WO2014156528A1 - Matériau de blindage vis-à-vis du rayonnement thermique, vitre de fenêtre utilisant un matériau de blindage vis-à-vis du rayonnement thermique, film intermédiaire pour verre stratifié, et verre stratifié - Google Patents

Matériau de blindage vis-à-vis du rayonnement thermique, vitre de fenêtre utilisant un matériau de blindage vis-à-vis du rayonnement thermique, film intermédiaire pour verre stratifié, et verre stratifié Download PDF

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Publication number
WO2014156528A1
WO2014156528A1 PCT/JP2014/055718 JP2014055718W WO2014156528A1 WO 2014156528 A1 WO2014156528 A1 WO 2014156528A1 JP 2014055718 W JP2014055718 W JP 2014055718W WO 2014156528 A1 WO2014156528 A1 WO 2014156528A1
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heat ray
ray shielding
shielding material
layer
containing layer
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PCT/JP2014/055718
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English (en)
Japanese (ja)
Inventor
克行 温井
柴山　繁
威史 濱
優樹 中川
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富士フイルム株式会社
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Publication of WO2014156528A1 publication Critical patent/WO2014156528A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
    • B32B17/10238—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer in the form of particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10614—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer comprising particles for purposes other than dyeing
    • B32B17/10633—Infrared radiation absorbing or reflecting agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J3/00—Antiglare equipment associated with windows or windscreens; Sun visors for vehicles
    • B60J3/007—Sunglare reduction by coatings, interposed foils in laminar windows, or permanent screens
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting filters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/105—Metal

Definitions

  • the present invention relates to a heat ray shielding material, a window glass using the heat ray shielding material, an interlayer film for laminated glass, and a laminated glass.
  • the present invention relates to a heat ray shielding material having excellent heat shielding performance, visible light transmittance, and wet heat durability.
  • 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. When considering application to windows of automobiles and buildings, it is preferable in the market that the appearance is highly transparent and the heat ray shielding performance is high. Furthermore, a heat ray shielding material excellent in durability is considered preferable.
  • Patent Document 1 when the resonance wavelength of light due to Ag fine particles is made longer by the particle size, a high dielectric constant is formed in the lower layer of the Ag fine particle layer in response to a problem that irregular reflection in the visible light wavelength region increases as the particle size increases.
  • a radio wave transmissive wavelength selection plate is described in which near-infrared light can be reflected by providing a dielectric layer having a refractive index and increasing the resonance wavelength while keeping the particle size as it is.
  • Patent Document 2 has a metal particle-containing layer containing at least one kind of metal particles, and the metal particles have hexagonal or circular plate-like metal particles of 60 number% or more, Reflection wavelength selectivity is achieved by a heat ray shielding material, wherein the main plane of the flat metal particles is plane-oriented in the range of 0 ° to ⁇ 30 ° with respect to one surface of the metal particle-containing layer.
  • a heat ray shielding material that has high selectivity in the reflection band and excellent transparency at a wavelength at which reflection is desired to be prevented.
  • Patent Document 3 describes a near-infrared cut film in which a near-infrared-absorbing dye and a near-infrared-absorbing layer containing silica fine particles are provided on a transparent substrate film, and the film winding property (sliding property) is described. It is described that it is possible to provide a near-infrared cut film that is excellent, has a small haze, has no particle feeling, and has an excellent average visible light transmittance, near-infrared transmittance (850 nm, 950 nm), heat resistance, and light resistance. .
  • the radio wave transmission wavelength selection plate obtained by the configuration of Patent Document 1 cannot be said to be sufficiently transparent and low haze, and further improvement has been desired. There was no disclosure or suggestion about the combined use with an infrared light absorbing material.
  • the method described in Patent Document 2 has not been studied at all such as providing a refractive index adjustment layer below the silver particle-containing layer for the purpose of further improving the visible light transmittance.
  • the near-infrared cut film described in Patent Document 3 is an infrared absorption type, and has a high heat transmissivity and inferior heat ray shielding performance as compared with an infrared reflection type heat ray shielding material.
  • Patent Document 3 uses silica fine particles of a specific size for imparting film winding property (sliding property) that deteriorates haze, but the silica fine particles are used for adjusting the refractive index of the infrared absorption layer. There was no disclosure or suggestion.
  • An object of the present invention is to solve the conventional problems and to provide a heat ray shielding material having better heat shielding performance, visible light transmittance, and wet heat durability than conventional techniques.
  • the present inventors diligently studied to have a metal particle-containing layer and an infrared-absorbing compound-containing layer, and to have at least one intermediate layer between the two layers.
  • a filler in at least one of the absorbing compound-containing layer or the intermediate layer, it is possible to provide a heat ray shielding material that has higher heat ray shielding ability, higher visible light transmittance, and superior wet heat durability compared to the conventional technology.
  • the headline and the present invention have been completed.
  • the present invention which is a specific means for solving the above-described problems is as follows.
  • a metal particle-containing layer containing at least one metal particle and an infrared-absorbing compound-containing layer containing an infrared-absorbing compound, and between the metal-particle-containing layer and the infrared-absorbing compound-containing layer
  • a heat ray shielding material comprising at least one intermediate layer and containing a filler in at least one of the infrared absorbing compound-containing layer or the intermediate layer.
  • R 1a and R 1b may be the same or different and each independently represents an alkyl group, an aryl group or a heteroaryl group.
  • R 2 and R 3 each independently represent a hydrogen atom.
  • R 2 and R 3 may combine to form a ring
  • R 4 represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a substituted group Represents a boron or metal atom, and may be a covalent bond or a coordinate bond with at least one group of R 1a , R 1b and R 3.
  • the tabular metal particles are silver tabular grains.
  • the plate-like metal particles are hexagonal or circular plate-like metal particles, and among the hexagonal or circular plate-like metal particles, a main plane is one of the metal particle-containing layers.
  • the heat ray shielding material according to ⁇ 4> or ⁇ 5>, wherein the flat metal particles whose plane orientation is in an average range of 0 ° to ⁇ 30 ° with respect to the surface is 50% by number or more of all the flat metal particles.
  • the filler is at least one selected from the group consisting of titanium oxide, zirconium oxide, zinc oxide, synthetic amorphous silica, colloidal silica, hollow silica, porous silica, magnesium fluoride, and hollow magnesium fluoride.
  • the intermediate layer has a thickness of 20 nm or more.
  • ⁇ 11> The heat ray shielding material according to any one of ⁇ 1> to ⁇ 10>, wherein the infrared absorbing compound-containing layer has a density of the infrared absorbing compound of 0.25 g / cm 3 or more.
  • ⁇ 12> The heat ray shielding material according to any one of ⁇ 1> to ⁇ 11>, further comprising an overcoat layer on a surface opposite to the surface having the intermediate layer of the metal particle-containing layer.
  • ⁇ 13> The heat ray shielding material according to any one of ⁇ 1> to ⁇ 12>, further comprising a support on the surface of the infrared absorbing compound-containing layer opposite to the surface having the metal particle-containing layer.
  • the support is polyethylene, polypropylene, polyolefin resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate resin, polyvinyl chloride resin, polyphenylene sulfide resin, polyether sulfone resin, polyethylene sulfide resin, polyphenylene
  • the heat ray shielding material according to ⁇ 12> or ⁇ 13> which is any one of an ether resin, a styrene resin, an acrylic resin, a polyamide resin, a polyimide resin, and a cellulose resin.
  • the heat ray shielding material according to ⁇ 13> or ⁇ 14> which has at least one layer between the infrared absorbing compound-containing layer and the support.
  • a hard coat layer on the surface opposite to the surface having the metal particle-containing layer of the support.
  • the hard coat layer contains metal oxide particles.
  • the metal oxide particles are at least one selected from tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), and cesium tungsten oxide (CWO).
  • ⁇ 19> The heat ray shielding material according to any one of ⁇ 1> to ⁇ 18>, further comprising an adhesive layer on a surface opposite to the surface having the intermediate layer of the metal particle-containing layer.
  • ⁇ 21> An interlayer film for laminated glass comprising the heat ray shielding material according to any one of ⁇ 1> to ⁇ 19>.
  • ⁇ 22> Laminated glass containing the heat ray shielding material according to any one of ⁇ 1> to ⁇ 19>.
  • ⁇ 23> ⁇ 21> An interlayer film for laminated glass and at least two glass plates, wherein the interlayer film for laminated glass is inserted into the two sheets of glass Laminated glass.
  • a heat ray shielding material having high heat ray shielding ability, high visible light transmittance, and excellent wet heat durability can be provided.
  • 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. 4 is a schematic view showing another example of the heat ray shielding material of the present invention.
  • FIG. 5A is a schematic view showing an example in which the heat ray shielding material of the present invention is installed on a window glass.
  • FIG. 5B is a schematic view showing an example of a laminated glass using the heat ray shielding material of the present invention.
  • FIG. 6A is a schematic cross-sectional view showing a state of existence of a metal particle-containing layer containing flat metal particles in the heat ray shielding material of the present invention, wherein the metal particle-containing layer containing flat metal particles (plane of the substrate) The figure explaining the angle ((theta)) which the main plane (surface which determines the equivalent circle diameter D) of a flat metal particle and a flat metal particle forms.
  • FIG. 6B is a schematic cross-sectional view showing the existence state of the metal particle-containing layer containing flat metal particles in the heat ray shielding material of the present invention, and is a flat plate shape in the depth direction of the heat ray shielding material of the metal particle-containing layer. It is a figure which shows the presence area
  • FIG. 6C is a schematic cross-sectional view showing another example of the existence state of the metal particle-containing layer containing flat metal particles in the heat ray shielding material of the present invention.
  • FIG. 6D is a schematic cross-sectional view showing another example of the presence state of the metal particle-containing layer containing flat metal particles in the heat ray shielding material of the present invention.
  • FIG. 6E is a schematic cross-sectional view showing another example of the presence state of the metal particle-containing layer containing flat metal particles in the heat ray shielding material of the present invention.
  • FIG. 6F is a schematic cross-sectional view showing another example of the presence state of the metal particle-containing layer containing flat metal particles in the heat ray shielding material of the present invention.
  • FIG. 6C is a schematic cross-sectional view showing another example of the existence state of the metal particle-containing layer containing flat metal particles in the heat ray shielding material of the present invention.
  • FIG. 6D is a schematic cross-sectional view showing another example of the presence
  • FIG. 7A is a schematic perspective view showing an example of the shape of a flat metal particle preferably used in the heat ray shielding material of the present invention, and shows a circular flat metal particle.
  • FIG. 7B is a schematic perspective view showing an example of the shape of flat metal particles preferably used for the heat ray shielding material of the present invention, and shows hexagonal flat metal particles.
  • 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 metal particle-containing layer containing at least one metal particle and an infrared-absorbing compound-containing layer containing an infrared-absorbing compound, the metal-particle-containing layer and the infrared-absorbing compound-containing It has at least one or more intermediate layers between the layers, and at least one of the infrared absorbing compound-containing layer or the intermediate layer contains a filler.
  • the heat ray shielding material has high heat ray shielding ability, high visible light transmittance, and excellent wet heat durability.
  • the heat ray shielding material having higher heat ray shielding ability, higher visible light transmittance and superior wet heat durability compared with the prior art could be provided by combining the following functions: ing. It is considered that there are two roles of the intermediate layer in the present invention. The first role of the intermediate layer is considered to be to weaken the interaction caused by the contact between the infrared absorbing compound and the metal particles due to the installation of the intermediate layer between the infrared absorbing compound-containing layer and the metal particle-containing layer. ing.
  • the second role of the intermediate layer is to obtain a smooth surface. It was found that when the infrared absorbing compound-containing layer was applied, random and minute irregularities were formed on the surface of the infrared absorbing compound-containing layer due to minute protrusions of the infrared absorbing compound. It was found that when the metal particle-containing layer was applied on a minute uneven surface, the metal particles were hardly arranged on the convex part, and the arrangement of the metal particles was disturbed along the uneven surface shape. On the other hand, by setting the intermediate layer between the infrared absorbing compound-containing layer and the metal particle-containing layer, the minute uneven surface shape of the infrared absorbing compound-containing layer can be canceled, and a smooth intermediate layer surface can be obtained.
