WO2017022579A1 - Matériau de réflexion de rayon de chaleur et fenêtre - Google Patents

Matériau de réflexion de rayon de chaleur et fenêtre Download PDF

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WO2017022579A1
WO2017022579A1 PCT/JP2016/071932 JP2016071932W WO2017022579A1 WO 2017022579 A1 WO2017022579 A1 WO 2017022579A1 JP 2016071932 W JP2016071932 W JP 2016071932W WO 2017022579 A1 WO2017022579 A1 WO 2017022579A1
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Prior art keywords
heat ray
ray reflective
reflective material
containing layer
conductive particle
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PCT/JP2016/071932
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English (en)
Japanese (ja)
Inventor
直井　憲次
清都　尚治
佑一 早田
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富士フイルム株式会社
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Priority to CN201680032132.XA priority Critical patent/CN107615116B/zh
Publication of WO2017022579A1 publication Critical patent/WO2017022579A1/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
    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B5/00—Doors, windows, or like closures for special purposes; Border constructions therefor
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting filters

Definitions

  • This disclosure relates to heat ray reflective materials and windows.
  • the heat insulating property can be expressed by a heat permeability.
  • JIS Japanese Industrial Standards
  • the thermal transmissivity can be determined from the reflection spectrum of far infrared rays having a wavelength of 5 ⁇ m to 50 ⁇ m. That is, it is preferable to increase the reflectivity of far-infrared rays having a wavelength of 5 ⁇ m to 50 ⁇ m in order to reduce the heat transmissivity.
  • JP 2012-252172 A discloses a heat ray shielding film including a heat ray reflective layer containing a transparent film and metal nanofibers.
  • the heat ray shielding film disclosed in Japanese Patent Application Laid-Open No. 2012-252172 since the heat ray reflective layer contains metal nanofibers, the heat ray from the room, such as heating, is not reflected and escaped, and the heat of the outside air is not reflected. It is said to have excellent heat insulation properties that are not taken into the room.
  • Japanese Patent Application Laid-Open No. 2004-238503 discloses a rod-shaped metal nanofiber having a major axis of less than 400 nm and an aspect ratio of greater than 1, and a major axis of 400 nm or more, although the application is not a heat ray reflective material.
  • a near-infrared light absorbing filter comprising a metal nanofiber-containing composition containing a wire-like metal nanofiber having a short axis of 50 nm or less is disclosed.
  • the heat ray reflective material used for the window may be used by being attached to an adherend through an adhesive.
  • As a method of sticking the heat ray reflective material to the adherend there is a method of sticking the heat ray reflective material after applying the construction liquid to the window.
  • the heat ray reflective material is required to have durability (particularly, scratch resistance when the surface is wet).
  • the layer is formed when the surface of the heat ray reflective material is rubbed with a squeegee or the like during construction. There is a risk of peeling. Moreover, when a curable resin is simply used as the resin component, the layer becomes too hard and cracking may occur during construction.
  • One embodiment of the present invention has been made in view of the above, and has excellent heat insulation and durability (particularly, scratch resistance in a wet state of the surface (hereinafter also referred to as wet film strength) and suppression of cracking). It is an object to provide a heat ray reflective material and a window.
  • ⁇ 1> having at least a support and a conductive particle-containing layer having a surface resistance of 1000 ⁇ / square or more on the side opposite to the side on which the support is disposed, including a fibrous conductive particle
  • the at least one layer selected from all the layers including the conductive particle-containing layer disposed on the side having the conductive particle-containing layer of the support comprises a bifunctional or lower functional monomer and a trifunctional or higher functional monomer.
  • a heat ray reflective material comprising an organic binder which is a polymer of a monomer composition having a mass ratio of a bifunctional or lower functional polymerizable monomer to a trifunctional or higher functional polymerizable monomer of 10/90 to 90/10.
