメチルフェニル)－１,３,５－トリアジン、２,４－ビス(２－ヒドロキシ－３－メチル－４－プロピルオキシフェニル)－６－(４－メチルフェニル)－１,３,５－トリアジン、２,４－ビス(２－ヒドロキシ－３－メチル－４－ヘキシルオキシフェニル)－６－(２,４－ジメチルフェニル)－１,３,５－トリアジン、２－フェニル－４,６－ビス[２－ヒドロキシ－４－[３－(メトキシヘプタエトキシ)－２－ヒドロキシプロピルオキシ]フェニル]－１,３,５－トリアジンなどが挙げられる。前記トリス（ヒドロキシフェニル）トリアジン化合物としては、例えば、２,４－ビス(２－ヒドロキシ－４－ブトキシフェニル)－６－(２,４－ジブトキシフェニル)－１,３,５－トリアジン、２,４,６－トリス(２－ヒドロキシ－４－オクチルオキシフェニル)－１,３,５－トリアジン、２,４,６－トリス[２－ヒドロキシ－４－(３－ブトキシ－２－ヒドロキシプロピルオキシ)フェニル]－１,３,５－トリアジン、２,４－ビス[２－ヒドロキシ－４－[１－(イソオクチルオキシカルボニル)エトキシ]フェニル]－６－(２,４－ジヒドロキシフェニル)－１,３,５－トリアジン、２,４,６－トリス[２－ヒドロキシ－４－[１－(イソオクチルオキシカルボニル)エトキシ]フェニル]－１,３,５－トリアジン、２,４－ビス[２－ヒドロキシ－４－[１－(イソオクチルオキシカルボニル)エトキシ]フェニル]－６－[２,４－ビス[１－(イソオクチルオキシカルボニル)エトキシ]フェニル]－１,３,５－トリアジンなどが挙げられる。 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. Is mentioned. 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. Examples of the tris (hydroxyphenyl) triazine compound 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- [1- (isooctyloxy) Carbonyl) ethoxy] phenyl] -6- [2,4-bis [1- (iso-octyloxy) ethoxy] phenyl] -1,3,5-triazine.
前記サリチレート系紫外線吸収剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、フェニルサリチレート、ｐ－ｔｅｒｔ－ブチルフェニルサリチレート、ｐ－オクチルフェニルサリチレート、２－エチルヘキシルサリチレートなどが挙げられる。
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.
前記シアノアクリレート系紫外線吸収剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、２－エチルヘキシル－２－シアノ－３，３－ジフェニルアクリレート、エチル－２－シアノ－３，３－ジフェニルアクリレートなどが挙げられる。
The cyanoacrylate-based ultraviolet absorber is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3 , 3-diphenyl acrylate and the like.
前記バインダーとしては、特に制限はなく、目的に応じて適宜選択することができるが、可視光透明性や日射透明性が高い方が好ましく、例えば、アクリル樹脂、ポリビニルブチラール、ポリビニルアルコールなどが挙げられる。なお、バインダーが熱線を吸収すると、金属平板粒子による反射効果が弱まってしまうことから、熱線源と金属平板粒子との間に形成される紫外線吸収層としては、４５０ｎｍ～１，５００ｎｍの領域に吸収を持たない材料を選択したり、該紫外線吸収層の厚みを薄くしたりすることが好ましい。
前記紫外線吸収層の厚みとしては、０．０１μｍ～１，０００μｍが好ましく、０．０２μｍ～５００μｍがより好ましい。前記厚みが、０．０１μｍ未満であると、紫外線の吸収が足りなくなることがあり、１，０００μｍを超えると、可視光の透過率が下がることがある。
前記紫外線吸収層の含有量としては、用いる紫外線吸収層によって異なり、一概に規定することができないが、本発明の熱線遮蔽材において所望の紫外線透過率を与える含有量を適宜選択することが好ましい。
前記紫外線透過率としては、５％以下が好ましく、２％以下がより好ましい。前記紫外線透過率が、５％を超えると、太陽光の紫外線により前記金属平板粒子層の色味が変化することがある。 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. . When 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 μm to 1,000 μm, more preferably 0.02 μm to 500 μm. When the thickness is less than 0.01 μm, the absorption of ultraviolet rays may be insufficient, and when it exceeds 1,000 μm, 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.
前記紫外線吸収層の厚みとしては、０．０１μｍ～１，０００μｍが好ましく、０．０２μｍ～５００μｍがより好ましい。前記厚みが、０．０１μｍ未満であると、紫外線の吸収が足りなくなることがあり、１，０００μｍを超えると、可視光の透過率が下がることがある。
前記紫外線吸収層の含有量としては、用いる紫外線吸収層によって異なり、一概に規定することができないが、本発明の熱線遮蔽材において所望の紫外線透過率を与える含有量を適宜選択することが好ましい。
前記紫外線透過率としては、５％以下が好ましく、２％以下がより好ましい。前記紫外線透過率が、５％を超えると、太陽光の紫外線により前記金属平板粒子層の色味が変化することがある。 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. . When 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 μm to 1,000 μm, more preferably 0.02 μm to 500 μm. When the thickness is less than 0.01 μm, the absorption of ultraviolet rays may be insufficient, and when it exceeds 1,000 μm, 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.
＜＜３－５．金属酸化物粒子＞＞
本発明の熱線遮蔽材は、長波赤外線を吸収するために、少なくとも１種の金属酸化物粒子を含有することが、熱線遮蔽と製造コストのバランスの観点から、好ましい。本発明の熱線遮蔽材では、前記金属酸化物粒子を含有する層が、前記金属粒子含有層の前記六角形状乃至円形状の平板状金属粒子が露出している方の前記金属粒子含有層の表面とは反対側の表面側に、有することが好ましい。この場合、図３Ａに示すように、例えばハードコート層５に金属酸化物粒子を含むことが好ましい。ハードコート層５は、基材１を介して、前記金属粒子含有層２と積層されていてもよい。図３Ａのような構成であると、金属粒子含有層２が太陽光などの熱線の入射方向側となるように本発明の熱線遮蔽材を配置したときに、金属粒子含有層２で熱線の一部（または全部でもよい）を反射した後、ハードコート層５で熱線の一部を吸収することとなり、金属酸化物含有層で吸収されずに熱線遮蔽材を透過した熱線に起因して熱線遮蔽材の内側で直接受ける熱量と、熱線遮蔽材の金属酸化物含有層で吸収されて間接的に熱線遮蔽材の内側に伝わる熱量の合計としての熱量を低減することができる。
前記金属酸化物粒子の材料としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、錫ドープ酸化インジウム（以下、「ＩＴＯ」と略記する。）、錫ドープ酸化アンチモン（以下、「ＡＴＯ」と略記する。）、酸化亜鉛、酸化チタン、酸化インジウム、酸化錫、酸化アンチモン、ガラスセラミックスなどが挙げられる。これらの中でも、熱線吸収能力に優れ、金属平板粒子と組み合わせることにより幅広い熱線吸収能を有する熱線遮蔽材が製造できる点で、ＩＴＯ、ＡＴＯ、酸化亜鉛がより好ましく、１，２００ｎｍ以上の赤外線を９０％以上遮蔽し、可視光透過率が９０％以上である点で、ＩＴＯが特に好ましい。
前記金属酸化物粒子の一次粒子の体積平均粒径としては、可視光透過率を低下させないため、０．１μｍ以下が好ましい。
前記金属酸化物粒子の形状としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、球状、針状、板状などが挙げられる。 << 3-5. Metal oxide particles >>
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. In the heat ray shielding material of the present invention, 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. In this case, as shown in FIG. 3A, for example, thehard 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. 3A, 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.
There is no restriction | limiting in particular as a material of the said metal oxide particle, According to the objective, it can select suitably, For example, a tin dope indium oxide (henceforth "ITO"), a tin dope antimony oxide (henceforth). , Abbreviated as “ATO”), zinc oxide, titanium oxide, indium oxide, tin oxide, antimony oxide, glass ceramics, and the like. Among these, 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. In particular, 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 μm or less in order not to reduce the visible light transmittance.
There is no restriction | 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.