  • the metal particle layer was applied on the surface of the smooth intermediate layer, the metal particles were applied in a uniform arrangement. It is known that the uniformity of the arrangement of metal particles contributes to the performance of the optical performance, and the effect of improving the visible light transmittance and the heat ray shielding ability was obtained by making the distance between the particles uniform. . As described above, the intermediate layer is considered to exhibit the above two functions simultaneously.
  • a further improvement effect of wet heat durability can be obtained by including a filler in at least one of the intermediate layer or the infrared ray absorbing compound-containing layer.
  • the filler has an effect of suppressing diffusion in the layer of the infrared absorbing compound.
  • a refractive index difference can be given between both layers, thereby reducing reflection in the visible light wavelength region and increasing reflection in the infrared wavelength region. An effect can be imparted.
  • the installation of the intermediate layer and the configuration including the filler in at least one of the intermediate layer or the infrared ray absorbing compound-containing layer can reduce the effects of improving the heat ray shielding ability, optical performance, and wet heat durability. It was found that this can be realized with a layer structure.
  • the heat ray shielding material of the present invention preferably has an average heat ray reflectance at 700 to 1200 nm of 5% or more, more preferably 7% or more, particularly preferably 8% or more, and 10% or more. More particularly preferred.
  • the heat ray shielding material of the present invention it is preferable from the viewpoint of lowering the heat ray transmittance that at least one layer has the lowest peak of the transmission spectrum in a region of 800 to 2000 nm.
  • the minimum peak wavelength of the transmission spectrum is more preferably in the band of 750 to 1400 nm, and particularly preferably in the band of 800 to 1100 nm.
  • the metal particle-containing layer preferably has the lowest peak of the transmission spectrum in the region of 800 to 2000 nm.
  • the heat ray shielding material of the present invention preferably has a maximum reflection wavelength in the band of 700 to 1800 nm from the viewpoint of increasing the efficiency of heat ray reflection.
  • the maximum reflection wavelength is more preferably in the band of 750 to 1400 nm, and particularly preferably in the band of 800 to 1100 nm.
  • the visible light transmittance of the heat ray shielding material of the present invention is preferably 60% or more, more preferably 65% or more, and particularly preferably 70% or more.
  • 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 heat ray shielding material of the present invention has a metal particle-containing layer and an infrared absorbing compound-containing layer, and has at least one intermediate layer between the two layers, and at least one of the infrared absorbing compound-containing layer and the intermediate layer. Contains a filler. Furthermore, if necessary, an overcoat layer, an adhesive layer, an ultraviolet absorbing layer, a support (hereinafter also referred to as a substrate), a metal oxide particle-containing layer, a backcoat layer, a hard coat layer, a heat insulating layer, a protective layer, etc. An embodiment having other layers is also preferable.
  • the heat ray shielding material of the present invention may form a laminate having the configuration of the heat ray shielding material on a substrate, or after forming a laminate having the configuration of the heat ray shielding material on a temporary support.
  • the laminate having the configuration of the heat ray shielding material may be taken out by peeling at the interface between the temporary support and the laminate.
  • the laminated body having the configuration of the heat ray shielding material taken out in this manner is incorporated into an interlayer film for laminated glass, and the laminated glass using the interlayer film for laminated glass incorporating the laminated body having the configuration of the heat ray shielding material.
  • a laminated glass body having a heat ray shielding function can be formed.
  • the preferable structure of the heat ray shielding material of this invention is demonstrated based on drawing.
  • the heat ray shielding material 100 includes a metal particle-containing layer 1, an intermediate layer 2, and an infrared absorbing compound-containing layer 3 on a substrate 40.
  • stacked in this order is mentioned.
  • the heat ray shielding material of the present invention contains a filler in at least one of the intermediate layer 2 or the infrared absorbing compound-containing layer 3.
  • FIG. 2 is another example of the present invention, which is an embodiment of an example in which the intermediate layer has two or more layers.
  • the infrared absorbing compound-containing layer 3 On the substrate 40, the infrared absorbing compound-containing layer 3, the intermediate layer 2C, the intermediate layer 2B, the intermediate layer 2A, And the metal particle-containing layer 1 are stacked in this order.
  • At least one of the intermediate layers 2A to 2C or the infrared absorbing compound-containing layer 3 contains a filler. There may be a plurality of layers containing a filler.
  • FIG. 3A is another example of the present invention, in which the infrared absorbing compound-containing layer 3 is sandwiched between the intermediate layer 2 and the lower layer 4.
  • FIG. 3B is another example of this invention, and is an aspect further including lower layer 4A, 4B from the aspect of FIG.
  • FIG. 4 shows an embodiment in which an overcoat layer 5, an adhesive layer 6, and a hard coat layer 7 are installed in the embodiment of FIG.
  • FIG. 1 is used as a representative, an embodiment in which the overcoat layer 5, the pressure-sensitive adhesive layer 6, and the hard coat layer 7 are installed in the embodiments of FIGS. 2, 3A, and 3B may be used.
  • the heat ray shielding material of the embodiment of FIG. 4 may be installed on the window glass 8 through the adhesive layer 6.
  • the upper part in FIG. 5A is the outdoor side, and the lower part is the indoor side.
  • FIG. 5B it is an aspect when both surfaces of the heat ray shielding material which installed the overcoat layer in the aspect of FIG.
  • the upper part in FIG. 5B is the outdoor side, and the lower part is the indoor side.
  • the heat ray shielding material of the present invention is characterized in that an intermediate layer comprising at least one layer is provided between the metal particle-containing layer and the infrared absorbing compound-containing layer. Moreover, the heat ray shielding material of this invention contains a filler in at least any one of an intermediate
  • the intermediate layer provides a heat ray shielding material having high heat ray shielding ability, high visible light transmittance, and excellent wet heat durability.
  • the material constituting the intermediate layer in the present invention may be a metal thin film, a metal oxide thin film, or a polymer-containing layer. From the viewpoint of electromagnetic wave permeability, a metal oxide thin film or a polymer-containing layer is preferable, and from the viewpoint of productivity, a polymer-containing layer that can be easily applied in water is preferable.
  • the polymer (binder) used for the intermediate layer is preferably a transparent polymer.
  • the polymer examples include polyvinyl acetal resin, polyvinyl alcohol resin, polyvinyl butyral resin, polyacrylate resin, polymethyl methacrylate resin, polycarbonate resin, poly Examples thereof include vinyl chloride resins, (saturated) polyester resins, polyurethane resins, and polymers such as natural polymers such as gelatin and cellulose.
  • the main polymer of the polymer is preferably a polyvinyl alcohol resin, a polyvinyl butyral resin, a polyvinyl chloride resin, a (saturated) polyester resin, or a polyurethane resin. preferable.
  • the polymer used for the intermediate layer is an aqueous dispersion from the viewpoint of environmental impact and the reduction of coating cost.
  • a water-soluble polyester resin, Pluscoat Z-592 (manufactured by Kyoyo Chemical Industry Co., Ltd.), a water-soluble polyurethane resin, Hydran HW-350 (manufactured by DIC Corporation), or the like is preferably used. be able to.
  • the thickness of the intermediate layer is preferably 20 nm or more, more preferably 30 nm or more, and further preferably 40 nm or more. Although there is no restriction
  • the heat ray shielding material of the present invention contains a filler in at least one of the intermediate layer and the infrared absorbing compound-containing layer.
  • the filler is selected from at least one selected from the group consisting of titanium oxide, zirconium oxide, zinc oxide, synthetic amorphous silica, colloidal silica, hollow silica, porous silica, magnesium fluoride, and hollow magnesium fluoride. It is preferable to become. Among these, it is more preferable to use titanium oxide, zirconium oxide, hollow silica, and magnesium fluoride.
  • the refractive index of the layer containing the filler can be adjusted, which is preferable. It is preferable to provide a refractive index difference between adjacent layers, and a multilayer optical interference film can be designed by adjusting the refractive index difference and the film thickness of each layer. By appropriately designing the multilayer optical interference film, for example, it is possible to provide an effect of reducing reflection in the visible light wavelength region and enhancing reflection in the infrared wavelength region.
  • the average particle size of the filler used in the heat ray shielding material of the present invention is 200 nm or less, preferably 100 nm or less, more preferably 60 nm or less.
  • the average particle size of the filler is 200 nm or more, it is difficult to make the layer containing the filler thin, and it is not preferable when optical interference design is considered.
  • the filler content in the intermediate layer is preferably 10 to 250 mg / m 2 , more preferably 30 to 150 mg / m 2 , and even more preferably 40 to 100 mg / m 2 .
  • the mass ratio of the filler to the binder is preferably 0.1 to 2.5, more preferably 0.1 to 2.0, and more preferably 0.5 to A ratio of 1.5 is particularly preferred. If the mass ratio of the filler to the binder is less than 0.1, the effect of preventing the infrared absorbing compound from penetrating into the metal particle-containing layer is low, and the wet heat aging resistance deteriorates. If it is larger than 5, the film physical strength of the intermediate layer becomes weak, which is not preferable.
  • layers having different refractive indexes may be laminated to form a multilayer structure of two or more layers.
  • layers having different refractive indexes it is possible to provide an effect of reducing reflection in the visible light wavelength region and enhancing reflection in the infrared wavelength region.
  • a method for adjusting layers having different refractive indexes a method comprising laminating a layer containing zirconium oxide having a high refractive index and a layer containing hollow silica having a low refractive index, a layer containing a binder having a high refractive index, and a refractive index And a method of laminating a layer containing a low binder.
  • an intermediate layer having a refractive index of n1 is provided as a layer A
  • a layer having a refractive index of n2 is a layer B (infrared absorbing compound-containing layer).
  • a layer C as a support and satisfying the condition (1-1) or the condition (2-1) are also preferred.
  • Formula (1-1) 3 ⁇ / 8 + m ⁇ / 2 ⁇ A ⁇ n1 ⁇ d1 ⁇ 3 ⁇ / 8 + m ⁇ / 2 + A
  • m represents an integer of 0 or more
  • ⁇ represents a wavelength (unit: nm) desired to prevent reflection
  • n1 represents the refractive index of the layer A
  • d1 represents the thickness of the layer A
  • n1 ⁇ d1 is preferably within a predetermined value ⁇ A
  • A represents any one of ⁇ / 8, ⁇ / 12, and ⁇ / 16, and the smaller A is, the more anti-reflection interference is.
  • m represents an integer of 0 or more
  • ⁇ represents a wavelength (unit: nm) desired to prevent reflection
  • n1 represents the refractive index of layer A
  • d1 represents the thickness of layer A
  • n1 ⁇ d1 is preferably within a predetermined value ⁇ A
  • A represents any one of ⁇ / 8, ⁇ / 12, and ⁇ / 16, and the smaller A is, the more anti-reflection interference is.
  • A represents any one of ⁇ / 8, ⁇ / 12, and ⁇ / 16, and the smaller A is, the more anti-reflection interference is.
  • the preferable range of the condition (1-1) or the condition (2-1) will be described.
  • the preferred range of the following formula (1-1) or condition (2-1) is the same in the multilayer structure of the present invention other than the configuration of FIG.
  • m represents an integer of 0 or more, and an integer of 0 to 5 is preferable from the viewpoint of manufacturing cost and film thickness robustness.
  • the m is more preferably an integer of 1 to 5 from the viewpoint of achieving both a visible light reflection suppression and a near infrared light reflection enhancement when the multilayer structure of the present invention is used as a heat ray shielding material.
  • the layer B satisfies the condition (3-1) or the condition (4-1).
  • Formula (3-1) n1 ⁇ n2 and the following formula (3-1) is satisfied.
  • Formula (3-1) ⁇ / 4 + L ⁇ / 4 ⁇ A ⁇ n2 ⁇ d2 ⁇ ⁇ / 4 + L ⁇ / 4 + A
  • L represents an integer of 1 or more
  • ⁇ represents a wavelength (unit: nm) desired to prevent reflection
  • n2 represents the refractive index of layer B
  • d2 represents the thickness of layer B
  • n2 ⁇ d2 preferably falls within a predetermined value ⁇ A
  • A represents any one of ⁇ / 8, ⁇ / 12, and ⁇ / 16, and the smaller A is, the more anti-reflection interference is. (It is preferable to approach the optimum condition for obtaining the effect.)