  • heat-reflecting material according to the content of the fibrous conductive particles is 0.020g / m 2 ⁇ 0.200g / m 2 ⁇ 1>.
  • ⁇ 5> The heat ray reflective material according to any one of ⁇ 1> to ⁇ 4>, wherein the bifunctional or lower functional polymerizable monomer includes a monofunctional polymerizable monomer and a bifunctional polymerizable monomer.
  • ⁇ 6> The heat ray reflective material according to ⁇ 5>, wherein the content of the bifunctional polymerizable monomer is greater than the content of the monofunctional polymerizable monomer.
  • ⁇ 7> The heat ray reflective material according to any one of ⁇ 1> to ⁇ 6>, wherein the fibrous conductive particles have an average minor axis length of 150 nm or less and an average major axis length of 5 ⁇ m to 50 ⁇ m.
  • ⁇ 8> The heat ray reflective material according to any one of ⁇ 1> to ⁇ 7>, wherein the mass ratio of the content of the fibrous conductive particles to the content of the organic binder is 1/20 to 1/10.
  • ⁇ 9> The heat ray according to any one of ⁇ 1> to ⁇ 8>, wherein the conductive particle-containing layer is an uppermost layer disposed at a position farthest from the support or a layer adjacent to the uppermost layer on the support side. Reflective material.
  • ⁇ 10> The heat ray reflective material according to any one of ⁇ 1> to ⁇ 9>, wherein the conductive particle-containing layer is an uppermost layer disposed at a position farthest from the support.
  • ⁇ 11> The heat ray reflective material according to any one of ⁇ 1> to ⁇ 10>, wherein the visible light transmittance in accordance with JIS A5759: 2008 is 70% or more.
  • a window comprising the heat ray reflective material according to any one of ⁇ 1> to ⁇ 11>, an adhesive layer, and a transparent substrate.
  • a heat ray reflective material and a window excellent in heat insulation and durability are provided.
  • heat ray reflective material and window of one embodiment of the present invention will be described in detail.
  • a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • (meth) acrylate means at least one of acrylate and methacrylate.
  • (meth) acryl means at least one of acrylic and methacryl.
  • heat insulation means that far infrared rays having a wavelength of 5 ⁇ m to 50 ⁇ m are reflected by an average reflectance of 5% or more.
  • the average reflectance of far-infrared rays is more preferably 7% or more, particularly preferably 8% or more, and particularly preferably 10% or more.
  • the far-infrared reflectance is a value measured by an infrared spectrometer (manufactured by Bruker Optics, IFS 66v / S).
  • the heat ray reflective material of one embodiment of the present invention is a material that is disposed on the indoor side of the window and keeps indoor far infrared rays in the room, and includes at least a support and fibrous conductive particles, and at least the support is A conductive particle-containing layer having a surface resistance of 1000 ⁇ / square or more on the surface opposite to the side on which the conductive particle is disposed, and disposed on the side of the support having the conductive particle-containing layer.
  • An organic binder (hereinafter also referred to as a specific organic binder) which is a polymer of a monomer composition having a ratio of 10/90 to 90/10.
  • the conductive particle-containing layer disposed on the support may be a layer (the uppermost layer) disposed farthest from the support, and the side of the conductive particle-containing layer having the support; Further, a layer (for example, a protective layer) may be provided on the opposite side to form the uppermost layer.
  • at least one layer arranged on the side having the conductive particle-containing layer of the support contains a specific organic binder.
  • the conductive particle-containing layer may contain a specific organic binder, and when a protective layer is provided on the conductive particle-containing layer, the protective layer may contain a specific organic binder, and both the conductive particle-containing layer and the protective layer are specific organic.
  • a binder may be included.
  • the fibrous conductive particles are fibrous, the reflectivity of the particles themselves with respect to far infrared rays is high, and if the fibrous conductive particles are present, a heat insulating effect can be obtained, so that the fibrous conductive particles are not necessarily in contact with each other. It is not necessary to be there. Therefore, when fibrous conductive particles are used for the heat ray reflective material, a material with high heat insulation can be obtained while maintaining high surface resistance (1000 ⁇ / square or more).