本発明の熱線遮蔽材は、長波赤外線を吸収するために、少なくとも１種の金属酸化物粒子を含有することが、熱線遮蔽と製造コストのバランスの観点から、好ましい。本発明の熱線遮蔽材では、前記金属酸化物粒子を含有する層が、前記金属粒子含有層の前記六角形状乃至円形状の平板状金属粒子が露出している方の前記金属粒子含有層の表面とは反対側の表面側に、有することが好ましい。この場合、図３Ａに示すように、例えばハードコート層５に金属酸化物粒子を含むことが好ましい。ハードコート層５は、基材１を介して、前記金属粒子含有層２と積層されていてもよい。図３Ａのような構成であると、金属粒子含有層２が太陽光などの熱線の入射方向側となるように本発明の熱線遮蔽材を配置したときに、金属粒子含有層２で熱線の一部（または全部でもよい）を反射した後、ハードコート層５で熱線の一部を吸収することとなり、金属酸化物含有層で吸収されずに熱線遮蔽材を透過した熱線に起因して熱線遮蔽材の内側で直接受ける熱量と、熱線遮蔽材の金属酸化物含有層で吸収されて間接的に熱線遮蔽材の内側に伝わる熱量の合計としての熱量を低減することができる。
前記金属酸化物粒子の材料としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、錫ドープ酸化インジウム（以下、「ＩＴＯ」と略記する。）、錫ドープ酸化アンチモン（以下、「ＡＴＯ」と略記する。）、酸化亜鉛、酸化チタン、酸化インジウム、酸化錫、酸化アンチモン、ガラスセラミックスなどが挙げられる。これらの中でも、熱線吸収能力に優れ、金属平板粒子と組み合わせることにより幅広い熱線吸収能を有する熱線遮蔽材が製造できる点で、ＩＴＯ、ＡＴＯ、酸化亜鉛がより好ましく、１，２００ｎｍ以上の赤外線を９０％以上遮蔽し、可視光透過率が９０％以上である点で、ＩＴＯが特に好ましい。
前記金属酸化物粒子の一次粒子の体積平均粒径としては、可視光透過率を低下させないため、０．１μｍ以下が好ましい。
前記金属酸化物粒子の形状としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、球状、針状、板状などが挙げられる。 << 3-5. Metal oxide particles >>
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. In the heat ray shielding material of the present invention, 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. In this case, as shown in FIG. 3A, for example, the
There is no restriction | limiting in particular as a material of the said metal oxide particle, According to the objective, it can select suitably, For example, a tin dope indium oxide (henceforth "ITO"), a tin dope antimony oxide (henceforth). , Abbreviated as “ATO”), zinc oxide, titanium oxide, indium oxide, tin oxide, antimony oxide, glass ceramics, and the like. Among these, 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. In particular, 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 μm or less in order not to reduce the visible light transmittance.
There is no restriction | 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.
前記金属酸化物粒子の前記金属酸化物粒子含有層における含有量としては、特に制限はなく、目的に応じて適宜選択することができるが、０．１ｇ／ｍ２～２０ｇ／ｍ２が好ましく、０．５ｇ／ｍ２～１０ｇ／ｍ２がより好ましく、１．０ｇ／ｍ２～４．０ｇ／ｍ２がより好ましい。
前記含有量が、０．１ｇ／ｍ２未満であると、肌に感じる日射量が上昇することがあり、２０ｇ／ｍ２を超えると、可視光透過率が悪化することがある。一方、前記含有量が、１．０ｇ／ｍ２～４．０ｇ／ｍ２であると、上記２点を回避できる点で有利である。
なお、前記金属酸化物粒子の前記金属酸化物粒子含有層における含有量は、例えば、前記熱線遮蔽層の超箔切片ＴＥＭ像及び表面ＳＥＭ像の観察から、一定面積における金属酸化物粒子の個数及び平均粒子径を測定し、該個数及び平均粒子径と、金属酸化物粒子の比重とに基づいて算出した質量（ｇ）を、前記一定面積（ｍ２）で除することにより算出することができる。また、前記金属酸化物粒子含有層の一定面積における金属酸化物微粒子をメタノールに溶出させ、蛍光Ｘ線測定により測定した金属酸化物微粒子の質量（ｇ）を、前記一定面積（ｍ２）で除することにより算出することもできる。 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. On the other hand, when the content is 1.0 g / m 2 to 4.0 g / m 2, it is advantageous in that the above two points can be avoided.
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 ). . Further, 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.
前記含有量が、０．１ｇ／ｍ２未満であると、肌に感じる日射量が上昇することがあり、２０ｇ／ｍ２を超えると、可視光透過率が悪化することがある。一方、前記含有量が、１．０ｇ／ｍ２～４．０ｇ／ｍ２であると、上記２点を回避できる点で有利である。
なお、前記金属酸化物粒子の前記金属酸化物粒子含有層における含有量は、例えば、前記熱線遮蔽層の超箔切片ＴＥＭ像及び表面ＳＥＭ像の観察から、一定面積における金属酸化物粒子の個数及び平均粒子径を測定し、該個数及び平均粒子径と、金属酸化物粒子の比重とに基づいて算出した質量（ｇ）を、前記一定面積（ｍ２）で除することにより算出することができる。また、前記金属酸化物粒子含有層の一定面積における金属酸化物微粒子をメタノールに溶出させ、蛍光Ｘ線測定により測定した金属酸化物微粒子の質量（ｇ）を、前記一定面積（ｍ２）で除することにより算出することもできる。 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. On the other hand, when the content is 1.0 g / m 2 to 4.0 g / m 2, it is advantageous in that the above two points can be avoided.
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 ). . Further, 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.
＜４．熱線遮蔽材の製造方法＞
本発明の熱線遮蔽材の製造方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、塗布方法により、前記基材の表面に前記金属粒子含有層、前記紫外線吸収層、更に必要に応じてその他の層を形成する方法が挙げられる。 <4. Manufacturing method of heat ray shielding material>
There is no restriction | limiting in particular as a manufacturing method of the heat ray shielding material of this invention, According to the objective, it can select suitably, For example, the said metal particle content layer and the said ultraviolet absorption layer are applied to the surface of the said base material by the apply | coating method. In addition, a method of forming other layers as necessary may be mentioned.
本発明の熱線遮蔽材の製造方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、塗布方法により、前記基材の表面に前記金属粒子含有層、前記紫外線吸収層、更に必要に応じてその他の層を形成する方法が挙げられる。 <4. Manufacturing method of heat ray shielding material>
There is no restriction | limiting in particular as a manufacturing method of the heat ray shielding material of this invention, According to the objective, it can select suitably, For example, the said metal particle content layer and the said ultraviolet absorption layer are applied to the surface of the said base material by the apply | coating method. In addition, a method of forming other layers as necessary may be mentioned.
－４－１．金属粒子含有層の形成方法－
本発明の金属粒子含有層の形成方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、前記基材などの下層の表面上に、前記金属平板粒子を有する分散液を、ディップコーター、ダイコーター、スリットコーター、バーコーター、グラビアコーター等により塗布する方法、ＬＢ膜法、自己組織化法、スプレー塗布などの方法で面配向させる方法が挙げられる。本発明の熱線遮蔽材を製造するとき、後述の実施例で用いた金属粒子含有層の組成とし、ラテックスを添加する等によって、前記六角形状乃至円形状の平板状金属粒子の８０個数％以上が、前記金属粒子含有層の表面からｄ／２の範囲に存在するようにすることが好ましい。前記六角形状乃至円形状の平板状金属粒子の８０個数％以上が、前記金属粒子含有層の表面からｄ／３の範囲に存在するようにすることがより好ましい。前記ラテックスの添加量に特に制限は無いが、例えば金属平板粒子に対して、１～１００００質量％添加することが好ましく、１０～１０００質量％添加することがより好ましく、２０～５００質量％添加することが特に好ましい。 4-1. 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. For example, 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. When producing the heat ray shielding material of the present invention, 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.
本発明の金属粒子含有層の形成方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、前記基材などの下層の表面上に、前記金属平板粒子を有する分散液を、ディップコーター、ダイコーター、スリットコーター、バーコーター、グラビアコーター等により塗布する方法、ＬＢ膜法、自己組織化法、スプレー塗布などの方法で面配向させる方法が挙げられる。本発明の熱線遮蔽材を製造するとき、後述の実施例で用いた金属粒子含有層の組成とし、ラテックスを添加する等によって、前記六角形状乃至円形状の平板状金属粒子の８０個数％以上が、前記金属粒子含有層の表面からｄ／２の範囲に存在するようにすることが好ましい。前記六角形状乃至円形状の平板状金属粒子の８０個数％以上が、前記金属粒子含有層の表面からｄ／３の範囲に存在するようにすることがより好ましい。前記ラテックスの添加量に特に制限は無いが、例えば金属平板粒子に対して、１～１００００質量％添加することが好ましく、１０～１０００質量％添加することがより好ましく、２０～５００質量％添加することが特に好ましい。 4-1. 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. For example, 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. When producing the heat ray shielding material of the present invention, 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.
なお、面配向を促進するために、金属平板粒子を塗布後、カレンダーローラーやラミローラーなどの圧着ローラーを通すことにより促進させてもよい。
In addition, in order to promote plane orientation, after applying metal tabular grains, it may be promoted by passing through a pressure roller such as a calender roller or a lami roller.