  • Formula (4-1) L ⁇ / 4 ⁇ A ⁇ n2 ⁇ d2 ⁇ L ⁇ / 4 + A
  • L represents an integer of 1 or more
  • ⁇ represents a wavelength (unit: nm) desired to prevent reflection
  • n2 represents the refractive index of the layer B
  • d2 represents the thickness of the layer B
  • n2 ⁇ d2 preferably falls within a predetermined value ⁇ A
  • A represents any one of ⁇ / 8, ⁇ / 12, and ⁇ / 16, and the smaller A is, the more anti-reflection interference is.
  • a preferable range of the condition (3-1) or the condition (4-1) will be described.
  • the preferred range of the following formula (3-1) or condition (4-1) is the same in the multilayer structure of the present invention other than the configuration of FIG.
  • L represents an integer of 1 or more, and is preferably 1 to 5, with 1 reducing the color change with respect to obliquely incident light. More preferable from the viewpoint.
  • the layer B satisfies the following formula (5-1) or the following formula (6-1) from the viewpoint of enhancing the reflection at the wavelength ⁇ ′ where a strong reflection is desired.
  • Formula (5-1) ⁇ / 4 + k ⁇ ′ / 4 ⁇ B ⁇ n2 ⁇ d2 ⁇ ⁇ / 4 + k ⁇ ′ / 4 + B (In the formula (5-1), k represents an integer of 1 or more, ⁇ ′ represents a wavelength (unit: nm) desired to have strong reflection, n2 represents the refractive index of the layer B, and d2 represents the layer B.
  • N2 ⁇ d2 is preferably within a predetermined value ⁇ B, B represents any one of ⁇ ′ / 8, ⁇ ′ / 12, and ⁇ ′ / 16, and B represents (The smaller the value, the closer to the optimum condition for obtaining the interference effect of reflection enhancement.)
  • Formula (6-1) k ⁇ ′ / 4 ⁇ B ⁇ n2 ⁇ d2 ⁇ k ⁇ ′ / 4 + B
  • k represents an integer of 1 or more
  • ⁇ ′ represents a wavelength (unit: nm) desired to have strong reflection
  • n2 represents the refractive index of layer B
  • d2 represents layer B.
  • N2 ⁇ d2 is preferably within a predetermined value ⁇ B
  • B represents any one of ⁇ ′ / 8, ⁇ ′ / 12, and ⁇ ′ / 16, and B is It is preferable that the smaller the value is, the closer to the optimum condition for obtaining the reflection enhancing interference effect.
  • a preferred range of the formula (5-1) or the formula (6-1) will be described.
  • k represents an integer of 1 or more, and is preferably 1 to 5, with 1 being small in color change with respect to obliquely incident light. More preferable from the viewpoint.
  • the wavelength ⁇ for preventing the strong reflection is not particularly limited, and examples thereof include visible light and ultraviolet light bands. Among them, visible light is preferable from the viewpoint of increasing visible light transmittance.
  • the wavelength ⁇ for preventing reflection is preferably 250 to 800 nm, more preferably 400 to 700 nm, and particularly preferably 550 ⁇ 100 nm.
  • the wavelength ⁇ ′ for giving strong reflection is not particularly limited, and examples thereof include visible light, infrared light, and ultraviolet light bands. Among them, infrared light is a heat ray shielding material.
  • the heat ray shielding material of the present invention preferably has a wavelength ⁇ ′ of 700 to 2500 nm, more preferably 800 to 1500 nm, and particularly preferably 900 to 1200 nm. preferable.
  • a strong reflection is given to a wavelength of less than 700 nm, the red reflected light is conspicuous and leads to a decrease in visible light transmittance.
  • reflection is given to a wavelength greater than 2500 nm, the solar spectrum has almost no energy of 2500 nm or more, and therefore the effect as a heat ray shielding material is reduced.
  • the intermediate layer is not particularly limited and may be appropriately selected depending on the intended purpose.
  • it contains a matting agent and a surfactant, and may further contain other components as necessary. .
  • the heat ray shielding material of the present invention may have a laminated structure including at least one intermediate layer, a metal particle-containing layer, and an infrared absorbing compound-containing layer, and including at least one lower layer (described later).
  • the refractive index of each layer and the thickness of the coating film are designed so as to satisfy any one of the above formulas (1-1) to (6-1), thereby reducing reflection at a specific wavelength (visible light Is preferable from the viewpoint of improving the visible light transmittance) and enhancing the reflection in the infrared wavelength region.
  • the metal particle-containing layer is a layer containing at least one metal particle.
  • the metal particles are preferably flat metal particles (flat metal particles), and preferably segregate the flat metal particles on one surface of the metal particle-containing layer.
  • the metal particles preferably have 60% by number or more of flat metal particles, and more preferably have 60% by number or more of hexagonal or circular plate metal particles.
  • 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 main planes of hexagonal or circular plate-like metal particles are preferably plane-oriented in the range of average 0 ° to ⁇ 30 °, and plane-oriented in the range of average 0 ° to ⁇ 20 °.
  • the plane orientation is particularly preferably in the range of 0 ° to ⁇ 10 ° on average.
  • the plate-like metal particles whose plane orientation is in the range of 0 ° to ⁇ 30 ° on average is preferably 50% by number or more, more preferably 70% by number or more of the total plate-like metal particles, More preferably, it is 90% by number or more.
  • 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, and silver is more preferable among them.
  • the tabular metal particles are not particularly limited as long as they are particles composed of two main planes (see FIGS. 7A and 7B), and can be appropriately selected according to the purpose, for example, hexagonal shape, circular shape, Examples include a triangle 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.
  • the circular shape means a shape in which the number of sides having a length of 50% or more of the average equivalent circle diameter of flat metal particles described later is 0 per flat metal particle. Say.
  • the circular plate-like metal particles are not particularly limited as long as the plate-like metal particles have no corners and are round when viewed from above the main plane with a transmission electron microscope (TEM). It can be appropriately selected depending on the case.
  • the hexagonal shape refers to a shape in which the number of sides having a length of 20% or more of the average equivalent circle diameter of the flat metal particles described later is 6 per flat metal particle. To tell. The same applies to other polygons.
  • the hexagonal plate-like metal particles are not particularly limited as long as they are hexagonal when the plate-like metal particles are observed from above the main plane with a transmission electron microscope (TEM), and are appropriately selected according to the purpose.
  • the hexagonal corner may be acute or dull, but the corner is preferably dull in that the absorption in the visible light region can be reduced.
  • the corner is preferably dull in that the absorption in the visible light region can be reduced.
  • the hexagonal or circular plate-like metal particles are preferably 60% by number or more, more preferably 65% by number or more based on the total number of metal particles. Preferably, 70% by number or more is particularly preferable.
  • the proportion of the flat metal particles is 60% by number or more, the visible light transmittance is increased.
  • 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).
  • the plane orientation is preferably in the range of average 0 ° to ⁇ 30 °, more preferably the plane is oriented in the range of average 0 ° to ⁇ 20 °, and the average is 0 ° to ⁇ 10 °. It is particularly preferable that the surface is oriented in a range.
  • the plate-like metal particles whose plane orientation is in the range of 0 ° to ⁇ 30 ° on average is preferably 50% by number or more, more preferably 70% by number or more of the total plate-like metal particles, More preferably, it is 90% by number or more.
  • the state of the presence of the flat metal particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably arranged as shown in FIGS. 6C to 6F described later.
  • FIG. 6A to FIG. 6F are schematic cross-sectional views showing the existence state of the metal particle-containing layer containing flat metal particles in the heat ray shielding material of the present invention.
  • 6D to 6F show the state of the presence of the flat metal particles 11 in the metal particle-containing layer 1.
  • FIG. 6A is a diagram for explaining an angle ( ⁇ ⁇ ) formed by the plane of the base material and the main plane of the tabular metal particles 11 (the plane that determines the equivalent circle diameter D).
  • FIG. 6B shows the existence range f in the depth direction of the heat ray shielding material of the metal particle-containing layer 1.
  • the angle ( ⁇ ⁇ ) formed between the surface of the base material and the main plane (plane that determines the equivalent circle diameter D) of the tabular metal particles 11 or the extension line of the main plane is a predetermined value in the plane orientation described above.
  • the plane orientation means a state where the inclination angle ( ⁇ ⁇ ) shown in FIG. 6A is small when the cross section of the heat ray shielding material is observed.
  • FIG. 6C shows the main surface of the base metal particles 11 and the surface of the base metal particles 11. A state where the flat surface is in contact, that is, a state where ⁇ is 0 ° is shown.
  • ⁇ in FIG. 6A exceeds ⁇ 30 °
  • a predetermined wavelength of the heat ray shielding material for example, near the visible light region long wavelength side
  • the main plane of the flat metal particles 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)
  • the surface of the substrate when the heat ray shielding material has a substrate there is no particular limitation.
  • a suitable cross section is prepared, and a metal particle-containing layer (a base material when the heat ray shielding material has a base material) and flat metal particles in this section It may be a method of observing and 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), a transmission electron microscope (TEM), etc.), and a method of evaluating from an image obtained by observation.
  • FE-SEM field emission scanning electron microscope
  • TEM transmission electron microscope
  • the surface of the metal particle-containing layer in the sample (the surface of the base material when the heat ray shielding material has a base material)
  • the surface of the metal particle-containing layer in the sample there is no particular limitation as long as it can confirm whether or not the main plane is plane-oriented, and it can be appropriately selected according to the purpose. Examples thereof include observation using FE-SEM, TEM, and the like.
  • observation may be performed by FE-SEM
  • observation may be performed by TEM.
  • TEM When evaluating by FE-SEM, it is preferable to have a spatial resolution with which the shape and inclination angle ( ⁇ ⁇ in FIG. 6A) of the flat metal particles can be clearly determined.
  • the projected area of the particles can be obtained by a known method of measuring the area on an electron micrograph and correcting the photographing magnification.
  • the equivalent circle diameter is represented by the diameter of a circle having an area equal to the projected area of individual particles obtained by the method.
  • a particle size distribution (particle size distribution) is obtained by the statistics of the equivalent circle diameter D of 200 flat metal particles, and the average particle diameter (average equivalent circle diameter) can be obtained by calculating the arithmetic average.
  • the coefficient of variation in the particle size distribution of the flat metal particles can be obtained by a value (%) obtained by dividing the standard deviation of the particle size distribution by the above-mentioned average particle diameter (average circle equivalent diameter).
  • the coefficient of variation in the particle size distribution of the flat metal particles is preferably 35% or less, more preferably 30% or less, and particularly preferably 20% or less.
  • the coefficient of variation is preferably 35% or less because the reflection wavelength region of heat rays in the heat ray shielding material becomes sharp.
  • the size of the metal particles is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the average particle size is preferably 10 to 500 nm, more preferably 20 to 300 nm, and even more preferably 50 to 200 nm.
  • the thickness of the tabular metal particles is preferably 14 nm or less, more preferably 5 to 14 nm, and particularly preferably 5 to 12 nm.
  • the aspect ratio of the flat metal particles is not particularly limited and may be appropriately selected depending on the intended purpose. However, since the reflectance in the infrared light region having a wavelength of 800 nm to 1,800 nm increases, 6 ⁇ 40 are preferred, and 10 to 35 are more preferred. When the aspect ratio is less than 6, 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 flat metal particles by the average particle thickness of the flat metal particles.
  • the particle thickness corresponds to the distance between the main planes of the flat metal particles, and is, for example, as shown as a in FIG. 7A and FIG. be able to.
  • the method for measuring the average particle thickness by the AFM is not particularly limited and can be appropriately selected according to the purpose. For example, a particle dispersion containing tabular metal particles is dropped onto a glass substrate and dried. And a method of measuring the thickness of one particle.