  • the heat ray reflective material may be attached after applying the application liquid to an adherend (for example, a window) because of the advantage that the attachment position can be easily adjusted.
  • the surface of the heat ray reflective material is affixed while being rubbed with a squeegee, etc., so the heat ray reflective material has durability (especially when the surface is wet). Desired.
  • the heat ray shielding film described in the above-mentioned JP2012-252172A is not assumed to be attached using the above-described construction liquid, and is severely rubbed by a squeegee in the wet state. It is considered that the Wet film strength is insufficient under such conditions.
  • the heat ray reflective material of one embodiment of the present invention contains a specific organic binder, and the specific organic binder is blended in a predetermined mass ratio.
  • a monomer composition containing the following polymerizable monomer and a tri- or higher functional polymerizable monomer is formed by polymerization. Therefore, it is considered that the heat ray reflective material has a Wet film strength that can withstand even if it is rubbed with a squeegee in a wet state, and on the other hand, it does not become too hard to cause cracks during construction.
  • the heat ray reflective material of one embodiment of the present invention is excellent in heat insulation and durability.
  • the heat ray reflective material of one embodiment of the present invention suppresses radio wave absorption in the conductive particle-containing layer when the surface resistance of the conductive particle-containing layer is 1000 ⁇ / square or more. That is, it is thought that the heat ray reflective material of one embodiment of the present invention has radio wave permeability.
  • the heat ray reflective material of one embodiment of the present invention has a conductive particle-containing layer containing fibrous conductive particles on the support and having a surface resistance of at least 1000 ⁇ / square on the side having no support.
  • the conductive particle-containing layer can contain a specific organic binder.
  • a heat ray reflective material shows heat insulation because a conductive particle content layer contains fibrous conductive particles.
  • the fibrous conductive particles in the conductive particle-containing layer are relatively small in quantity, but the thermal conductivity is low, that is, the heat insulation is good.
  • the heat ray reflective material also exhibits radio wave permeability.
  • the surface resistance of the conductive particle-containing layer is more preferably 1500 ⁇ / square or more, further preferably 2000 ⁇ / square or more, and particularly preferably 3000 ⁇ / square or more.
  • the conductive particle-containing layer includes a specific organic binder
  • durability is imparted to the heat ray reflective material by including the specific organic binder.
  • the surface resistance can be measured using a non-contact resistance meter (Napson, EC-80) in an environment of a temperature of 23 ° C. and a humidity of 50%.
  • the content of the fibrous conductive particles in the conductive particle-containing layer is preferably 0.010g / m 2 ⁇ 0.300g / m 2, a 0.020g / m 2 ⁇ 0.200g / m 2 More preferably, it is 0.020 g / m 2 to 0.100 g / m 2 .
  • Heat insulation can be improved more because content of a fibrous conductive particle is 0.010 g / m ⁇ 2 > or more.
  • the conductivity of the heat ray reflective material can be kept low, and the haze of the heat ray reflective material can be further lowered.
  • the specific organic binder is formed by polymerizing a monomer composition including a bifunctional or lower polymerizable monomer and a trifunctional or higher functional polymerizable monomer.
  • the mass ratio of the bifunctional or lower polymerizable monomer to the trifunctional or higher polymerizable monomer in the monomer composition is 10/90 to 90/10, preferably 30/70 to 70/30, More preferably, it is ⁇ 60 / 40.
  • the range of the mass ratio of the monomer is equal to or higher than the lower limit, cracking during construction of the heat ray reflective material is suppressed.
  • the range of the mass ratio of the monomer is not more than the upper limit value, the strength of the Wet film at the time of applying the heat ray reflective material is excellent.