－４－２．オーバーコート層の形成方法－
オーバーコート層は、塗布により形成することが好ましい。このときの塗布方法としては、特に限定はなく、公知の方法を用いることができ、例えば、前記紫外線吸収剤を含有する分散液を、ディップコーター、ダイコーター、スリットコーター、バーコーター、グラビアコーター等により塗布する方法などが挙げられる。 -4-2. Formation method of overcoat layer
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. For example, 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.
オーバーコート層は、塗布により形成することが好ましい。このときの塗布方法としては、特に限定はなく、公知の方法を用いることができ、例えば、前記紫外線吸収剤を含有する分散液を、ディップコーター、ダイコーター、スリットコーター、バーコーター、グラビアコーター等により塗布する方法などが挙げられる。 -4-2. Formation method of overcoat layer
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. For example, 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.
－４－３．ハードコート層の形成方法－
ハードコート層は、塗布により形成することが好ましい。このときの塗布方法としては、特に限定はなく、公知の方法を用いることができ、例えば、前記紫外線吸収剤を含有する分散液を、ディップコーター、ダイコーター、スリットコーター、バーコーター、グラビアコーター等により塗布する方法などが挙げられる。 -4-3. Formation method of hard coat layer
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. For example, 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.
ハードコート層は、塗布により形成することが好ましい。このときの塗布方法としては、特に限定はなく、公知の方法を用いることができ、例えば、前記紫外線吸収剤を含有する分散液を、ディップコーター、ダイコーター、スリットコーター、バーコーター、グラビアコーター等により塗布する方法などが挙げられる。 -4-3. Formation method of hard coat layer
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. For example, 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.
－４－４．粘着層の形成方法－
前記粘着層は、塗布により形成することが好ましい。例えば、前記基材、前記金属粒子含有層、前記紫外線吸収層などの下層の表面上に積層することができる。このときの塗布方法としては、特に限定はなく、公知の方法を用いることができる。 -4-4. Formation method of adhesive layer
The adhesive layer is preferably formed by coating. For example, 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. There is no limitation in particular as the coating method at this time, A well-known method can be used.
前記粘着層は、塗布により形成することが好ましい。例えば、前記基材、前記金属粒子含有層、前記紫外線吸収層などの下層の表面上に積層することができる。このときの塗布方法としては、特に限定はなく、公知の方法を用いることができる。 -4-4. Formation method of adhesive layer
The adhesive layer is preferably formed by coating. For example, 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. There is no limitation in particular as the coating method at this time, A well-known method can be used.
本発明の熱線遮蔽材の日射反射率としては、６００ｎｍ～２，０００ｎｍの範囲（好ましくは８００ｎｍ～１，８００ｎｍ）で最大値を有することが、熱線反射率の効率を上げることができる点で好ましい。
本発明の熱線遮蔽材の可視光線透過率としては、６０％以上が好ましく、７０％以上がより好ましい。前記可視光線透過率が、６０％未満であると、例えば、自動車用ガラスや建物用ガラスとして用いた時に、外部が見にくくなることがある。
本発明の熱線遮蔽材の紫外線透過率としては、５％以下が好ましく、２％以下がより好ましい。前記紫外線透過率が、５％を超えると、太陽光の紫外線により前記金属平板粒子層の色味が変化することがある。
本発明の熱線遮蔽材のヘイズは、２０％以下であることが好ましい。前記ヘイズが２０％を超えると、例えば、自動車用ガラスや建物用ガラスとして用いた時に外部が見にくくなるなど、安全上好ましくないことがある。 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. When the ultraviolet transmittance exceeds 5%, the color of the metal tabular grain layer may change due to ultraviolet rays of sunlight.
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.
本発明の熱線遮蔽材の可視光線透過率としては、６０％以上が好ましく、７０％以上がより好ましい。前記可視光線透過率が、６０％未満であると、例えば、自動車用ガラスや建物用ガラスとして用いた時に、外部が見にくくなることがある。
本発明の熱線遮蔽材の紫外線透過率としては、５％以下が好ましく、２％以下がより好ましい。前記紫外線透過率が、５％を超えると、太陽光の紫外線により前記金属平板粒子層の色味が変化することがある。
本発明の熱線遮蔽材のヘイズは、２０％以下であることが好ましい。前記ヘイズが２０％を超えると、例えば、自動車用ガラスや建物用ガラスとして用いた時に外部が見にくくなるなど、安全上好ましくないことがある。 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. When the ultraviolet transmittance exceeds 5%, the color of the metal tabular grain layer may change due to ultraviolet rays of sunlight.
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.
－４－５．ドライラミネーションによる粘着剤層積層－
本発明の熱線遮蔽材フィルムを使って、既設窓ガラスの類に機能性付与する場合は、粘着剤を積層してガラスの室内側に貼り付ける。その際、反射層をなるべく太陽光側に向けた方が発熱を防ぐことになるので、銀ナノディスク粒子層の上に粘着剤層を積層し、その面から窓ガラスへ貼合するのが適切である。
銀ナノディスク層表面への粘着剤層積層に当っては、当該表面に直接粘着剤入りの塗布液を塗工することもできるが、粘着剤に含まれる各種添加剤、可塑剤や、使用溶剤などが、場合によっては銀ナノディスク層の配列を乱したり、銀ナノディスク自身を変質させたりすることがある。そうした弊害を最小限に留めるためには、粘着剤を予め離型フィルム上に塗工及び乾燥させたフィルムを作製しておいて、当該フィルムの粘着剤面と本発明フィルムの銀ナノディスク層表面とをラミネートすることにより、ドライな状態のままの積層をすることが有効である。 -4--5. 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.
When laminating the pressure-sensitive adhesive layer on the surface of the silver nanodisk layer, 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. In order to minimize such harmful effects, 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.
本発明の熱線遮蔽材フィルムを使って、既設窓ガラスの類に機能性付与する場合は、粘着剤を積層してガラスの室内側に貼り付ける。その際、反射層をなるべく太陽光側に向けた方が発熱を防ぐことになるので、銀ナノディスク粒子層の上に粘着剤層を積層し、その面から窓ガラスへ貼合するのが適切である。
銀ナノディスク層表面への粘着剤層積層に当っては、当該表面に直接粘着剤入りの塗布液を塗工することもできるが、粘着剤に含まれる各種添加剤、可塑剤や、使用溶剤などが、場合によっては銀ナノディスク層の配列を乱したり、銀ナノディスク自身を変質させたりすることがある。そうした弊害を最小限に留めるためには、粘着剤を予め離型フィルム上に塗工及び乾燥させたフィルムを作製しておいて、当該フィルムの粘着剤面と本発明フィルムの銀ナノディスク層表面とをラミネートすることにより、ドライな状態のままの積層をすることが有効である。 -4--5. 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.
When laminating the pressure-sensitive adhesive layer on the surface of the silver nanodisk layer, 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. In order to minimize such harmful effects, 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.
［貼合せ構造体］
本発明の熱線遮蔽材と、ガラス及びプラスチックのいずれかとを貼り合わせてなる貼合せ構造体を製造することができる。
前記貼合せ構造体の製造方法としては、特に制限はなく、目的に応じて適宜選択することができ、上述のように製造した本発明の熱線遮蔽材を、自動車等の乗り物用ガラスまたはプラスチックや、建材用ガラスまたはプラスチックに貼合せる方法などが挙げられる。 [Laminated structure]
A bonded structure obtained by bonding the heat ray shielding material of the present invention and either glass or plastic can be produced.
There is no restriction | limiting in particular as a manufacturing method of the said bonding structure, According to the objective, it can select suitably, 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.
本発明の熱線遮蔽材と、ガラス及びプラスチックのいずれかとを貼り合わせてなる貼合せ構造体を製造することができる。
前記貼合せ構造体の製造方法としては、特に制限はなく、目的に応じて適宜選択することができ、上述のように製造した本発明の熱線遮蔽材を、自動車等の乗り物用ガラスまたはプラスチックや、建材用ガラスまたはプラスチックに貼合せる方法などが挙げられる。 [Laminated structure]
A bonded structure obtained by bonding the heat ray shielding material of the present invention and either glass or plastic can be produced.
There is no restriction | limiting in particular as a manufacturing method of the said bonding structure, According to the objective, it can select suitably, 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.
［熱線遮蔽材及び貼合せ構造体の使用態様］
本発明の熱線遮蔽材は、熱線（近赤外線）を選択的に反射または吸収するために使用される態様であれば、特に制限はなく、目的に応じて適宜選択すればよく、例えば、乗り物用フィルムや貼合せ構造体、建材用フィルムや貼合せ構造体、農業用フィルムなどが挙げられる。これらの中でも、省エネルギー効果の点で、乗り物用フィルムや貼合せ構造体、建材用フィルムや貼合せ構造体であることが好ましい。
なお、本発明において、熱線（近赤外線）とは、太陽光に約５０％含まれる近赤外線（７８０ｎｍ～１，８００ｎｍ）を意味する。 [Usage of heat ray shielding material and bonded structure]
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.