  • the method for measuring the average particle thickness by the TEM is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a particle dispersion containing flat metal particles is dropped on a silicon substrate and dried. Thereafter, a coating process by carbon vapor deposition or metal vapor deposition is performed, a cross-section is created by focused ion beam (FIB) processing, and the cross-section is observed by TEM to measure the thickness of the particles.
  • FIB focused ion beam
  • the coating film thickness d of the metal particle-containing layer containing the flat metal particles is preferably 5 to 120 nm, more preferably 7 to 80 nm, and more preferably 10 to 40 nm. It is particularly preferred.
  • the hexagonal to circular flat metal particles 80 is preferably present in the range of d / 2 from the surface of the metal particle-containing layer, more preferably in the range of d / 3, and the hexagonal to circular plate-like metal particles More preferably, 60% by number or more is exposed on one surface of the metal particle-containing layer. That the flat metal particles are present in the range of d / 2 from the surface of the metal particle-containing layer means that at least a part of the flat metal particles is included in the range of d / 2 from the surface of the metal particle-containing layer.
  • FIG. 6D means that the flat metal particles described in FIG. 6D in which some of the flat metal particles protrude from the surface of the metal particle-containing layer are also flat plates existing in the range of d / 2 from the surface of the metal particle-containing layer. Treated as metal particles.
  • FIG. 6D means that a part of the thickness direction of each flat metal particle is buried in the metal particle-containing layer, and each flat metal particle is stacked on the surface of the metal particle-containing layer.
  • 6B to 6D are schematic views showing the case where the thickness d of the metal particle-containing layer is d> D / 2.
  • FIG. 6B includes 80% by number or more of the plate-like metal particles in the range of f.
  • the flat metal particle presence distribution 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 coating film thickness d of the metal particle-containing layer is preferably d ⁇ D / 2 with respect to the average equivalent circle diameter D of the metal particles, more preferably d ⁇ D / 4. d ⁇ D / 8 is more preferable.
  • 6E and 6F are schematic views showing a case where the thickness d of the metal particle-containing layer is d ⁇ D / 2.
  • the plasmon resonance wavelength of the metal constituting the flat metal particles 11 in the metal particle-containing layer 1 is ⁇
  • the refractive index of the medium in the metal particle-containing layer 1 is n.
  • the metal particle-containing layer 1 is preferably present in the range of ( ⁇ / n) / 4 in the depth direction from the horizontal plane of the heat ray shielding material. Within this range, the effect of increasing the amplitude of the reflected wave by the phase of the reflected wave at the interface between the upper and lower metal particle-containing layers of the heat ray shielding material is sufficiently large, and the visible light transmittance and the maximum heat ray Reflectivity is good.
  • the plasmon resonance wavelength ⁇ of the metal constituting the flat metal particles in the metal particle-containing layer is not particularly limited and can be appropriately selected according to the purpose. However, in terms of imparting heat ray reflection performance, 400 nm to 2 , 500 nm, and more preferably 700 nm to 2500 nm from the viewpoint of imparting visible light transmittance.
  • the metal particle-containing layer preferably contains a polymer, and more preferably contains a transparent polymer.
  • 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, 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.
  • 80% by number or more of hexagonal or circular plate-like metal particles are more preferable from the viewpoint of being easily present in a range of d / 2 from the surface of the metal particle-containing layer, and are polyester resins and polyurethane resins. It is particularly preferable from the viewpoint of further improving the rubbing resistance of the heat ray shielding material.
  • a saturated polyester resin is more particularly preferable from the viewpoint of imparting excellent weather resistance since it does not contain a double bond. Moreover, it is more preferable to have a hydroxyl group or a carboxyl group at the molecular terminal from the viewpoint of obtaining high hardness, durability, and heat resistance by curing with a water-soluble / water-dispersible curing agent or the like.
  • Commercially available polymers can be preferably used as the polymer, and examples thereof include PLUSCOAT Z-867, which is a water-soluble polyester resin manufactured by Kyoyo Chemical Industry Co., Ltd.
  • the main polymer of the polymer contained in the metal-containing layer refers to a polymer component occupying 50% by mass or more of the polymer contained in the metal-containing layer.
  • the content of the polyester resin and the polyurethane 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, and 20 to 500% by mass. It is particularly preferred that By setting the binder contained in the metal particle-containing layer to be in the above range or more, physical properties such as rubbing resistance can be improved.
  • 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 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.
  • 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 aspect of FIG. 6C and FIG. 6E is more preferable than the aspect of FIG. 6D and FIG. 6F for the heat ray shielding material of this invention.
  • 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.
  • 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 arrangement of the flat metal particles in the metal particle-containing layer is preferably uniform.
  • the variation coefficient of the closest interparticle distance is preferably as small as possible, preferably 30% or less, more preferably 20% or less, more preferably 10% or less, and ideally 0%.
  • the distance between the closest particles can be measured by observing the coated surface of the metal particle-containing layer with an SEM or the like.
  • the flat metal particles are arranged in the form of a metal particle-containing layer containing flat metal particles, as shown in FIGS. 6A to 6F.
  • the metal particle-containing layer may be composed of a single layer as shown in FIGS. 6A to 6F, 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.
  • each layer of the metal particle-containing layer can be measured, for example, by observing a cross-sectional sample of the heat ray shielding material with a SEM or observing a cross-sectional slice sample with a TEM.
  • 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 flat metal particles is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a liquid phase method such as a chemical reduction method, a photochemical reduction method, or an electrochemical reduction method may have a hexagonal shape. It is mentioned as what can synthesize
  • 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 particles After synthesizing hexagonal to triangular tabular metal particles, for example, by performing etching treatment with a dissolved species that dissolves silver such as nitric acid and sodium sulfite, aging treatment by heating, etc., hexagonal to triangular tabular shapes are obtained. Hexagonal or circular tabular metal particles may be obtained by blunting the corners of the metal particles.
  • the metal particles for example, Ag
  • the metal particles may be crystal-grown in a flat shape.
  • the flat metal particles may be subjected to further treatment in order to impart desired characteristics.
  • the further treatment is not particularly limited and may be appropriately selected depending on the purpose.
  • the formation of a high refractive index shell layer the addition of various additives such as a dispersant and an antioxidant may be included. Can be mentioned.
  • the flat metal particles may be coated with a high refractive index material having high visible light region transparency in order to further enhance visible light region transparency.
  • a high refractive index material is not particularly limited and may be appropriately selected depending on the purpose, for example, TiO x, BaTiO 3, ZnO, etc. SnO 2, ZrO 2, NbO x and the like.
  • an SiO 2 or polymer shell layer is appropriately formed. Further, 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 plate-like metal particles are dispersed. After forming the TiO x layer on the flat metal particles, an SiO 2 layer may be appropriately formed.
  • the metal particle-containing layer contains a polymer and the main polymer of the polymer is a polyester resin
  • a crosslinking agent from the viewpoint of film strength.
  • the crosslinking agent is not particularly limited, and examples thereof include epoxy-based, isocyanate-based, melamine-based, carbodiimide-based, and oxazoline-based crosslinking agents. Of these, carbodiimide and oxazoline crosslinking agents are preferred. Specific examples of the carbodiimide-based crosslinking agent include Carbodilite V-02-L2 (manufactured by Nisshinbo Chemical Co., Ltd.).
  • the surfactant a known surfactant such as an anionic or nonionic surfactant can be used as a specific example of the surfactant.
  • Lapisol A-90 manufactured by NOF Corporation
  • NAROACTY HN-100 manufactured by Sanyo Chemical Industries.
  • the surfactant is preferably contained in an amount of 0.05 to 10% by weight, more preferably 0.1 to 5% by weight, based on the total binder in the metal particle-containing layer.
  • the tabular metal particles may adsorb an antioxidant such as mercaptotetrazole or ascorbic acid in order to prevent oxidation of metals such as silver constituting the tabular metal particles.
  • an oxidation sacrificial layer such as Ni may be formed on the surface of the flat metal particles. Further, it may be covered with a metal oxide film such as SiO 2 for the purpose of blocking oxygen.
  • the flat metal particles are, for example, a low molecular weight dispersant, a high molecular weight dispersant or the like containing at least one of an N element such as a quaternary ammonium salt and amines, an S element, and a P element. A dispersant may be added.
  • the flat metal particle dispersion contains a preservative from the viewpoint of improving the visible light transmittance while maintaining the heat shielding performance.
  • the reason why the visible light transmittance can be improved while maintaining the heat shielding performance by containing the preservative is unknown.
  • the present inventors have found that the rot phenomenon due to microorganisms is related to the stability over time, and by introducing a preservative, the time-lapse of the plate-like metal particle dispersion liquid. It has been found that stability can be improved.
  • the stability over time of the flat metal particle dispersion is improved, the storage of the flat metal particle dispersion becomes substantially possible, and the flat metal particle dispersion is made and stored and supplied to the application all at once.
  • the productivity of the heat ray shielding material of the present invention described later is remarkably improved.
  • the conventional flat metal particle dispersion has poor stability over time and is not suitable for mass production. Especially when silver is used, the antibacterial property exhibited by silver was expected, but the conventional flat metal particle dispersion The metal particle dispersion had poor stability over time.
  • the filterability of the tabular metal particle dispersion can be improved by introducing a preservative into the tabular metal particle dispersion.
  • the filterability means that the increase in pressure when passing through the filtration filter is remarkably improved, and it becomes possible to feed a large amount continuously for a long time.
  • a filtration filter is put in the middle of the liquid feed to aggregate particles and dust Can be removed, and a high-quality heat ray shielding material according to the present invention, which will be described later, can be provided in a large area.
  • the problem of productivity drop due to stoppage of liquid feeding due to an increase in filtration pressure, that is, stoppage of coating is also solved.
  • the conventional flat metal particle dispersion liquid has poor filterability, and when passing through the filter, the pressure rises and the liquid cannot be fed, so it is difficult to capture and remove the aggregated particles and dust with the filter, It was not easy to obtain a heat ray shielding material with little coating surface failure.
  • By improving the stability over time and the filterability of the plate-like metal particle dispersion a large amount of coating raw materials are prepared and applied at once to give high productivity and high quality with less surface failure. It becomes possible to provide a heat ray shielding material in a large area.
  • the preservative is preferably a compound represented by the following general formula (11) or the following general formula (12), and is represented by the following general formula (11). More preferably, it is a compound.
  • R 13 is a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, (R 16 ) (R 17 ) —N—C ( ⁇ O) — or (R 16 ) (R 17 ) —N—C ( ⁇ S) —, wherein R 14 and R 15 each independently represent a hydrogen atom, an alkyl group, an aryl group, a cyano group, a heterocyclic group, an alkylthio group, or an alkylsulfoxy group.
  • R 14 and R 15 may be bonded to each other to form an aromatic ring, and R 16 and R 17 each independently represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. .)
  • R 20 represents a lower alkylene group.
  • X represents a halogen atom, a nitro group, a hydroxy group, a cyano group, a lower alkyl group, a lower alkoxy group, —COR 21 , —N (R 22 ) ( R 23 ) or —SO 2 M.
  • R 21 represents a hydrogen atom, —O M, a lower alkyl group, an aryl group, an aralkyl group, a lower alkoxy group, an aryloxy group, an aralkyloxy group, or —N (R 24 ) ( R 25 )
  • R 22 and R 23 each independently represents a hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group, —COR 26 or —SO 2 R 26, and may be the same or different from each other.
  • R 24 and R 25 each independently represent a hydrogen atom, a lower alkyl group, an aryl group, or an aralkyl group, and may be the same or different from each other.
  • R 26 represents a lower alkyl group, an aryl group or an aralkyl group
  • M represents a hydrogen atom, an alkali metal atom and an atomic group necessary for forming a monovalent cation
  • p represents 0 or 1.
  • Q represents an integer from 0 to 5.