  • Said mass ratio can be adjusted with the compounding quantity of the bifunctional or less polymerizable monomer and trifunctional or more polymerizable monomer in a monomer composition.
  • the bifunctional or lower polymerizable monomer preferably contains at least one monofunctional polymerizable monomer and one bifunctional polymerizable monomer.
  • the bifunctional or lower polymerizable monomer includes a monofunctional polymerizable monomer and a bifunctional polymerizable monomer
  • the content of the bifunctional polymerizable monomer is greater than the content of the monofunctional polymerizable monomer. Is more preferable.
  • the mass ratio of the content of the fibrous conductive particles to the content of the organic binder in the conductive particle-containing layer is preferably 1/120 to 1 / 1.5, and preferably 1/100 to 1/2. Is more preferably 1/20 to 1/10.
  • the range of the mass ratio of the content of the fibrous conductive particles to the content of the organic binder is not less than the lower limit value, the strength of the Wet film can be further improved.
  • the range of the mass ratio of the content of the fibrous conductive particles to the content of the organic binder is not more than the upper limit value, the surface resistance of the conductive particle-containing layer can be easily adjusted to a predetermined range.
  • the fibrous conductive particles are particles having fibrous conductivity.
  • the “fibrous” includes particles in a wire shape, a linear shape, or a rod shape.
  • particles having conductivity means that when pellets having a thickness of 0.01 mm or more are produced by molding fibrous particles with a tablet molding machine or dispersing the fibrous particles in a liquid and then drying.
  • grains from which the resistance value between the one end surface and other end surface of a pellet becomes 10 ohms or less are pointed out.
  • the resistance value is a value measured by a two-point tester (MR-4060, manufactured by MONOTARO).
  • fibrous conductive particles examples include fibrous metal particles such as metal nanowires and rod-shaped metal particles, carbon nanotubes, and fibrous conductive resins.
  • metal nanowires are preferable.
  • Metal nanowires are conductive, have a long axis length longer than a diameter (short axis length), and a short axis length (that is, the length of a cross section perpendicular to the longitudinal direction) of nano-order size. Metal particles with a shape.
  • the metal nanowire may be a solid fiber or a hollow fiber.
  • the conductive particle-containing layer preferably contains fibrous conductive particles having an average minor axis length of 150 nm or less. It is preferable for the average minor axis length to be 150 nm or less because the heat insulation is improved and the optical properties are hardly deteriorated due to light scattering or the like. It is preferable that the fibrous conductive particles have a solid structure.
  • the fibrous conductive particles preferably have an average minor axis length of 1 nm to 150 nm.
  • the average minor axis length (average diameter) of the fibrous conductive particles is preferably 100 nm or less, more preferably 60 nm or less, and even more preferably 50 nm or less, In particular, it is preferable that the thickness is 25 nm or less because a further excellent haze can be obtained.
  • the average minor axis length is more preferably 5 nm or more, further preferably 10 nm or more, and particularly preferably 15 nm or more.
  • the average minor axis length of the fibrous conductive particles is preferably 1 nm to 100 nm, more preferably 5 nm to 60 nm, and more preferably 10 nm to 60 nm from the viewpoints of haze value, oxidation resistance, and weather resistance. Is more preferable, and it is particularly preferably 15 nm to 50 nm.
  • the average long axis length of the fibrous conductive particles is preferably about the same as the far-infrared reflection band desired to be reflected because the far-infrared reflection band desired to be reflected is easily reflected.
  • the average major axis length of the fibrous conductive particles is preferably 5 ⁇ m to 50 ⁇ m from the viewpoint of easy reflection of far infrared rays having a wavelength of 5 ⁇ m to 50 ⁇ m, more preferably 10 ⁇ m to 40 ⁇ m, still more preferably 15 ⁇ m to 40 ⁇ m.