In the present invention, heat rays (near infrared rays) mean near infrared rays (780 nm to 1,800 nm) contained in sunlight by about 50%.
本発明の熱線遮蔽材は、熱線（近赤外線）を選択的に反射または吸収するために使用される態様であれば、特に制限はなく、目的に応じて適宜選択すればよく、例えば、乗り物用フィルムや貼合せ構造体、建材用フィルムや貼合せ構造体、農業用フィルムなどが挙げられる。これらの中でも、省エネルギー効果の点で、乗り物用フィルムや貼合せ構造体、建材用フィルムや貼合せ構造体であることが好ましい。
なお、本発明において、熱線（近赤外線）とは、太陽光に約５０％含まれる近赤外線（７８０ｎｍ～１，８００ｎｍ）を意味する。 [Usage of heat ray shielding material and bonded structure]
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.
In the present invention, heat rays (near infrared rays) mean near infrared rays (780 nm to 1,800 nm) contained in sunlight by about 50%.
以下に実施例を挙げて本発明の特徴をさらに具体的に説明する。
以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。 The features of the present invention will be described more specifically with reference to the following examples.
The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.
以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。 The features of the present invention will be described more specifically with reference to the following examples.
The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.
（製造例１：銀平板粒子分散液Ｂ１の調製）
－銀平板粒子の合成（銀平板粒子分散液Ａの調製）－
－－平板核粒子の合成工程－－
２．５ｍＭのクエン酸ナトリウム水溶液５０ｍＬに０．５ｇ／Ｌのポリスチレンスルホン酸水溶液を２．５ｍＬ添加し、３５℃まで加熱した。この溶液に１０ｍＭの水素化ほう素ナトリウム水溶液を３ｍＬ添加し、０．５ｍＭの硝酸銀水溶液５０ｍＬを２０ｍＬ／ｍｉｎで攪拌しながら添加した。この溶液を３０分間攪拌し、種溶液を作製した。 (Production Example 1: Preparation of silver tabular grain dispersion liquid B1)
-Synthesis of silver tabular grains (Preparation of silver tabular grain dispersion A)-
--- Synthesis of tabular core grains--
2.5 mL of 0.5 g / L polystyrene sulfonic acid aqueous solution was added to 50 mL of 2.5 mM sodium citrate aqueous solution and heated to 35 ° C. To this solution, 3 mL of 10 mM sodium borohydride aqueous solution was added, and 50 mL of 0.5 mM silver nitrate aqueous solution was added with stirring at 20 mL / min. This solution was stirred for 30 minutes to prepare a seed solution.
－銀平板粒子の合成（銀平板粒子分散液Ａの調製）－
－－平板核粒子の合成工程－－
２．５ｍＭのクエン酸ナトリウム水溶液５０ｍＬに０．５ｇ／Ｌのポリスチレンスルホン酸水溶液を２．５ｍＬ添加し、３５℃まで加熱した。この溶液に１０ｍＭの水素化ほう素ナトリウム水溶液を３ｍＬ添加し、０．５ｍＭの硝酸銀水溶液５０ｍＬを２０ｍＬ／ｍｉｎで攪拌しながら添加した。この溶液を３０分間攪拌し、種溶液を作製した。 (Production Example 1: Preparation of silver tabular grain dispersion liquid B1)
-Synthesis of silver tabular grains (Preparation of silver tabular grain dispersion A)-
--- Synthesis of tabular core grains--
2.5 mL of 0.5 g / L polystyrene sulfonic acid aqueous solution was added to 50 mL of 2.5 mM sodium citrate aqueous solution and heated to 35 ° C. To this solution, 3 mL of 10 mM sodium borohydride aqueous solution was added, and 50 mL of 0.5 mM silver nitrate aqueous solution was added with stirring at 20 mL / min. This solution was stirred for 30 minutes to prepare a seed solution.
－－平板粒子の第１成長工程－－
次に、前記種溶液２５０ｍＬに１０ｍＭのアスコルビン酸水溶液を２ｍＬ添加し、３５℃まで加熱した。この溶液に０．５ｍＭの硝酸銀水溶液７９．６ｍＬを１０ｍＬ／ｍｉｎで攪拌しながら添加した。
－－平板粒子の第２成長工程－－
さらに、前記溶液を３０分間攪拌した後、０．３５Ｍのヒドロキノンスルホン酸カリウム水溶液を７１．１ｍＬ添加し、７質量％ゼラチン（数平均分子量２０万以上）水溶液を２００ｇ添加した。この溶液に、０．２５Ｍの亜硫酸ナトリウム水溶液１０７ｍＬと０．４７Ｍの硝酸銀水溶液１０７ｍＬを混合してできた亜硫酸銀の白色沈殿物混合液を添加した。銀が十分に還元されるまで攪拌し、０．１７ＭのＮａＯＨ水溶液７２ｍＬを添加した。このようにして銀平板粒子分散液Ａを得た。 --First tabular grain growth process--
Next, 2 mL of 10 mM ascorbic acid aqueous solution was added to 250 mL of the seed solution and heated to 35 ° C. To this solution, 79.6 mL of 0.5 mM aqueous silver nitrate solution was added at 10 mL / min with stirring.
--Tabular grain second growth process--
Furthermore, 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 (number average molecular weight 200,000 or more) aqueous solution was added. To this solution, 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.
次に、前記種溶液２５０ｍＬに１０ｍＭのアスコルビン酸水溶液を２ｍＬ添加し、３５℃まで加熱した。この溶液に０．５ｍＭの硝酸銀水溶液７９．６ｍＬを１０ｍＬ／ｍｉｎで攪拌しながら添加した。
－－平板粒子の第２成長工程－－
さらに、前記溶液を３０分間攪拌した後、０．３５Ｍのヒドロキノンスルホン酸カリウム水溶液を７１．１ｍＬ添加し、７質量％ゼラチン（数平均分子量２０万以上）水溶液を２００ｇ添加した。この溶液に、０．２５Ｍの亜硫酸ナトリウム水溶液１０７ｍＬと０．４７Ｍの硝酸銀水溶液１０７ｍＬを混合してできた亜硫酸銀の白色沈殿物混合液を添加した。銀が十分に還元されるまで攪拌し、０．１７ＭのＮａＯＨ水溶液７２ｍＬを添加した。このようにして銀平板粒子分散液Ａを得た。 --First tabular grain growth process--
Next, 2 mL of 10 mM ascorbic acid aqueous solution was added to 250 mL of the seed solution and heated to 35 ° C. To this solution, 79.6 mL of 0.5 mM aqueous silver nitrate solution was added at 10 mL / min with stirring.
--Tabular grain second growth process--
Furthermore, 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 (number average molecular weight 200,000 or more) aqueous solution was added. To this solution, 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.
得られた銀平板粒子分散液Ａ中には、平均円相当径２４０ｎｍの銀の六角平板粒子（以下、Ａｇ六角平板粒子と称する）が生成していることを確認した。また、原子間力顕微鏡（ＮａｎｏｃｕｔｅＩＩ、セイコーインスツル社製）で、六角平板粒子の厚みを測定したところ、平均８ｎｍであり、アスペクト比が１７．５の平板粒子が生成していることが分かった。結果を表１に示す。
In the 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.
－銀平板粒子分散液Ｂ１の調製－
前記銀平板粒子分散液Ａ １２ｍＬに１ＮのＮａＯＨを０．５ｍＬ添加し、イオン交換水１８ｍＬ添加し、遠心分離器（コクサン社製Ｈ－２００Ｎ、アンブルローターＢＮ）で遠心分離を行い、Ａｇ六角平板粒子を沈殿させた。遠心分離後の上澄み液を捨て、水を２ｍＬ添加し、沈殿したＡｇ六角平板粒子を再分散させ、製造例１の銀平板粒子分散液Ｂ１を得た。 -Preparation of silver tabular grain dispersion B1-
0.5 mL of 1N NaOH is added to 12 mL of the silver tabular grain dispersion A, 18 mL of ion-exchanged water is added, and the mixture is centrifuged with a centrifuge (Hokusan H-200N, Amble Rotor BN). Particles were allowed to settle. The supernatant liquid after centrifugation was discarded, 2 mL of water was added, and the precipitated Ag hexagonal tabular grains were redispersed to obtain a silver tabular grain dispersion liquid B1 of Production Example 1.