  • R 13 represents a hydrogen atom, a linear or branched substituted or unsubstituted alkyl group (for example, methyl, ethyl, tert-butyl, n-octadecyl, 2-hydroxyethyl, 2-carboxyethyl, 2-cyanoethyl, sulfobutyl, N N-dimethylaminoethyl), substituted or unsubstituted cyclic alkyl groups (eg cyclohexyl, 3-methylcyclohexyl, 2-oxocyclopentyl), substituted or unsubstituted alkenyl groups (eg allyl, methylallyl), substituted or unsubstituted Aralkyl groups (eg benzyl, p-methoxybenzyl, o-chlorobenzyl, p-iso-propylbenzyl), substituted or unsubstituted aryl groups (eg phen
  • R 14 and R 15 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl, ethyl, chloromethyl, 2-hydroxyethyl, tert-butyl, n-octyl), substituted or unsubstituted cyclic alkyl Groups (eg cyclohexyl, 2-oxocyclopentyl), substituted or unsubstituted aryl groups (eg phenyl, 2-methylphenyl, 3,4-dichlorophenyl, naphthyl, 4-nitrophenyl, 4-aminophenyl, 3-acetamidophenyl) , Cyano group, heterocyclic group (for example, 2-imidazolyl, 2-thiazolyl, 2-pyridyl), substituted or unsubstituted alkylthio group (for example, methylthio, 2-cyanoethylthio, 2-ethoxycarbonylthio
  • R 16 and R 17 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl, ethyl, iso-propyl, 2-cyanoethyl, 2-n-butoxycarbonylethyl, 2-cyanoethyl), substituted or unsubstituted Substituted aryl groups (eg phenyl, naphthyl, 2-methoxyphenyl, m-nitrophenyl, 3,5-dichlorophenyl, 3-acetamidophenyl), substituted or unsubstituted aralkyl groups (eg benzyl, phenethyl, p-iso-propyl) Benzyl, o-chlorobenzyl, m-methoxybenzyl).
  • aryl groups eg phenyl, naphthyl, 2-methoxyphenyl, m-nitrophenyl, 3,5-dichloropheny
  • R 13 represents a hydrogen atom or a lower alkyl group
  • R 14 and R 15 are bonded to each other to form an aromatic ring
  • R 13 is a hydrogen atom.
  • R 14 and R 15 are more preferably bonded to each other to form a benzene ring.
  • R 20 represents a lower alkylene group (for example, ethylene group, propylene group, methylethylene group, etc.), and an alkylene group having 1 to 6 carbon atoms is particularly preferable.
  • X is a halogen atom (eg, chlorine atom, bromine atom, fluorine atom), nitro group, hydroxyl group, cyano group, lower alkyl group (eg, methyl, ethyl, iso-propyl, tert-butyl), lower alkoxy group —COR 21 , — N (R 22 ) (R 23 ) or —SO 2 M is represented.
  • R 21 represents a hydrogen atom, -O M, a lower alkyl group (eg, methyl, n-butyl, tert-octyl), an aryl group (eg, phenyl, 4-chlorophenyl, 3-nitrophenyl), an aralkyl group (eg, benzyl, p-iso-propylbenzyl, o-methylbenzyl), lower alkoxy groups (eg methoxy, n-butoxy, 2-methoxyethoxy), aryloxy groups (eg phenoxy, naphthoxy, 4-nitrophenoxy), aralkyloxy groups (eg Represents benzyloxy, p-chlorobenzyloxy, or —N (R 24 ) (R 25 ).
  • aralkyl group eg, methyl, n-butyl, tert-octyl
  • an aryl group eg, phenyl, 4-chlorophen
  • R 22 and R 23 are each independently a hydrogen atom, a lower alkyl group (eg, methyl, ethyl, 2-ethylhexyl), an aryl group (eg, phenyl, naphthyl, 2-methoxyphenyl, 3-acetamidophenyl), an aralkyl group ( For example, benzyl, o-chlorobenzyl), —COR 26 or —SO 2 R 26 may be the same or different.
  • a lower alkyl group eg, methyl, ethyl, 2-ethylhexyl
  • an aryl group eg, phenyl, naphthyl, 2-methoxyphenyl, 3-acetamidophenyl
  • an aralkyl group For example, benzyl, o-chlorobenzyl
  • —COR 26 or —SO 2 R 26 may be the same or different.
  • R 24 and R 25 are each independently a hydrogen atom, a lower alkyl group (eg, methyl, iso-propyl, 2-cyanoethyl), an aryl group (eg, phenyl, 4-ethoxycarbonylphenyl, 3-nitrophenyl), an aralkyl group ( For example, benzyl, p-chlorobenzyl) may be the same or different.
  • R 26 represents a lower alkyl group (eg, ethyl, 2-methoxyethyl, 2-hydroxyethyl) or an aryl group (eg, phenyl, naphthyl, 4-sulfophenyl, 4-carboxyphenyl).
  • M represents a hydrogen atom, an alkali metal atom (for example, sodium or potassium) and an atomic group necessary for forming a monovalent cation (for example, an ammonium cation or a phosphonium cation).
  • p represents 0 or 1;
  • q represents an integer of 0 to 5.
  • R 20 is an alkyl group represented by 1 to 3 carbon atoms
  • X is a lower alkyl group
  • p is 1
  • q is a compound represented by 0 or 1.
  • the preservative is a compound represented by the general formula (11)
  • the addition amount of the preservative is suitably in the range of 1 to 500 ppm with respect to the total weight of the dispersion
  • the range of 10 to 5000 ppm is appropriate with respect to the total weight of the dispersion.
  • the preservative may be dissolved in water or an organic solvent such as methanol, isopropurate, acetone, or ethylene glycol, and may be added as a solution to the flat metal particle dispersion of the present invention, or a high-boiling solvent, low-boiling point. After dissolving in a solvent or a mixed solvent of both, and then emulsifying and dispersing in the presence of a surfactant, it may be added to the flat metal particle dispersion of the present invention.
  • an organic solvent such as methanol, isopropurate, acetone, or ethylene glycol
  • an antifoaming agent in the steps of preparing the plate-like metal particles and redispersing.
  • the reaction solution and the coarse dispersion may be vigorously stirred.
  • foaming is often promoted by the presence of a surfactant or a dispersant.
  • the antifoaming agent can be selected from general ones such as surfactants, polyethers, esters, higher alcohols, mineral oils, and silicones.
  • surfactants are preferably used because they can exhibit a high defoaming effect when added in a small amount and are excellent in stability over time.
  • those having high lipophilicity and easily spreading on the liquid surface that is, those having a low HLB value are preferably used.
  • the HLB value is preferably 7 or less, more preferably 5 or less, and most preferably 3 or less.
  • Pluronic 31R1 manufactured by BASF
  • the heat ray shielding material of the present invention has an infrared absorbing compound-containing layer containing a compound having absorption in the infrared region.
  • the layer containing a compound having absorption in the infrared region is also referred to as an infrared absorbing compound-containing layer.
  • the infrared absorbing compound-containing layer may serve as another functional layer.
  • the absorption peak wavelength of the infrared absorbing compound is preferably shorter than the reflection peak wavelength of the metal particles from the viewpoint of efficiently shielding heat rays.
  • the heat ray shielding material of the present invention preferably contains 10 to 190 mg / m 2 of the infrared absorbing compound in the infrared absorbing compound-containing layer.
  • dye contained in the said infrared rays absorption compound content layer into the range of 190 mg / m ⁇ 2 > or less, the planar shape of a heat ray shielding material can be improved.
  • a method for controlling the pigment contained in the infrared absorbing compound-containing layer within this range a method of adjusting the pigment coating amount when the infrared absorbing compound-containing layer is formed by coating can be used.
  • the upper limit of the content of the dye contained in the infrared absorbing compound-containing layer is preferably 150 mg / m 2 or less from the viewpoint of improving the surface shape, and 120 mg / m 2 or less of the heat ray shielding material. It is more preferable from the viewpoint of increasing the maximum reflectance and suppressing the transmittance at the maximum reflection wavelength, and particularly preferably 100 mg / m 2 or less.
  • the lower limit value of the content of the infrared ray absorbing compound contained in the infrared ray absorbing compound-containing layer is 10 mg / m 2 or more to increase the maximum reflectance of the heat ray shielding material, and the transmittance at the maximum reflection wavelength. Is preferably 20 mg / m 2 or more, more preferably 30 mg / m 2 or more, and particularly preferably 30 mg / m 2 or more.
  • the transmittance at the maximum reflection wavelength is lowered, and the ratio of the absorbance to the reflectance at the maximum reflection wavelength is reduced.
  • it is preferably 0.15 to 1.0 g / cm 3 , more preferably 0.15 to 0.40 g / cm 3 , and 0.15 to 0.30 g / cm 3 . More particularly preferred.
  • the thickness of the infrared absorbing compound-containing layer is preferably 200 nm or less from the viewpoint of improving the surface shape, more preferably 50 to 200 nm, and more preferably 100 to 200 nm. This is particularly preferable from the viewpoint of increasing the maximum reflectance and reducing the transmittance at the maximum reflection wavelength.
  • the refractive index of the infrared absorbing compound-containing layer is not particularly limited, but although it is related to the film thickness, the conditions (1-1), (2-1), (3-1), (4-1), ( 5-1), adjusting the refractive index by adjusting the composition so as to satisfy (6-1), or adjusting the thickness can increase the visible light transmittance and the infrared light reflectance. To preferred.
  • the infrared-absorbing compound-containing layer may be disposed adjacent to the support or may be disposed via another layer therebetween. That is, in the heat ray shielding material of the present invention, the infrared absorbing compound-containing layer may be disposed adjacent to the support, and the infrared absorbing compound-containing layer is opposite to the surface having the metal particle-containing layer. It may have at least one layer (lower layer) on the surface. The lower layer will be described later.
  • the infrared absorbing compound is not particularly limited as long as it has absorption in the infrared region, and a known dye can be used.
  • the pigment include dyes and pigments, and infrared pigments are preferable.
  • the pigment is not particularly limited, and a known pigment can be used.
  • a known pigment can be used.
  • pigments described in JP-A-2005-17322, [0032] to [0039] and the like can be mentioned.
  • limiting in particular in the said dye A well-known dye can be used. Dyes that can be stably dissolved or dispersed in an aqueous dispersion of the polymer are preferred, and these dyes preferably have a water-soluble group.
  • water-soluble group examples include a carboxyl group and a salt thereof, a sulfo group and a salt thereof.
  • water-soluble dyes such as cyanine dyes and barbituric acid oxonol dyes described below can be applied as aqueous solutions without dissolving them in organic solvents. preferable. These dyes are preferably used as aggregates, and particularly preferably used as J aggregates. By using a J-aggregate, it becomes easy to set the absorption wavelength of a dye having an absorption maximum in the visible region in a desired near-infrared region in a non-association state. Moreover, durability, such as heat resistance of a dye, heat-and-moisture resistance, and light resistance, can be improved.
  • the dye is preferably an infrared absorbing dye from the viewpoint of selectively reflecting heat rays (near infrared rays).
  • the infrared absorbing dye include a near infrared absorbing dye described in JP-A-2008-181096, JP-A-2001-228324, JP-A-2009-244493, and the like, and JP-A 2010-90313. Near infrared absorbing compounds and the like can be preferably used.
  • the infrared absorbing pigment include cyanine dyes, oxonol dyes, and pyrrolopyrrole compounds.
  • the infrared absorbing compound is preferably a compound represented by the following general formula (1) or a compound represented by the following general formula (2).
  • the pyrrolopyrrole compound represented is more preferable from the viewpoint of enhancing the fastness and improving the storage stability.
  • Z 1 and Z 2 are each independently a non-metallic atom group that forms a 5- or 6-membered nitrogen-containing heterocycle.
  • R 1 and R 2 are each independently a fatty group.
  • L 1 is a methine chain composed of 3 methines.
  • a and b are each independently 0 or 1.
  • R 1a and R 1b may be the same or different and each independently represents an alkyl group, an aryl group or a heteroaryl group.
  • R 2 and R 3 each independently represent a hydrogen atom. Or at least one is an electron-withdrawing group, and R 2 and R 3 may combine to form a ring, and
  • R 4 represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a substituted group Represents a boron or metal atom, and may be a covalent bond or a coordinate bond with at least one group of R 1a , R 1b and R 3.
  • the preferred range of the compound represented by the general formula (1) is the same as the preferred range of the general formula (I) in JP-A-2001-228324.