  • the average major axis length of the fibrous conductive particles is 50 ⁇ m or less, when forming the fibrous conductive particles, it becomes easy to synthesize while suppressing the generation of aggregates of the fibrous conductive particles, and the average major axis length is 5 ⁇ m. It becomes easy to obtain sufficient heat insulation as it is the above.
  • the average minor axis length (average diameter) and average major axis length of the fibrous conductive particles can be determined by observing a TEM image and an optical microscope image using, for example, a transmission electron microscope (TEM) and an optical microscope. .
  • the average minor axis length (average diameter) and average major axis length of the fibrous conductive particles are randomly selected using a transmission electron microscope (trade name: JEM-2000FX, manufactured by JEOL Ltd.). With respect to the 300 fibrous conductive particles thus obtained, the minor axis length and the major axis length can be measured, respectively, and the average minor axis length and the average major axis length of the fibrous conductive particles can be obtained from the average values thereof.
  • the short-axis length when the short-axis direction cross section of the fibrous conductive particles is not circular is the length of the longest portion measured in the short-axis direction.
  • a circle having the arc as an arc is approximated, and a value calculated from the radius and the curvature is taken as the major axis length.
  • the fibrous conductive particles preferably have an average minor axis length of 150 nm or less and an average major axis length of 5 ⁇ m to 50 ⁇ m from the viewpoint of heat insulation and radio wave transmission.
  • the content of fibrous conductive particles having an average minor axis length (diameter) of 150 nm or less and an average major axis length of 5 ⁇ m or more and 50 ⁇ m or less with respect to the content of all the fibrous conductive particles in the conductive particle-containing layer is metal.
  • the amount is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 75% by mass or more.
  • the average minor axis length is 150 nm or less and the ratio of the fibrous conductive particles having an average major axis length of 5 ⁇ m or more and 50 ⁇ m or less is 50% by mass or more, sufficient conductivity is obtained, and This is preferable because voltage concentration is unlikely to occur and a decrease in durability due to voltage concentration can be suppressed. In a configuration in which non-fibrous conductive particles other than the fibrous conductive particles are not substantially contained in the conductive particle-containing layer, a decrease in transparency can be avoided even when plasmon absorption is strong.
  • the variation coefficient of the average minor axis length (diameter) of the fibrous conductive particles used in the conductive particle-containing layer is preferably 40% or less, more preferably 35% or less, and even more preferably 30% or less.
  • the coefficient of variation of the average minor axis length (diameter) of the fibrous conductive particles is obtained by, for example, measuring the average minor axis length (diameter) of 300 nanowires randomly selected from a transmission electron microscope (TEM) image. It can be obtained by calculating the deviation and the arithmetic average value, and dividing the standard deviation by the arithmetic average value.
  • the aspect ratio of the fibrous conductive particles is preferably 10 or more.
  • the aspect ratio means the ratio of the average major axis length to the average minor axis length (average major axis length / average minor axis length).
  • the aspect ratio can be calculated from the average major axis length and the average minor axis length calculated by the method described above.
  • the aspect ratio of the fibrous conductive particles is not particularly limited as long as it is 10 or more, and can be appropriately selected according to the purpose, but is preferably 10 to 100,000, more preferably 50 to 100,000, and 100 to 100,000 is more preferred.
  • the aspect ratio is 10 or more, a network in which fibrous conductive particles are in contact with each other is easily formed, and a conductive particle-containing layer having high heat insulation can be easily obtained.
  • the aspect ratio is 100,000 or less, for example, in the coating liquid when the conductive particle-containing layer is provided on the support by coating, it is suppressed that the fibrous conductive particles are entangled to form an aggregate, Since a stable coating solution is obtained, the production of the conductive particle-containing layer is facilitated.
  • the content of the fibrous conductive particles having an aspect ratio of 10 or more with respect to the mass of all the fibrous conductive particles contained in the conductive particle-containing layer is not particularly limited. For example, it is preferably 70% by mass or more, more preferably 75% by mass or more, and further preferably 80% by mass or more.