前記銀平板粒子分散液Ａ １２ｍＬに１ＮのＮａＯＨを０．５ｍＬ添加し、イオン交換水１８ｍＬ添加し、遠心分離器（コクサン社製Ｈ－２００Ｎ、アンブルローターＢＮ）で遠心分離を行い、Ａｇ六角平板粒子を沈殿させた。遠心分離後の上澄み液を捨て、水を２ｍＬ添加し、沈殿したＡｇ六角平板粒子を再分散させ、製造例１の銀平板粒子分散液Ｂ１を得た。 -Preparation of silver tabular grain dispersion B1-
0.5 mL of 1N NaOH is added to 12 mL of the silver tabular grain dispersion A, 18 mL of ion-exchanged water is added, and the mixture is centrifuged with a centrifuge (Hokusan H-200N, Amble Rotor BN). Particles were allowed to settle. The supernatant liquid after centrifugation was discarded, 2 mL of water was added, and the precipitated Ag hexagonal tabular grains were redispersed to obtain a silver tabular grain dispersion liquid B1 of Production Example 1.
＜＜金属粒子の評価＞＞
次に、得られた金属粒子について、以下のようにして諸特性を評価した。結果を下記表１に示す。 << Evaluation of metal particles >>
Next, various properties of the obtained metal particles were evaluated as follows. The results are shown in Table 1 below.
次に、得られた金属粒子について、以下のようにして諸特性を評価した。結果を下記表１に示す。 << Evaluation of metal particles >>
Next, various properties of the obtained metal particles were evaluated as follows. The results are shown in Table 1 below.
－平板粒子の割合、平均粒子径（平均円相当径）、変動係数－
Ａｇ平板粒子の形状均一性は、観察したＳＥＭ画像から任意に抽出した２００個の粒子の形状を、六角形状乃至円形状の平板状金属粒子をＡ、涙型などの不定形形状及び略六角形未満の多角形状の粒子をＢとして画像解析を行い、Ａに該当する粒子個数の割合（個数％）を求めた。
また同様にＡに該当する粒子１００個の粒子径をデジタルノギスで測定し、その平均値を平板粒子Ａの平均粒子径（平均円相当径）とし、粒径分布の標準偏差を平均粒子径（平均円相当径）で割った平板粒子Ａの粒度分布の変動係数（％）を求めた。 -Ratio of tabular grains, average grain size (average equivalent circle diameter), coefficient of variation-
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.
Similarly, 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.
Ａｇ平板粒子の形状均一性は、観察したＳＥＭ画像から任意に抽出した２００個の粒子の形状を、六角形状乃至円形状の平板状金属粒子をＡ、涙型などの不定形形状及び略六角形未満の多角形状の粒子をＢとして画像解析を行い、Ａに該当する粒子個数の割合（個数％）を求めた。
また同様にＡに該当する粒子１００個の粒子径をデジタルノギスで測定し、その平均値を平板粒子Ａの平均粒子径（平均円相当径）とし、粒径分布の標準偏差を平均粒子径（平均円相当径）で割った平板粒子Ａの粒度分布の変動係数（％）を求めた。 -Ratio of tabular grains, average grain size (average equivalent circle diameter), coefficient of variation-
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.
Similarly, 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.
－平均粒子厚み－
得られた金属平板粒子を含む分散液を、ガラス基板上に滴下して乾燥し、Ａに該当する金属平板粒子１個の厚みを、原子間力顕微鏡（ＡＦＭ）（ＮａｎｏｃｕｔｅＩＩ、セイコーインスツル社製）を用いて測定した。なお、ＡＦＭを用いた測定条件としては、自己検知型センサー、ＤＦＭモード、測定範囲は５μｍ、走査速度は１８０秒／１フレーム、データ点数は２５６×２５６とした。得られたデータの平均値を平板粒子Ａの平均粒子厚みとした。 -Average particle thickness-
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 μm, 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.
得られた金属平板粒子を含む分散液を、ガラス基板上に滴下して乾燥し、Ａに該当する金属平板粒子１個の厚みを、原子間力顕微鏡（ＡＦＭ）（ＮａｎｏｃｕｔｅＩＩ、セイコーインスツル社製）を用いて測定した。なお、ＡＦＭを用いた測定条件としては、自己検知型センサー、ＤＦＭモード、測定範囲は５μｍ、走査速度は１８０秒／１フレーム、データ点数は２５６×２５６とした。得られたデータの平均値を平板粒子Ａの平均粒子厚みとした。 -Average particle thickness-
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 μm, 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.
－アスペクト比－
得られたＡに該当する金属平板粒子の平均粒子径（平均円相当径）及び平均粒子厚みから、平均粒子径（平均円相当径）を平均粒子厚みで除算して、平板粒子Ａのアスペクト比を算出した。 -aspect ratio-
By dividing the average particle diameter (average equivalent circle diameter) by the average grain thickness from the average grain diameter (average equivalent circle diameter) and average grain thickness of the obtained tabular metal grains corresponding to A, the aspect ratio of the tabular grain A is obtained. Was calculated.
得られたＡに該当する金属平板粒子の平均粒子径（平均円相当径）及び平均粒子厚みから、平均粒子径（平均円相当径）を平均粒子厚みで除算して、平板粒子Ａのアスペクト比を算出した。 -aspect ratio-
By dividing the average particle diameter (average equivalent circle diameter) by the average grain thickness from the average grain diameter (average equivalent circle diameter) and average grain thickness of the obtained tabular metal grains corresponding to A, the aspect ratio of the tabular grain A is obtained. Was calculated.
－銀平板分散液の透過スペクトル－
得られた銀平板分散液の透過スペクトルは、水で希釈し、紫外可視近赤外分光機（日本分光株式会社製、Ｖ－６７０）を用いて評価した。 -Transmission spectrum of silver plate dispersion-
The transmission spectrum of the obtained silver flat plate dispersion was diluted with water and evaluated using an ultraviolet-visible-near infrared spectrometer (manufactured by JASCO Corporation, V-670).
得られた銀平板分散液の透過スペクトルは、水で希釈し、紫外可視近赤外分光機（日本分光株式会社製、Ｖ－６７０）を用いて評価した。 -Transmission spectrum of silver plate dispersion-
The transmission spectrum of the obtained silver flat plate dispersion was diluted with water and evaluated using an ultraviolet-visible-near infrared spectrometer (manufactured by JASCO Corporation, V-670).
（実施例１）
－塗布液１の調製－
下記に示す組成の塗布液１を調製した。
塗布液１の組成：
・ポリエステルラテックス水分散液：ファインテックスＥＳ－６５０
（ＤＩＣ社製、固形分濃度３０質量％） ２８．２質量部
・界面活性剤Ａ：ラピゾールＡ－９０
（日本油脂（株）製、固形分１質量％） １２．５質量部
・界面活性剤Ｂ：アロナクティーＣＬ－９５
（三洋化成工業（株）製、固形分１質量％） １５．５質量部
・製造例１の銀平板粒子分散液Ｂ１ ２００質量部
・水 ８００質量部 Example 1
-Preparation of coating solution 1-
Acoating 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 1% by mass) 12.5 parts by mass 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
－塗布液１の調製－
下記に示す組成の塗布液１を調製した。
塗布液１の組成：
・ポリエステルラテックス水分散液：ファインテックスＥＳ－６５０
（ＤＩＣ社製、固形分濃度３０質量％） ２８．２質量部
・界面活性剤Ａ：ラピゾールＡ－９０
（日本油脂（株）製、固形分１質量％） １２．５質量部
・界面活性剤Ｂ：アロナクティーＣＬ－９５
（三洋化成工業（株）製、固形分１質量％） １５．５質量部
・製造例１の銀平板粒子分散液Ｂ１ ２００質量部
・水 ８００質量部 Example 1
-Preparation of coating solution 1-
A
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.,
(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
－金属粒子含有層の形成－
ＰＥＴフィルム（コスモシャインＡ４３００、東洋紡（株）製、厚み：７５μｍ）の表面上に、塗布液１を、ワイヤーバーを用いて、乾燥後の平均厚みが０．０８μｍ（８０ｎｍ）になるように塗布した。その後、１５０℃で１０分間加熱し、乾燥、固化し、金属粒子含有層を形成し、実施例１の熱線遮蔽材を得た。
なお、前記金属粒子含有層の乾燥後の平均厚みは、レーザー顕微鏡（ＶＫ－８５１０、キーエンス社製）を用いて上記塗布液１を塗布前のＰＥＴフィルムの厚みと、上記塗布液１をＰＥＴフィルムに塗布し、加熱、乾燥、固化後の厚みとの差を厚みとして測定し、これら１０点の厚みを平均することにより算出することができる。 -Formation of metal particle containing layer-
On the surface of a PET film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd., thickness: 75 μm), thecoating liquid 1 is applied using a wire bar so that the average thickness after drying is 0.08 μm (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 thecoating 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.