  • the preferred range of the compound represented by the general formula (2) is the same as the preferred range of the general formula (1) in JP-A-2009-263614.
  • Cyanine dye is preferably a methine dye such as a pentamethine cyanine dye, a heptamethine cyanine dye, or a nonamethine cyanine dye, and a methine dye described in JP-A-2001-228324 is preferred.
  • a methine dye such as a pentamethine cyanine dye, a heptamethine cyanine dye, or a nonamethine cyanine dye
  • a methine dye described in JP-A-2001-228324 is preferred.
  • the cyclic group of the cyanine dye those having a thiazole ring, an indolenine ring or a benzoindolenine ring are preferable.
  • Examples of the cyanine dye used in the present invention include the cyanine dye represented by the general formula (1), that is, the general formula (I) of JP-A-2001-228324, and among them, a pentamethine cyanine dye.
  • Heptamethine cyanine dyes or nonamethine cyanine dyes (especially their aggregates) are preferred, and pentamethine cyanine dye, heptamethine cyanine dye or nonamethine cyanine represented by the general formula (II) of JP-A No. 2001-228324 Dyes (particularly, aggregates thereof) are more preferable, and heptamethine cyanine dyes represented by the general formula (II) in JP-A-2001-228324 are particularly preferable.
  • the oxonol dye is preferably an oxonol dye represented by the general formula (II) of JP-A No. 2009-244493, and more preferably a barbituric acid oxonol dye having a barbituric acid ring.
  • Examples of oxonol dyes represented by the general formula (II) in JP-A-2009-244493 are shown below, but the present invention is not limited to the following specific examples.
  • the pyrrolopyrrole compound As the pyrrolopyrrole compound, the pyrrolopyrrole compound represented by the above general formula (2), that is, the general formula (1) of JP2009-263614A or JP2010-90313A is exemplified. A pyrrolopyrrole compound represented by any one of the general formulas (2), (3), and (4) described in JP-A-2009-263614 and 2010-90313 is more preferable.
  • pyrrolopyrrole compound (dye) represented by the general formula (2) that is, any one of the general formulas (1) to (4) in JP2009-263614A and JP2010-90313A is described below. Specific examples will be shown, but the present invention is not limited to the following specific examples.
  • the heat ray shielding material of the present invention preferably contains a polymer in the infrared absorbing compound-containing layer.
  • the polymer can be used as a so-called binder in the infrared absorbing compound-containing layer.
  • the mass ratio of the polymer to the dye (polymer / dye ratio) in the infrared absorbing compound-containing layer is 5 or less, the transmittance at the maximum reflection wavelength is lowered, and the maximum reflection is achieved. This is preferable from the viewpoint of reducing the ratio of the absorptance to the reflectance at the wavelength.
  • the mass ratio of the polymer to the dye in the infrared absorbing compound-containing layer is more preferably 0.1 to 4, particularly preferably 0.2 to 3.0, and 0.5 to 3. More preferably, it is 0.
  • the preferred range of the content of the polymer contained in the infrared absorbing compound-containing layer is also related to the preferred range of the mass ratio of the polymer to the dye, but for example from the planar viewpoint that it is 350 mg / m 2 or less. Preferably, it is 30 mg / m 2 or more from the viewpoint of close contact with the support.
  • the type of the polymer is not particularly limited, and a known polymer can be used, and a transparent polymer is more preferable.
  • 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, and cellulose.
  • polymers such as natural polymers.
  • the polymer is preferably polyester, polyurethane, or polyacrylate resin, and polyester or polyurethane is more preferable from the viewpoint of adhesion to the support.
  • the polymer is an aqueous dispersion from the viewpoint of environmental influence and the reduction of coating cost.
  • the heat ray shielding material of this invention contains the said filler in at least any layer of an infrared rays absorption compound content layer and an intermediate
  • the kind and content of the filler contained in the infrared absorbing compound-containing layer are the same as the kind and content of the filler contained in the intermediate layer, and the preferred range is also the same.
  • the heat ray shielding material of the present invention preferably has a support.
  • limiting in particular as said support body A well-known support body can be used.
  • the support is not particularly limited as long as it is an optically transparent support and can be appropriately selected according to the purpose.
  • the visible light transmittance is 70% or more, preferably 80% or more. And those with high transmittance in the near infrared region.
  • the shape includes 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 for the support is not particularly limited and may be appropriately selected depending on the intended purpose.
  • polyolefin resins such as polyethylene, polypropylene, poly-4-methylpentene-1, polybutene-1, polyethylene terephthalate
  • Polyester resins such as polyethylene naphthalate
  • polycarbonate resins polyvinyl chloride resins
  • polyphenylene sulfide resins polyether sulfone resins
  • polyethylene sulfide resins polyphenylene ether resins
  • styrene resins acrylic resins
  • polyamides examples thereof include a film made of a cellulose resin such as a cellulose resin, a polyimide resin, and cellulose acetate, or a laminated film thereof.
  • a polyethylene terephthalate film is particularly preferable.
  • the thickness of the support is not particularly limited and may be appropriately selected depending on the purpose of use of the heat ray shielding material. Usually, the thickness is about 10 ⁇ m to 500 ⁇ m, but the thinner is preferable from the viewpoint of thinning. preferable.
  • the thickness of the support is preferably 10 ⁇ m to 100 ⁇ m, more preferably 20 to 75 ⁇ m, and particularly preferably 35 to 75 ⁇ m. When the thickness of the support is sufficiently thick, adhesion failure tends to hardly occur. Moreover, when the thickness of the said support body is thin enough, when it bonds together to a building material or a motor vehicle as a heat ray shielding material, there exists a tendency for the construction as it is not too strong and to become easy to construct.
  • the support when the support is sufficiently thin, the visible light transmittance is increased, and the raw material cost tends to be suppressed.
  • the refractive index nC at the wavelength ⁇ where the reflection of the layer C is to be prevented is larger than the refractive index nB at the wavelength ⁇ where the reflection of the layer B is to be prevented. This is preferable from the viewpoint that optical interference with the reflected light occurs and a better antireflection effect can be obtained.
  • the layer C is a support
  • a support having a refractive index of 1.5 or more, which is higher than ordinary glass (refractive index n is 1.5 or less) at a wavelength ⁇ to prevent reflection It is preferable from the viewpoint that the refractive index can be easily larger than the refractive index n2 of the layer B and can be used as the layer C by making use of the refractive index of the support itself.
  • the heat ray shielding material of the present invention preferably has a pressure-sensitive adhesive layer (hereinafter also referred to as a pressure-sensitive 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 10 ⁇ 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 hard coat layer may be provided on the outermost surface of the film for the purpose of protecting the outermost surface of the heat ray shielding material. Specifically, after the heat ray shielding material is bonded to the window glass, the surface of the heat ray shielding material opposite to the window glass is exposed to the environment, and the exposed surface is soiled or scratched by human contact. Since there is a possibility of entering, it is preferable to install the hard coat layer having a high physical strength in order to protect the exposed surface.
  • the heat ray shielding material of the present invention in order to prevent oxidation / sulfurization of the plate-like metal particles due to mass transfer and to provide scratch resistance, the heat ray shielding material of the present invention comprises the hexagonal or circular plate-like metal particles. It may have an overcoat layer in close contact with the surface of the metal particle-containing layer that is exposed. 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 prevents contamination of the manufacturing process due to peeling off of the tabular metal particles, disordered arrangement of the tabular metal particles during coating of another layer
  • An overcoat layer may be provided for preventing the above.
  • the overcoat layer may contain an ultraviolet absorber.
  • the overcoat layer is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the overcoat layer contains a binder, a matting agent, and a surfactant, and further contains other components as necessary. It becomes.
  • the binder is not particularly limited and may be appropriately selected depending on the purpose.
  • the thickness of the overcoat layer is preferably 0.01 ⁇ m to 1,000 ⁇ m, more preferably 0.02 ⁇ m to 500 ⁇ m, particularly preferably 0.1 to 10 ⁇ m, and particularly preferably 0.2 to 5 ⁇ m.
  • a back coat layer may be provided on the surface of the support opposite to the metal particle-containing layer.
  • the backcoat layer is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the backcoat layer may be a layer containing a compound having absorption in the infrared region, or may be a metal oxide particle-containing layer described later.
  • the preferred composition and thickness in the case of a layer containing a compound having absorption in the infrared region or a metal oxide particle-containing layer described later are the same as the preferred composition and thickness of the overcoat layer.
  • ⁇ Lower Layer In the heat ray shielding material of the present invention, having at least one layer (hereinafter, also referred to as a lower layer) between the infrared absorbing compound-containing layer and the support, rather than visible light transmittance, This is preferable from the viewpoint of giving priority to the improvement of the change in the reflection intensity after wet heat aging.
  • the lower layer the same binder materials, fillers and additives as in the intermediate layer can be used, and the preferred ranges are also the same.
  • the refractive index of the lower layer is not particularly limited, but although it is related to the film thickness, the conditions (1-1), (2-1), (3-1), (4-1), (5-1) Therefore, it is preferable to adjust the refractive index by adjusting the composition so as to satisfy (6-1) or to adjust the thickness from the viewpoint of increasing the visible light transmittance and increasing the infrared light reflectance.
  • the layer between the support and the metal particle-containing layer, that is, the lower layer, the infrared absorbing compound-containing layer, and the intermediate layer are collectively referred to as an undercoat layer. To give each layer a function.
  • the heat ray shielding material of the present invention preferably has a layer containing an ultraviolet 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, it is preferable that the ultraviolet absorber is 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-based ultraviolet absorber is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include mono (hydroxyphenyl) triazine compounds, bis (hydroxyphenyl) triazine compounds, and tris (hydroxyphenyl) triazine compounds. Etc. Examples of the mono (hydroxyphenyl) triazine compound include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethyl).
  • Phenyl) -1,3,5-triazine 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) ) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy- 4-isooctyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis ( 2,4-dimethylphenyl) -1,3,5-triazine, etc.
  • Examples of the bis (hydroxyphenyl) triazine compound include 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2 , 4-Bis (2-hydroxy-3-methyl-4-propyloxyphenyl) -6- (4-methylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl) -4-hexyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2-phenyl-4,6-bis [2-hydroxy-4- [3- (methoxyheptaethoxy ) -2-hydroxypropyloxy] phenyl] -1,3,5-triazine and the like.
  • tris (hydroxyphenyl) triazine compound examples include 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2 , 4,6-Tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropyloxy) ) Phenyl] -1,3,5-triazine, 2,4-bis [2-hydroxy-4- [1- (isooctyloxycarbonyl) ethoxy] phenyl] -6- (2,4-dihydroxyphenyl) -1 , 3,5-triazine, 2,4,6-tris [2-hydroxy-4- [1- (isooctyloxycarbonyl) ethoxy] phenyl] -1,3,5-triazine, 2,4-bis [2 -Hydroxy-4
  • the salicylate-based ultraviolet absorber is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, Examples include 2-ethylhexyl salicylate.
  • the cyanoacrylate-based ultraviolet absorber is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the binder is not particularly limited and may be appropriately selected depending on the intended purpose, but preferably has higher visible light transparency and higher solar transparency, and examples thereof include acrylic resin, polyvinyl butyral, and polyvinyl alcohol. .
  • the ultraviolet absorbing layer formed between the heat ray source and the flat metal particles is 450 nm to 1,500 nm. It is preferable to select a material that does not absorb light 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 thickness is less than 0.01 ⁇ m, ultraviolet absorption may be insufficient, and when it exceeds 1,000 ⁇ m, the visible light transmittance may be reduced.
  • 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 flat metal particle layer may change due to ultraviolet rays of sunlight.
  • the heat ray shielding material of the present invention is preferable from the viewpoint of balance between heat ray shielding and production cost even if it contains at least one kind of metal oxide particles in order to absorb long wave infrared rays. In this case, it is preferable that metal oxide particles are included in the back surface layer of the hard coat layer or other support.
  • the heat ray shielding material of the present invention is arranged so that the flat metal particle-containing layer is on the incident direction side of heat rays such as sunlight, a part of the heat rays are reflected by the metal particle-containing layer, but some of the heat rays are To Penetrate. As shown in FIG.