  • the shape of the fibrous conductive particles may be any shape such as a columnar shape, a rectangular parallelepiped shape, or a columnar shape with a polygonal cross section.
  • the columnar shape or the cross section is 5
  • a polygon that is a polygon larger than a square and has a cross-sectional shape that does not have an acute angle is preferable.
  • the cross-sectional shape of the fibrous conductive particles can be detected by applying an aqueous dispersion of the fibrous conductive particles on the support and observing the cross section with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the metal forming the fibrous metal particles is not particularly limited, and any metal may be used. In addition to one metal, two or more metals may be used in combination, or an alloy may be used. Among these, those formed from simple metals or metal compounds are preferable, and those formed from simple metals are more preferable.
  • the metal is preferably at least one metal selected from the group consisting of the fourth period, the fifth period, and the sixth period of the periodic table (IUPAC 1991), and at least one metal selected from Groups 2 to 14 More preferably, at least one metal selected from Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, Group 13, and Group 14 is more preferable. It is particularly preferable to contain a metal as a main component.
  • metals include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, titanium, bismuth, antimony, Examples thereof include lead and alloys containing any of these.
  • copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, or alloys thereof are preferable, and palladium, copper, silver, gold, platinum, tin, or any of these An alloy containing these is more preferable, and silver or an alloy containing silver is particularly preferable.
  • the silver content in the alloy containing silver is preferably 50 mol% or more, more preferably 60 mol% or more, and further preferably 80 mol% or more based on the total amount of the alloy. .
  • the fibrous conductive particles contained in the conductive particle-containing layer are preferably fibrous metal particles, more preferably metal nanowires, and even more preferably silver nanowires.
  • the silver nanowire is preferably a silver nanowire having an average minor axis length of 1 nm to 150 nm and an average major axis length of 1 ⁇ m to 100 ⁇ m, an average minor axis length of 5 nm to 30 nm, and an average major axis length of 5 ⁇ m to A 30 ⁇ m silver nanowire is more preferred.
  • the content of silver nanowires with respect to the mass of all the fibrous conductive particles contained in a conductive particle content layer is not restrict
  • the content of silver nanowires with respect to the mass of all fibrous conductive particles contained in the conductive particle-containing layer is preferably 50% by mass or more, more preferably 80% by mass or more. More preferably, it is substantially a silver nanowire.
  • “substantially” means that metal atoms other than silver inevitably mixed are allowed.
  • the content of the fibrous conductive particles contained in the conductive particle-containing layer is such that the resistivity, total light transmittance, and haze value of the conductive particle-containing layer are in a desired range depending on the type of the fibrous conductive particles. It is preferable to be a small amount.
  • the amount of the fibrous conductive particles with respect to the conductive particle-containing layer is preferably 1% by mass to 35% by mass, more preferably 3% by mass to 30% by mass, and 5% by mass to 25% by mass. Is particularly preferred.
  • the solvent used for the production of the fibrous conductive particles is preferably a hydrophilic solvent, and examples thereof include water, alcohol solvents, ether solvents, ketone solvents, and these may be used alone. Two or more kinds may be used in combination.
  • alcohol solvents include methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, and the like.
  • ether solvent include dioxane and tetrahydrofuran.
  • Examples of the ketone solvent include acetone.
  • the heating temperature is preferably 250 ° C or lower, more preferably 20 ° C or higher and 200 ° C or lower, further preferably 30 ° C or higher and 180 ° C or lower, and 40 ° C or higher and 170 ° C or lower.
  • the following are particularly preferred: By setting the temperature to 20 ° C. or higher, the length of the fibrous conductive particles to be formed is in a preferable range in which dispersion stability can be ensured, and by setting the temperature to 250 ° C.
  • the outer periphery of the cross section of the fibrous conductive particles Since it has a smooth shape with no acute angle, coloring due to surface plasmon absorption of the metal particles is suppressed, which is preferable from the viewpoint of transparency.