ＰＥＴフィルム（コスモシャインＡ４３００、東洋紡（株）製、厚み：７５μｍ）の表面上に、塗布液１を、ワイヤーバーを用いて、乾燥後の平均厚みが０．０８μｍ（８０ｎｍ）になるように塗布した。その後、１５０℃で１０分間加熱し、乾燥、固化し、金属粒子含有層を形成し、実施例１の熱線遮蔽材を得た。
なお、前記金属粒子含有層の乾燥後の平均厚みは、レーザー顕微鏡（ＶＫ－８５１０、キーエンス社製）を用いて上記塗布液１を塗布前のＰＥＴフィルムの厚みと、上記塗布液１をＰＥＴフィルムに塗布し、加熱、乾燥、固化後の厚みとの差を厚みとして測定し、これら１０点の厚みを平均することにより算出することができる。 -Formation of metal particle containing layer-
On the surface of a PET film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd., thickness: 75 μm), the
The average thickness of the metal particle-containing layer after drying is as follows: the thickness of the PET film before applying the
＜＜熱線遮蔽材の評価＞＞
次に、得られた熱線遮蔽材について、以下のようにして諸特性を評価した。結果を下記表２に示す。 << Evaluation of heat ray shielding material >>
Next, various characteristics of the obtained heat ray shielding material were evaluated as follows. The results are shown in Table 2 below.
次に、得られた熱線遮蔽材について、以下のようにして諸特性を評価した。結果を下記表２に示す。 << Evaluation of heat ray shielding material >>
Next, various characteristics of the obtained heat ray shielding material were evaluated as follows. The results are shown in Table 2 below.
－粒子傾き角－
エポキシ樹脂で熱線遮蔽材を包埋処理した後、液体窒素で凍結した状態で剃刀で割断し、熱線遮蔽材の垂直方向断面試料を作製した。この垂直方向断面試料を走査型電子顕微鏡（ＳＥＭ）で観察して、１００個の金属平板粒子について、基板の水平面に対する傾角（図５Ｄにおいて±θに相当）を平均値として算出した。
［評価基準］
○：傾角が±３０°以下
×：傾角が±３０°を超える
また、あわせて得られた実施例１の熱線遮蔽材の垂直方向断面試料について、ＳＥＭ画像より、六角形状乃至円形状の平板状金属粒子の厚みをａとしたとき、８０個数％以上の前記六角形状乃至円形状の平板状金属粒子について、厚み方向のａ／８～４ａが金属粒子含有層に埋没していることがわかった。 -Particle tilt angle-
After embedding the heat ray shielding material with an epoxy resin, 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 ± θ in FIG. 5D) of the 100 metal tabular grains with respect to the horizontal plane was calculated as an average value.
[Evaluation criteria]
○: Inclination angle is ± 30 ° or less ×: Inclination angle exceeds ± 30 ° In addition, a hexagonal or circular flat plate shape was obtained from the SEM image of the vertical cross-sectional sample of the heat ray shielding material of Example 1 obtained together. It was found that a / 8 to 4a in the thickness direction were buried in the metal particle-containing layer with respect to the hexagonal or circular plate-shaped metal particles of 80% by number or more when the thickness of the metal particles was a. .
エポキシ樹脂で熱線遮蔽材を包埋処理した後、液体窒素で凍結した状態で剃刀で割断し、熱線遮蔽材の垂直方向断面試料を作製した。この垂直方向断面試料を走査型電子顕微鏡（ＳＥＭ）で観察して、１００個の金属平板粒子について、基板の水平面に対する傾角（図５Ｄにおいて±θに相当）を平均値として算出した。
［評価基準］
○：傾角が±３０°以下
×：傾角が±３０°を超える
また、あわせて得られた実施例１の熱線遮蔽材の垂直方向断面試料について、ＳＥＭ画像より、六角形状乃至円形状の平板状金属粒子の厚みをａとしたとき、８０個数％以上の前記六角形状乃至円形状の平板状金属粒子について、厚み方向のａ／８～４ａが金属粒子含有層に埋没していることがわかった。 -Particle tilt angle-
After embedding the heat ray shielding material with an epoxy resin, 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 ± θ in FIG. 5D) of the 100 metal tabular grains with respect to the horizontal plane was calculated as an average value.
[Evaluation criteria]
○: Inclination angle is ± 30 ° or less ×: Inclination angle exceeds ± 30 ° In addition, a hexagonal or circular flat plate shape was obtained from the SEM image of the vertical cross-sectional sample of the heat ray shielding material of Example 1 obtained together. It was found that a / 8 to 4a in the thickness direction were buried in the metal particle-containing layer with respect to the hexagonal or circular plate-shaped metal particles of 80% by number or more when the thickness of the metal particles was a. .
－反射スペクトル及び透過スペクトル測定－
作製した各熱線遮蔽材の反射スペクトル及び透過スペクトルを、紫外可視近赤外分光機（日本分光株式会社製、Ｖ－６７０）を用いて測定した。反射スペクトル測定には、絶対反射率測定ユニット（ＡＲＶ－４７４、日本分光株式会社製）を用い、入射光は４５°偏光板を通し、無偏光とみなせる入射光とした。 -Reflection spectrum and transmission spectrum measurement-
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). For the reflection spectrum measurement, 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.
作製した各熱線遮蔽材の反射スペクトル及び透過スペクトルを、紫外可視近赤外分光機（日本分光株式会社製、Ｖ－６７０）を用いて測定した。反射スペクトル測定には、絶対反射率測定ユニット（ＡＲＶ－４７４、日本分光株式会社製）を用い、入射光は４５°偏光板を通し、無偏光とみなせる入射光とした。 -Reflection spectrum and transmission spectrum measurement-
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). For the reflection spectrum measurement, 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.
－－可視光透過率－－
作製した各熱線遮蔽材について、３８０ｎｍ～７８０ｎｍまで測定した各波長の透過率を、各波長の分光視感度により補正した値を可視光透過率とした。 --- Visible light transmittance ---
With respect to each of the produced heat ray shielding materials, a value obtained by correcting the transmittance at each wavelength measured from 380 nm to 780 nm with the spectral sensitivity of each wavelength was defined as the visible light transmittance.
作製した各熱線遮蔽材について、３８０ｎｍ～７８０ｎｍまで測定した各波長の透過率を、各波長の分光視感度により補正した値を可視光透過率とした。 --- Visible light transmittance ---
With respect to each of the produced heat ray shielding materials, a value obtained by correcting the transmittance at each wavelength measured from 380 nm to 780 nm with the spectral sensitivity of each wavelength was defined as the visible light transmittance.
－－遮熱性能評価－－
作製した各熱線遮蔽材について、３５０ｎｍ～２，１００ｎｍまで測定した各波長の透過率から、ＪＩＳ５７５９記載の方法に基づき、日射反射率を求め、判定を行った。遮熱性能の評価としては、反射率が高いことが好ましい。
［評価基準］
◎：反射率２０％以上
○：反射率１７％以上２０％未満
△：反射率１３％以上１７％未満
×：反射率１３％未満 --- Thermal insulation performance evaluation ---
About each produced heat ray shielding material, the solar reflectance was calculated | required and determined based on the method of JIS5759 from the transmittance | permeability of each wavelength measured from 350 nm to 2,100 nm. As an evaluation of the heat shielding performance, it is preferable that the reflectance is high.
[Evaluation criteria]
◎: Reflectance 20% or more ○: Reflectance 17% or more and less than 20% △: Reflectance 13% or more and less than 17% ×: Reflectance 13% or less
作製した各熱線遮蔽材について、３５０ｎｍ～２，１００ｎｍまで測定した各波長の透過率から、ＪＩＳ５７５９記載の方法に基づき、日射反射率を求め、判定を行った。遮熱性能の評価としては、反射率が高いことが好ましい。
［評価基準］
◎：反射率２０％以上
○：反射率１７％以上２０％未満
△：反射率１３％以上１７％未満
×：反射率１３％未満 --- Thermal insulation performance evaluation ---
About each produced heat ray shielding material, the solar reflectance was calculated | required and determined based on the method of JIS5759 from the transmittance | permeability of each wavelength measured from 350 nm to 2,100 nm. As an evaluation of the heat shielding performance, it is preferable that the reflectance is high.
[Evaluation criteria]
◎: Reflectance 20% or more ○: Reflectance 17% or more and less than 20% △: Reflectance 13% or more and less than 17% ×: Reflectance 13% or less
－密着評価－
ＪＩＳ Ｋ５６００－５－６に従い、クロスカット法によりポリマーフィルムと光学機能層の密着試験を行った。
［評価基準］
剥離しにくいもの：分類０
剥離しやすいもの：分類５
の6段階で評価した。 -Adhesion evaluation-
According to JIS K5600-5-6, an adhesion test between the polymer film and the optical functional layer was performed by a cross-cut method.