  • ATO Abbreviated as “ATO”
  • ZnO 2 zinc oxide
  • ZnO 2 zinc antimonate
  • titanium oxide indium oxide
  • tin oxide lanthanum hexaboride
  • Cs 0.33 cesium tungsten oxide
  • WO 3 hereinafter abbreviated as “CWO”.
  • ITO, ATO, CWO, and lanthanum hexaboride (LaB 6 ) are more preferable in that heat ray absorbing ability is excellent and a heat ray shielding material having a wide range of heat ray absorbing ability can be produced by combining with flat metal particles.
  • ITO is particularly preferable in that infrared rays of 1,200 nm or more are shielded by 90% or more and visible light transmittance is 90% or more.
  • the volume average particle size of the primary particles of the metal oxide particles is preferably 0.1 ⁇ m or less in order not to reduce the visible light transmittance.
  • a shape of the said metal oxide particle According to the objective, it can select suitably, For example, spherical shape, needle shape, plate shape, etc. are mentioned.
  • the content of the metal oxide particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 g / m 2 to 20 g / m 2 , and preferably 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 is, for example, by measuring the number and average particle diameter of the metal oxide particles in a certain area from the observation of the super foil section TEM image and the surface SEM image of the heat ray shielding layer, It can be calculated by 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.
  • the method for producing the heat ray shielding material of the present invention is not particularly limited and can be appropriately selected according to the purpose.
  • a dispersion having the dye on the surface of the lower layer such as the support examples thereof include a method of coating with a dip coater, a die coater, a slit coater, a bar coater, a gravure coater, and the like, and a method of plane orientation by a method such as an LB film method, a self-organization method, and spray coating.
  • the infrared absorbing compound-containing layer is preferably formed by coating. That is, the infrared ray absorbing compound-containing layer is preferably a dye coating layer. Among them, the method of applying with a bar coater is preferable.
  • the infrared absorbing compound-containing layer is formed by coating
  • other additives such as a solvent and a surfactant may be added to the coating solution in addition to the infrared absorbing compound and the polymer.
  • the solvent is not particularly limited and water or a known organic solvent can be used.
  • the solvent may be used in combination of two or more, in addition to being used alone. In the present invention, specifically, it is more preferable to use as an aqueous solvent in which water and methanol are combined.
  • Examples of other additives include surfactants and additives described in paragraph numbers [0027] to [0031] of JP-A-2005-17322.
  • the surfactant is not particularly limited, but may be any of aliphatic, aromatic, and fluorine surfactants, and may be any nonionic, anionic, or cationic surfactant.
  • Examples of the surfactant include those described in JP 2011-218807 A.
  • As the surfactant specifically, Rapisol A-90 manufactured by Nippon Oil & Fats Co., Ltd., NAROACTY CL95 manufactured by Sanyo Chemical Industries, Ltd., and the like are preferably used.
  • the surfactants may be used in combination of two or more in addition to being used alone.
  • the preferred ranges of the infrared absorbing compound coating amount and the polymer coating amount are the contents of the infrared absorbing compound and the polymer included in the infrared absorbing compound-containing layer, respectively. The same as the preferable range of the amount.
  • the infrared absorbing compound-containing layer is formed by coating, it is preferable to form the infrared absorbing compound-containing layer by applying the coating liquid and then drying and solidifying by a known method. As a drying method, drying by heating is preferable.
  • 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.
  • the dispersion having the flat metal particles on the surface of the lower layer such as the substrate A method of applying a liquid (flat metal particle dispersion) with a dip coater, a die coater, a slit coater, a bar coater, a gravure coater, or the like, a method of aligning the surface by a method such as LB film method, self-organization method, spray coating, Is mentioned.
  • a pressure roller such as a calendar roller or a laminating 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. 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.
  • the coating method at this time A well-known method can be used.
  • a film in which the pressure-sensitive adhesive is previously applied and dried on a release film is prepared, and the film is left in a dry state by laminating the pressure-sensitive adhesive surface of the film and the heat ray shielding material surface of the present invention. It is possible to laminate the pressure-sensitive adhesive layer.
  • a well-known method can be used.
  • Window glass As an example shown in FIG. 5A, when using the heat-shielding material of the present invention to provide functionality to existing window glass, it is preferable to laminate an adhesive and paste it on the indoor side of the window glass. .
  • the infrared reflection layer is installed on the sunlight side as much as possible because it can reflect the infrared rays to be incident on the room in advance.
  • the metal particle containing layer is installed on the sunlight incidence side.
  • a pressure-sensitive adhesive layer is provided on the metal particle-containing layer or a functional layer such as an overcoat layer provided on the metal particle-containing layer, and bonded to the window glass via the pressure-sensitive adhesive layer.
  • a heat ray shielding material When a heat ray shielding material is attached to a window glass, a heat ray shielding material provided by coating or laminating an adhesive layer is prepared, and a surfactant (on the surface of the window glass and the pressure ray adhesive layer of the heat ray shielding material is previously prepared). After spraying an aqueous solution containing mainly anionic), a heat ray shielding material may be installed on the window glass through the adhesive layer. Until the moisture evaporates, the adhesive force of the pressure-sensitive adhesive layer decreases, so that the position of the heat ray shielding material can be adjusted on the glass surface.
  • the water remaining between the window glass and the heat ray shielding material is swept from the glass center toward the edge by using a squeegee or the like.
  • the heat ray shielding material can be fixed. In this way, it is possible to install the heat ray shielding material on the window glass.
  • FIG. 5B for example, two glass plates, two polyvinyl butyral interlayer films (PVB sheets) for laminated glass, and the heat ray shielding material are prepared to produce a laminated glass body.
  • PVB sheet first sheet
  • heat ray shielding material PVB sheet
  • glass plate second sheet
  • This laminated body is preliminarily pressure-bonded at 95 ° C. for 30 minutes under vacuum, and then pressure-bonded with heating under conditions of 1.3 MPa and 120 ° C. in an autoflavor to obtain a laminated glass to which a heat ray shielding material is applied. be able to.
  • FIG. 5B for example, two glass plates, two polyvinyl butyral interlayer films (PVB sheets) for laminated glass, and the heat ray shielding material are prepared to produce a laminated glass body.
  • PVB sheet first sheet
  • heat ray shielding material PVB sheet
  • second sheet glass plate
  • the heat ray shielding material has the base material 40, but the base material is not necessarily required when the interlayer film for laminated glass body using the heat ray shielding material is formed, and the heat ray formed on the surface of the base material.
  • the laminated body of the heat ray shielding material may be incorporated into the laminated glass body intermediate film after the laminated body of the shielding material is peeled off from the base material, and the laminated body for laminated glass incorporating the thus obtained laminated body of the heat ray shielding material.
  • a laminated glass body may be formed in the same procedure as described above, and a laminated glass body to which a heat ray shielding material is applied may be formed.
  • the heat ray shielding material of the present invention is not particularly limited as long as it is an embodiment used for selectively reflecting (absorbing as necessary) heat rays (near infrared rays), and may be appropriately selected according to the purpose.
  • the film include a vehicle film and a laminated structure, a building material film and a laminated structure, and an agricultural film. 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.
  • 0.68 L of 8.0 g / L polystyrene sulfonic acid aqueous solution was added, and 0.041 L of sodium borohydride aqueous solution prepared to 23 g / L using 0.04 N sodium hydroxide aqueous solution was further added.
  • 13 L of 0.10 g / L silver nitrate aqueous solution was added at 5.0 L / min.
  • 1.0 L of 10 g / L trisodium citrate (anhydride) aqueous solution and 11 L of ion exchange water were added, and 0.68 L of 80 g / L potassium hydroquinone sulfonate aqueous solution was further added.
  • the absorption peak wavelength was 900 nm and the full width at half maximum was 270 nm. Met.
  • the obtained silver tabular grain dispersion liquid A was stored in a 20 L container of Union Container Type II (manufactured by Low Density Polyethylene, distributor: ASONE Co., Ltd.) and stored at 30 ° C.
  • a 0.2 mM NaOH aqueous solution was added to the precipitated silver tabular grains to make a total of 400 g, and the mixture was hand-stirred with a stirring rod to obtain a coarse dispersion.
  • 24 coarse dispersions were prepared to a total of 9600 g, added to a SUS316L tank and mixed.
  • 10 cc of a 10 g / L solution of Pluronic 31R1 manufactured by BASF
  • the dispersion liquid A was subjected to desalting treatment and redispersion treatment to prepare a silver tabular grain dispersion liquid B.
  • the spectral transmittance of the tabular silver particle dispersion B was measured by the same method as that for the tabular silver particle dispersion A, the absorption peak wavelength and the half width were almost the same as those of the tabular silver particle dispersion A.
  • the obtained silver tabular grain dispersion liquid A was stored in a 20 L container of Union Container II type and stored at 30 ° C.
  • Silver tabular grain dispersion liquid B was dropped on a silicon substrate and dried, and the individual thicknesses of the tabular silver grains were measured by the FIB-TEM method. Ten silver tabular grains in the silver tabular grain dispersion B were measured, and the average thickness was 8 nm.
  • coating liquid I1 for intermediate layer -Visible light reflectance reduction high refractive index coating liquid- Aqueous urethane resin: Hydran HW350 (Manufactured by DIC Corporation, solid content 30% by mass) 11.77 parts by mass
  • Surfactant B NAROACTY CL-95 (Manufactured by Sanyo Chemical Industry Co., Ltd., diluted with 1% solid content ion exchange water) 1.11 parts by weight crosslinking agent: Carbodilite V-02-L2 (Nisshinbo Chemical Co., Ltd., solid content concentration 20% by mass ion-exchanged water dilution) 7.56 parts by weight distilled water 73.27 parts by weight
  • aqueous dye dispersion BD-10- Water was added to 3 parts by mass of pyrrolopyrrole dye (D-10) having the structure shown below and 2 parts by mass of DisperBYK2091 (manufactured by Big Chemie) to make 100 parts by mass. Further, 50 parts by mass of 0.1 mm ⁇ zirconia beads were added, and the mixture was treated with a planetary ball mill at 300 rpm for 5 hours to produce an aqueous dye dispersion BD-10 composed of pyrrolopyrrole dye (D-10) fine particles. did. Thereafter, beads were separated and removed from the water product by filtration. When the obtained fine particles were observed with an electron microscope, they were irregular fine particles having an average particle diameter of 40 nm.
  • a dye aqueous dispersion BD-28 was prepared in the same manner as the dye aqueous dispersion BD-10, except that the pyrrolopyrrole dye (D-10) was changed to a pyrrolopyrrole dye (D-28) having the structure shown below. .
  • the obtained fine particles were observed with an electron microscope and found to be irregular fine particles having an average particle diameter of 60 nm.
  • surfactant B NAROACTY CL-95 (Manufactured by Sanyo Chemical Industry Co., Ltd., diluted with 1% solid content ion exchange water) 1.19 parts by mass Dye water-soluble dispersion BD-28 2.60 parts by mass Methanol 26.84 parts by mass Distilled water 65.36 parts by mass
  • coating liquid D4 for containing an infrared absorbing compound -Infrared absorbing compound-containing low refractive index coating liquid- Aqueous urethane resin: Hydran HW350 (Manufactured by DIC Corporation, solid content 30% by mass) 1.29 parts by mass hollow silica particles: through rear 4110 (Average particle size 60 nm, JGC Catalysts & Chemicals Co., Ltd., solid content 20% by mass) 3.16 parts by mass Surfactant B: NAROACTY CL-95 (Manufactured by Sanyo Chemical Industry Co., Ltd., diluted with 1% solid content ion exchange water) 1.19 parts by mass Dye water-soluble dispersion BD-28 1.26 parts by mass Methanol 26.84 parts by mass Distilled water 65.36 parts by mass
  • surfactant B NAROACTY CL-95 (Manufactured by Sanyo Chemical Industry Co., Ltd., diluted with 1% solid content ion exchange water) 1.19 parts by mass
  • Dye water-soluble dispersion BD-10 2.60 parts by mass Methanol 26.84 parts by mass Distilled water 65.36 parts by mass
  • colloidal silica fine particles Snowtex XL (average particle size 50 nm) (Nissan Chemical Industry Co., Ltd., diluted with 10% solids by distilled water) 0.0033 parts by mass Colloidal silica fine particle dispersion A 0.079 parts by mass Acrylic polymer aqueous dispersion: AS-563A (Daicel Finechem Co., Ltd., solid content 27.5% by mass) 0.13 parts by weight wax: cellosol 524 (Manufactured by Chukyo Yushi Co., Ltd., diluted with 3% solids by distilled water) 0.78 parts by mass Crosslinker: Carbodilite V-02-L2 (Nisshinbo Chemical Co., Ltd., diluted with distilled water with a solid concentration of 20% by mass) 0.46 parts by mass of surfactant A: Lipal 870P (Manufactured by Lion Corporation, diluted with distilled water at a solid content of 1% by mass) 0.63 parts by mass
  • colloidal silica fine particle dispersion A- 0.10 kg of Aerosil OX-50 (manufactured by Nippon Aerosil Co., Ltd.), a colloidal silica fine particle with an average primary particle diameter of 40 nm, is weighed into a SUS304 container, 0.9 kg of ion-exchanged water is added, and a desktop quick Using a homomixer LR-1 (manufactured by Mizuho Kogyo Co., Ltd.), coarse dispersion was performed at 3000 rpm for 60 minutes.
  • ITO paint PI-3 (Mitsubishi Materials Kasei Co., Ltd.) is made of ITO (tin-doped indium oxide), dispersant, polyacrylate, initiator, toluene, 4-hydroxy-4-methyl-2-pentanone, 2- It is a heat ray-cut paint mainly composed of methyl-1-propanol and ethanol.
  • the ITO content is 28% by mass.
  • a roll-shaped PET film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd., width: 1320 mm, thickness: 75 ⁇ m, double-sided easy-adhesive layer treatment, refractive index: 1.66) is conveyed at a speed of 15 m / min and supported.
  • the infrared absorbing compound-containing layer coating solution D2 is applied on one side of the body using a wire bar to 10.6 cc / m 2 and dried at 130 ° C. to provide an infrared absorbing compound-containing layer. It was.
  • the film thickness after coating and drying was 205 nm and the refractive index was 1.40.
  • the density of the infrared absorbing compound in the infrared absorbing compound-containing layer (expressed as dye density in Table 1) was 0.20 g / cm 3 .
  • the content density of the infrared compound in the infrared absorbing compound-containing layer was calculated from the thickness of the infrared absorbing compound-containing layer and the content of the infrared absorbing compound in the solid content in the coating solution.
  • the coating liquid I1 is applied on the infrared absorbing compound-containing layer so as to be 5.30 cc / m 2 using a wire bar, and subjected to a drying treatment at 140 ° C., An intermediate layer was provided.
  • the film thickness after coating and drying was 200 nm, and the refractive index was 1.60.
  • the coated support was wound up under the temperature and humidity conditions of 23 ⁇ 2 ° C. and 70 ⁇ 5% RH to obtain a coated film A in roll form.
  • the coated film A in roll form is conveyed at a speed of 15 m / min, and the coating liquid M1 of the metal particle-containing layer is applied on the intermediate layer so as to be 10.6 cc / m 2 using a wire bar.
  • a drying treatment was performed at 140 ° C. to provide a metal particle-containing layer containing silver tabular grains.
  • the film thickness after coating and drying was 10 nm.
  • the protective layer coating solution O1 is applied onto the metal particle-containing layer using a wire bar so as to be 5.30 cc / m 2, and a drying treatment is performed at 135 ° C.
  • An overcoat layer (protective layer) was provided.
  • the film thickness after coating and drying was 33 nm and the refractive index was 1.51.
  • the coated support was wound under temperature and humidity conditions of 23 ⁇ 2 ° C. and relative humidity 55 ⁇ 5% to obtain a coated film B in roll form.
  • the winding length was 2200 m.
  • the back surface first layer coating solution B1 is applied and dried using a slot die coating method. It apply
  • the back surface second layer coating solution B2 is applied onto the back surface first layer using a slot die coating method so that the film thickness after coating and drying UV curing is 3 ⁇ m. And a drying treatment at 80 ° C.
  • the dried coating layer is irradiated with 500 mJ / cm 2 of ultraviolet light under atmospheric pressure using a 160 W / cm high-pressure mercury lamp (manufactured by Eye Graphics Co., Ltd.), and metal oxidation is performed.
  • a 3 ⁇ m hard coat layer (back surface second layer) was provided on the product particle-containing layer (back surface first layer). In this way, a hard coat layer having a refractive index of 1.66 was obtained.
  • Example 101 which is a heat ray heat shielding material was produced.
  • the average thickness is determined by measuring the difference between before and after coating as a thickness using a laser microscope VK-8510 (manufactured by Keyence Co., Ltd.), and observing the cross section of the heat ray shielding material with SEM or TEM.
  • the method of calculating by the above, the method of calculating by performing cross-section cutting and observation by the FIB-TEM method, and the method of measuring the reflection spectrum and calculating by fitting were used as appropriate.
  • coating and observing only one object layer to the film used as a support body was also used suitably.
  • a roll-shaped PET film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd., width: 1320 mm, thickness: 75 ⁇ m, double-sided easy-adhesive layer treatment) is conveyed at a speed of 15 m / min, and a lower layer is formed on one side of the support.
  • the coating liquid U1 was applied using a wire bar to 6.9 cc / m 2 and dried at 140 ° C. to provide a lower layer.
  • the film thickness after coating and drying was 132 nm, and the refractive index was 1.85.
  • the coating solution D2 for the infrared absorbing compound-containing layer is coated on the lower layer so as to be 5.3 cc / m 2 using a wire bar, and dried at 130 ° C.
  • An absorbing compound-containing layer was provided.
  • the film thickness after coating and drying was 102 nm and the refractive index was 1.40.
  • the coating solution I3 for the first intermediate layer is applied onto the infrared absorbing compound-containing layer using a wire bar so that the film thickness after coating and drying is 135 nm, A drying treatment was performed at 140 ° C.
  • the coating liquid I2 for the second intermediate layer was applied using a wire bar so that the film thickness after coating and drying was 102 nm, and a drying treatment was performed at 140 ° C.
  • the third intermediate layer coating solution I3 is applied using a wire bar so that the film thickness after coating and drying is 185 nm, and is subjected to a drying treatment at 140 ° C. to form three intermediate layers. Formed. After the three intermediate layers were coated, the coated support was wound up under temperature and humidity conditions of 23 ⁇ 2 ° C. and a relative humidity of 70 ⁇ 5% to obtain a coated film C in roll form.
  • the coated film C in roll form is conveyed at a speed of 15 m / min, and the coating liquid M1 of the metal particle-containing layer is applied onto the intermediate layer so as to be 10.6 cc / m 2 using a wire bar, A drying treatment was performed at 140 ° C. to provide a metal particle-containing layer containing silver tabular grains. The film thickness after coating and drying was 10 nm.
  • the protective layer coating solution O1 is applied onto the metal particle-containing layer using a wire bar so as to be 5.30 cc / m 2, and a drying treatment is performed at 135 ° C.
  • An overcoat layer (protective layer) was provided.
  • the film thickness after coating and drying was 33 nm and the refractive index was 1.51.
  • the coated support was wound under temperature and humidity conditions of 23 ⁇ 2 ° C. and relative humidity 55 ⁇ 5% to obtain a coated film B in roll form.
  • the winding length was 2200 m.
  • the back surface first layer coating solution B1 is applied and dried using a slot die coating method. It apply
  • the dried coating layer was cured by irradiating 300 mJ / cm 2 of ultraviolet rays under atmospheric pressure using a 160 W / cm metal halide lamp (manufactured by Eye Graphics Co., Ltd.).
  • An oxide particle-containing layer (back surface first layer) was provided, and wound up under temperature and humidity conditions of 23 ⁇ 2 ° C. and 55 ⁇ 5% RH.
  • the heat ray shielding material 104 was produced.
  • the VLT value and the SC value of the heat ray shielding material change with a certain relationship.
  • the VLT value decreases and the SC value decreases (this indicates that the amount of transmitted light decreases to darken and the heat ray shielding ability increases). That is, when comparing between test samples, it is necessary to compare the VLT value with the same SC value (or compare the SC value with the same VLT value).
  • a plurality of heat ray shielding material sample groups are prepared by appropriately changing the coating amount of the metal particle-containing layer, and the VLT value and SC value of each sample are obtained. Then, a VLT value at a desired SC value is obtained by a function (approximate curve) obtained by plotting data of the heat ray shielding material sample group. Thereby, a valid evaluation can be performed.
  • the other heavy release separator (silicone-coated PET) of PD-S1 is peeled off, and a soda-lime silicate glass (sheet glass) using a 0.5% by weight diluted solution of Real Perfect (manufactured by Lintec Co., Ltd.), which is a film construction solution. (Thickness: 3 mm) and optical characteristics were evaluated.
  • the said plate glass uses the thing which wiped off the dirt with isopropyl alcohol, and dried naturally, and when bonded, it is pressure-bonded with a surface pressure of 0.5 kg / cm 2 using a rubber roller in an environment of 25 ° C. and 65% RH. did.
  • These heat ray shielding material sample groups (glass bonded) were used as test samples.
  • the visible light transmittance and shielding coefficient of the heat ray shielding material can be changed depending on the amount of coating at the time of forming the metal particle-containing layer.
  • a large number of heat ray shielding materials were produced by changing the coating amount of the coating solution for the metal particle-containing layer including the plate-like metal particle-containing solution of each example and comparative example.
  • the visible light transmittance and the shielding coefficient were calculated by the method.
  • the transmission spectrum and reflection spectrum of the heat ray shielding material prepared in each example and comparative example were measured using an ultraviolet-visible-near infrared spectrometer (manufactured by JASCO Corporation, V-670, using integrating sphere unit ISN-723). Visible light transmittance and shielding factor were calculated according to JIS R 3106 and JIS A 5759.
  • VLT visible light transmittance
  • the smaller change in the reflectance means that the heat shielding performance of the heat ray shielding material is less changed before and after the wet heat aging.
  • the window glass with a heat ray shielding material of the example group of the present invention was visually confirmed to be highly transparent.
  • a laminated glass body to which heat ray shielding material is applied was produced in the following manner.
  • two glass plates, two polyvinyl butyral interlayer films (PVB sheet) for laminated glass, and the heat ray shielding material are prepared, and the glass plate (first sheet), PVB sheet (1 Sheet), a heat ray shielding material, a PVB sheet (second sheet), and a glass plate (second sheet).
  • This laminated body is preliminarily pressure-bonded at 95 ° C.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Optical Filters (AREA)

Abstract

L'invention porte sur un matériau de blindage vis-à-vis du rayonnement thermique, lequel matériau comprend : une couche contenant des particules métalliques, qui contient au moins un type de particules métalliques; une couche contenant un composé absorbant les infrarouges, qui contient un composé absorbant les infrarouges; et au moins une couche intermédiaire, qui est disposée entre la couche contenant des particules métalliques et la couche contenant un composé absorbant les infrarouges. Ce matériau de blindage vis-à-vis du rayonnement thermique contient une charge dans la couche contenant un composé absorbant les infrarouges et/ou dans la couche intermédiaire. Par conséquent, ce matériau de blindage vis-à-vis du rayonnement thermique a une aptitude au blindage vis-à-vis du rayonnement thermique élevée, un facteur de transmission de la lumière visible élevé et une excellente durabilité à la chaleur humide.
PCT/JP2014/055718 2013-03-25 2014-03-06 Matériau de blindage vis-à-vis du rayonnement thermique, vitre de fenêtre utilisant un matériau de blindage vis-à-vis du rayonnement thermique, film intermédiaire pour verre stratifié, et verre stratifié WO2014156528A1 (fr)

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JP2013-062541 2013-03-25
JP2013062541A JP2014184688A (ja) 2013-03-25 2013-03-25 熱線遮蔽材ならびに熱線遮蔽材を用いた窓ガラス、合わせガラス用中間膜および合わせガラス

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