[Evaluation criteria]
Difficult to peel:Classification 0
Easy to peel:Category 5
The 6 grades were evaluated.
ＪＩＳ Ｋ５６００－５－６に従い、クロスカット法によりポリマーフィルムと光学機能層の密着試験を行った。
［評価基準］
剥離しにくいもの：分類０
剥離しやすいもの：分類５
の6段階で評価した。 -Adhesion evaluation-
According to JIS K5600-5-6, an adhesion test between the polymer film and the optical functional layer was performed by a cross-cut method.
[Evaluation criteria]
Difficult to peel:
Easy to peel:
The 6 grades were evaluated.
（実施例２）
実施例１において、塗布液１のポリエステルラテックス水分散液の添加量を３．２質量部に変え、乾燥後の平均厚みが０．００９μｍ（９ｎｍ）になるように塗布したこと以外は実施例１と同様にして、実施例２の熱戦遮蔽材を作成した。 (Example 2)
In Example 1, except that the amount of the polyester latex aqueous dispersion added to thecoating liquid 1 was changed to 3.2 parts by mass and the average thickness after drying was 0.009 μm (9 nm). In the same manner as described above, a thermal battle shielding material of Example 2 was prepared.
実施例１において、塗布液１のポリエステルラテックス水分散液の添加量を３．２質量部に変え、乾燥後の平均厚みが０．００９μｍ（９ｎｍ）になるように塗布したこと以外は実施例１と同様にして、実施例２の熱戦遮蔽材を作成した。 (Example 2)
In Example 1, except that the amount of the polyester latex aqueous dispersion added to the
（実施例３）
実施例１において、塗布液１のポリエステルラテックス水分散液の添加量を７．０質量部に変え、乾燥後の平均厚みが０．０２μｍ（２０ｎｍ）になるように塗布したこと以外は実施例１と同様にして、実施例３の熱戦遮蔽材を作成した。 (Example 3)
In Example 1, the amount of the polyester latex aqueous dispersion added to thecoating 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 μm (20 nm). In the same manner as described above, a thermal battle shielding material of Example 3 was prepared.
実施例１において、塗布液１のポリエステルラテックス水分散液の添加量を７．０質量部に変え、乾燥後の平均厚みが０．０２μｍ（２０ｎｍ）になるように塗布したこと以外は実施例１と同様にして、実施例３の熱戦遮蔽材を作成した。 (Example 3)
In Example 1, the amount of the polyester latex aqueous dispersion added to the
（実施例４）
実施例１において、塗布液１のポリエステルラテックス水分散液の添加量を５２．９質量部に変え、乾燥後の平均厚みが０．１５μｍ（１５０ｎｍ）になるように塗布したこと以外は実施例１と同様にして、実施例４の熱戦遮蔽材を作成した。 (Example 4)
In Example 1, the amount of the polyester latex aqueous dispersion added to thecoating 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 μm (150 nm). In the same manner as described above, a thermal battle shielding material of Example 4 was prepared.
実施例１において、塗布液１のポリエステルラテックス水分散液の添加量を５２．９質量部に変え、乾燥後の平均厚みが０．１５μｍ（１５０ｎｍ）になるように塗布したこと以外は実施例１と同様にして、実施例４の熱戦遮蔽材を作成した。 (Example 4)
In Example 1, the amount of the polyester latex aqueous dispersion added to the
（実施例５）
実施例１において、塗布液１のポリエステルラテックス水分散液の添加量を６３．５質量部に変え、乾燥後の平均厚みが０．１８μｍ（１８０ｎｍ）になるように塗布したこと以外は実施例１と同様にして、実施例５の熱戦遮蔽材を作成した。 (Example 5)
Example 1 except that the amount of the polyester latex aqueous dispersion added to thecoating solution 1 was changed to 63.5 parts by mass in Example 1 and the average thickness after drying was 0.18 μm (180 nm). In the same manner as described above, a thermal battle shielding material of Example 5 was prepared.
実施例１において、塗布液１のポリエステルラテックス水分散液の添加量を６３．５質量部に変え、乾燥後の平均厚みが０．１８μｍ（１８０ｎｍ）になるように塗布したこと以外は実施例１と同様にして、実施例５の熱戦遮蔽材を作成した。 (Example 5)
Example 1 except that the amount of the polyester latex aqueous dispersion added to the
（比較例１）
実施例１において、塗布液１の界面活性剤Ａと界面活性剤Ｂとポリエステルラテックス水分散液を加えず、代わりに塗布液１に界面活性剤Ｃ（下記Ｗ－１：固形分２質量％）を２００質量加えたこと以外は実施例１と同様にして、比較例１の熱線遮蔽材を作製した。
なお、比較例１の熱線遮蔽材の金属粒子含有層はポリマーを含まず、その膜厚ｄが１００ｎｍであった。
(Comparative Example 1)
In Example 1, surfactant A, surfactant B and polyester latex aqueous dispersion ofcoating 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.
In addition, 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.
実施例１において、塗布液１の界面活性剤Ａと界面活性剤Ｂとポリエステルラテックス水分散液を加えず、代わりに塗布液１に界面活性剤Ｃ（下記Ｗ－１：固形分２質量％）を２００質量加えたこと以外は実施例１と同様にして、比較例１の熱線遮蔽材を作製した。
なお、比較例１の熱線遮蔽材の金属粒子含有層はポリマーを含まず、その膜厚ｄが１００ｎｍであった。
In Example 1, surfactant A, surfactant B and polyester latex aqueous dispersion of
In addition, 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.
（比較例２）
実施例１において、塗布液１に数平均分子量２０万以上であるゼラチン１００質量部をさらに添加したこと以外は、実施例１と同様にして、金属粒子含有層の膜厚ｄが８０ｎｍである比較例２の熱線遮蔽材を作製した。
なお、ゼラチンの添加により、金属粒子の配列が乱れ、面配向性が悪化することがわかった（後述する表２参照）。 (Comparative 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 thecoating 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).
実施例１において、塗布液１に数平均分子量２０万以上であるゼラチン１００質量部をさらに添加したこと以外は、実施例１と同様にして、金属粒子含有層の膜厚ｄが８０ｎｍである比較例２の熱線遮蔽材を作製した。
なお、ゼラチンの添加により、金属粒子の配列が乱れ、面配向性が悪化することがわかった（後述する表２参照）。 (Comparative 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
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).
実施例２～５、比較例１および２の熱線遮蔽材について、実施例１と同様にして、諸特性を評価した。得られた結果を下記表２に示す。
The characteristics of the heat ray shielding materials of Examples 2 to 5 and Comparative Examples 1 and 2 were evaluated in the same manner as in Example 1. The obtained results are shown in Table 2 below.
上記表２の結果から、本発明の熱線遮蔽材は、可視光透過性、遮熱性能（日射反射率）、およびクロスカット密着性の評価結果が全て良好であることが分かった。金属平板粒子を表面偏在させるための機構は十分に解明されていないが、塗布乾燥時に液面上に金属粒子を浮かせることが必須であり、乾燥時に変化するであろう表面張力のバランスが取れていることが重要と考えている。
比較例１は金属粒子含有層の金属平板粒子の偏在が本発明の範囲を満たさないものであり、クロスカット密着性が悪いことがわかった。
比較例２は、金属粒子含有層用の塗布液にさらに主ポリマーとなるようにゼラチンを添加したものであり、得られた熱線遮蔽材の遮熱性能（日射反射率）が低下したことがわかった。なお、遮熱性能の低下した理由は、金属粒子の配列が乱れて面配向性が悪化した結果と考えられる。 From the results of Table 2 above, it was found that the heat ray shielding material of the present invention had all good evaluation results of visible light transmittance, heat shielding performance (solar reflectance), and cross-cut adhesion. Although the mechanism for unevenly distributing the surface of the metal tabular grains has not been fully elucidated, it is essential that the metal particles float on the liquid surface during coating and drying, and the surface tension that will change during drying is balanced. I think it is important.
In Comparative Example 1, it was found that the uneven distribution of the metal tabular grains in the metal particle-containing layer did not satisfy the scope of the present invention, and the cross-cut adhesion was poor.
In Comparative Example 2, gelatin was further added to the coating solution for the metal particle-containing layer so as to become a main polymer, and it was found that the heat shielding performance (solar reflectance) of the obtained heat ray shielding material was lowered. It was. In addition, it is thought that the reason for the decrease in the heat shielding performance is a result of deterioration of the plane orientation due to disorder of the arrangement of the metal particles.
比較例１は金属粒子含有層の金属平板粒子の偏在が本発明の範囲を満たさないものであり、クロスカット密着性が悪いことがわかった。
比較例２は、金属粒子含有層用の塗布液にさらに主ポリマーとなるようにゼラチンを添加したものであり、得られた熱線遮蔽材の遮熱性能（日射反射率）が低下したことがわかった。なお、遮熱性能の低下した理由は、金属粒子の配列が乱れて面配向性が悪化した結果と考えられる。 From the results of Table 2 above, it was found that the heat ray shielding material of the present invention had all good evaluation results of visible light transmittance, heat shielding performance (solar reflectance), and cross-cut adhesion. Although the mechanism for unevenly distributing the surface of the metal tabular grains has not been fully elucidated, it is essential that the metal particles float on the liquid surface during coating and drying, and the surface tension that will change during drying is balanced. I think it is important.
In Comparative Example 1, it was found that the uneven distribution of the metal tabular grains in the metal particle-containing layer did not satisfy the scope of the present invention, and the cross-cut adhesion was poor.
In Comparative Example 2, gelatin was further added to the coating solution for the metal particle-containing layer so as to become a main polymer, and it was found that the heat shielding performance (solar reflectance) of the obtained heat ray shielding material was lowered. It was. In addition, it is thought that the reason for the decrease in the heat shielding performance is a result of deterioration of the plane orientation due to disorder of the arrangement of the metal particles.
本発明の熱線遮蔽材は、可視光透過性及び日射反射率が高く、遮熱性能に優れ、金属粒子含有層と基材であるポリマーフィルムとのクロスカット密着性が高いために金属平板粒子の配列を維持できるので、例えば自動車、バス等の乗り物用フィルムや貼合せ構造体、建材用フィルムや貼合せ構造体などとして、熱線の透過を防止することの求められる種々の部材として好適に利用可能である。
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.
１ 基材であるポリマーフィルム
２ 金属粒子含有層
２ａ 金属粒子含有層の表面
３ 金属平板粒子
４ オーバーコート層
５ ハードコート層
１０ 熱線遮蔽材
１１ 粘着層
Ｄ 直径
Ｌ 厚み
Ｆ（λ） 粒子存在域厚み DESCRIPTION OFSYMBOLS 1 Polymer film which is base material 2 Metal particle content layer 2a Surface of metal particle content layer 3 Metal flat particle 4 Overcoat layer 5 Hard coat layer 10 Heat ray shielding material 11 Adhesive layer D Diameter L Thickness F (λ) Particle existing region thickness
２ 金属粒子含有層
２ａ 金属粒子含有層の表面
３ 金属平板粒子
４ オーバーコート層
５ ハードコート層
１０ 熱線遮蔽材
１１ 粘着層
Ｄ 直径
Ｌ 厚み
Ｆ（λ） 粒子存在域厚み DESCRIPTION OF
Claims (10)
- 基材であるポリマーフィルムと、
該ポリマーフィルムの少なくとも一方の面上に配置され、かつ、少なくとも１種の金属粒子を含有する金属粒子含有層を有し、
前記金属粒子が、六角形状乃至円形状の平板状金属粒子を６０個数％以上有し、
前記六角形状乃至円形状の平板状金属粒子の主平面が、前記金属粒子含有層の一方の表面に対して平均０°～±３０°の範囲で面配向し、
前記金属粒子含有層がポリマーを含み、
前記金属粒子含有層と前記ポリマーフィルムの密着がＪＩＳ Ｋ５６００－５－６に定められたクロスカットセロテープ（登録商標）剥離試験で2点以下であることを特徴とする熱線遮蔽材。 A polymer film as a substrate;
A metal particle-containing layer disposed on at least one surface of the polymer film and containing at least one metal particle;
The metal particles have 60% by number or more of hexagonal or circular tabular metal particles,
The main plane of the hexagonal or circular tabular metal particles is plane-oriented in an average range of 0 ° to ± 30 ° with respect to one surface of the metal particle-containing layer,
The metal particle-containing layer contains a polymer;
A heat ray shielding material, wherein the adhesion between the metal particle-containing layer and the polymer film is 2 points or less in a cross-cut cello tape (registered trademark) peel test defined in JIS K5600-5-6. - 前記金属粒子含有層に含まれるポリマーがポリエステル樹脂を含むことを特徴とする請求項１に記載の熱線遮蔽材。 The heat ray shielding material according to claim 1, wherein the polymer contained in the metal particle-containing layer contains a polyester resin.
- 前記金属粒子含有層に含まれる前記ポリマーの主ポリマーが、ポリエステル樹脂であることを特徴とする請求項１または２に記載の熱線遮蔽材。 The heat ray shielding material according to claim 1 or 2, wherein a main polymer of the polymer contained in the metal particle-containing layer is a polyester resin.
- 前記金属粒子含有層に含まれる前記金属粒子に対する前記ポリエステル樹脂の含有量が１～１００００質量％であることを特徴とする請求項２または３に記載の熱線遮蔽材。 The heat ray shielding material according to claim 2 or 3, wherein the content of the polyester resin with respect to the metal particles contained in the metal particle-containing layer is 1 to 10000 mass%.
- 前記金属粒子含有層の膜厚が、１０～１６０ｎｍであることを特徴とする請求項１～４のいずれか一項に記載の熱線遮蔽材。 The heat ray shielding material according to any one of claims 1 to 4, wherein the metal particle-containing layer has a thickness of 10 to 160 nm.
- 前記ポリマーフィルムがＰＥＴフィルムであることを特徴とする請求項１～５のいずれか一項に記載の熱線遮蔽材。 The heat ray shielding material according to any one of claims 1 to 5, wherein the polymer film is a PET film.
- 前記六角形状乃至円形状の平板状金属粒子の平均粒子径が７０ｎｍ～５００ｎｍであり、
前記六角形状乃至円形状の平板状金属粒子のアスペクト比（平均粒子径／平均粒子厚み）が８～４０であることを特徴とする請求項１～６のいずれか一項に記載の熱線遮蔽材。 The hexagonal or circular tabular metal particles have an average particle diameter of 70 nm to 500 nm,
The heat ray shielding material according to any one of claims 1 to 6, wherein the hexagonal or circular tabular metal particles have an aspect ratio (average particle diameter / average particle thickness) of 8 to 40. . - 前記六角形状乃至円形状の平板状金属粒子が、少なくとも銀を含むことを特徴とする請求項１～７のいずれか一項に記載の熱線遮蔽材。 The heat ray shielding material according to any one of claims 1 to 7, wherein the hexagonal or circular plate-like metal particles contain at least silver.
- 可視光透過率が７０％以上であることを特徴とする請求項１～８のいずれか一項に記載の熱線遮蔽材。 The heat ray shielding material according to any one of claims 1 to 8, wherein the visible light transmittance is 70% or more.
- 赤外光を反射することを特徴とする請求項１～９のいずれか一項に記載の熱線遮蔽材。 The heat ray shielding material according to any one of claims 1 to 9, which reflects infrared light.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2011202385 | 2011-09-15 | ||
| JP2011-202385 | 2011-09-15 |
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| WO2013039215A1 true WO2013039215A1 (en) | 2013-03-21 |
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|---|---|---|---|
| PCT/JP2012/073662 WO2013039215A1 (en) | 2011-09-15 | 2012-09-14 | Heat-ray shielding material |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2013077007A (en) |
| WO (1) | WO2013039215A1 (en) |
Families Citing this family (4)
| 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 (en) * | 2013-04-29 | 2014-11-06 | Sharp Kabushiki Kaisha | Energy-efficient transparent solar film, method for fabricating solar film optical absorption material, and energy-efficient window |
| JP6375272B2 (en) * | 2015-07-31 | 2018-08-15 | 富士フイルム株式会社 | Heat shielding material, heat insulating material, and window glass |
| 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)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005095097A1 (en) * | 2004-03-31 | 2005-10-13 | Toray Industries, Inc. | Laminated film |
| JP2009139925A (en) * | 2007-11-16 | 2009-06-25 | Epson Toyocom Corp | Optical multilayer film filter, method for producing optical multilayer film filter and electronic apparatus |
| JP2011118347A (en) * | 2009-11-06 | 2011-06-16 | Fujifilm Corp | Heat-ray shielding material |
-
2012
- 2012-09-14 WO PCT/JP2012/073662 patent/WO2013039215A1/en active Application Filing
- 2012-09-14 JP JP2012203448A patent/JP2013077007A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005095097A1 (en) * | 2004-03-31 | 2005-10-13 | Toray Industries, Inc. | Laminated film |
| JP2009139925A (en) * | 2007-11-16 | 2009-06-25 | Epson Toyocom Corp | Optical multilayer film filter, method for producing optical multilayer film filter and electronic apparatus |
| JP2011118347A (en) * | 2009-11-06 | 2011-06-16 | Fujifilm Corp | Heat-ray shielding material |
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| JP2013077007A (en) | 2013-04-25 |
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