  • the temperature may be changed during the formation process of the fibrous conductive particles, and the temperature change during the process improves the monodispersity by controlling nucleation, suppressing renucleation, and promoting selective growth. There may be an effect of.
  • the heat treatment is preferably performed by adding a reducing agent.
  • a reducing agent there is no restriction
  • the reducing agent include borohydride metal salts, aluminum hydride salts, alkanolamines, aliphatic amines, heterocyclic amines, aromatic amines, aralkylamines, alcohols, organic acids, reducing sugars, sugar alcohols, sulfurous acid.
  • Sodium, hydrazine compound, dextrin, hydroquinone, hydroxylamine, ethylene glycol, glutathione and the like can be mentioned.
  • reducing sugars, sugar alcohols as derivatives thereof, or ethylene glycol are particularly preferable.
  • there is a compound that functions as a dispersant or a solvent as a function there is a compound that functions as a dispersant or a solvent as a function, and can be preferably used in the same manner.
  • the production of the fibrous conductive particles is preferably performed by adding a dispersant and a halogen compound or metal halide fine particles.
  • the timing of addition of the dispersant and the halogen compound may be before or after the addition of the reducing agent, and may be before or after the addition of metal ions or metal halide fine particles. From the viewpoint of obtaining higher fibrous conductive particles, the addition of the halogen compound is preferably divided into two or more stages because nucleation and growth can be controlled.
  • the timing for adding the dispersant is not particularly limited. It may be added before preparing the fibrous conductive particles, and the fibrous conductive particles may be added in the presence of a dispersant, or may be added after the preparation of the fibrous conductive particles for controlling the dispersion state.
  • the dispersant include amino group-containing compounds, thiol group-containing compounds, sulfide group-containing compounds, amino acids or derivatives thereof, peptide compounds, polysaccharides, polysaccharide-derived natural polymers, synthetic polymers, or these. Examples thereof include polymer compounds such as gel. Among these, various polymer compounds used as a dispersant are compounds included in the polymer described later.
  • polymer suitably used as the dispersant examples include gelatin, polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, polyalkyleneamine, polyalkyleneamine, partial alkyl ester of polyacrylic acid, polyvinylpyrrolidone, and polyvinylpyrrolidone structure, which are protective colloidal polymers.
  • a polymer having a hydrophilic group such as a polyacrylic acid having an amino group or a thiol group is preferable.
  • the polymer used as the dispersant preferably has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 3,000 to 300,000, more preferably 5,000 to 100,000.
  • the description of “Encyclopedia of Pigments” (edited by Seijiro Ito, published by Asakura Shoin Co., Ltd., 2000) can be referred to.
  • the shape of the obtained fibrous conductive particles can be changed depending on the type of dispersant used.
  • the halogen compound is not particularly limited as long as it is a compound containing at least one atom of bromine, chlorine, and iodine, and can be appropriately selected according to the purpose.
  • sodium bromide, sodium chloride, sodium iodide Further, alkali halides such as potassium iodide, potassium bromide and potassium chloride, or compounds that can be used in combination with the following dispersion additives are preferred.
  • the halogen compound may function as a dispersion additive, it can be preferably used in the same manner.
  • silver halide fine particles may be used, or a halogen compound and silver halide fine particles may be used in combination.
  • a single substance having both the function of a dispersant and the function of a halogen compound may be used. That is, by using a halogen compound having a function as a dispersant, the functions of both the dispersant and the halogen compound are expressed with one compound.
  • the halogen compound having the function of a dispersant include hexadecyl-trimethylammonium bromide (HTAB) containing an amino group and a bromide ion, hexadecyl-trimethylammonium chloride (HTAC) containing an amino group and a chloride ion, an amino group and a bromide.
  • the method for producing metal nanowires it is preferable to perform a desalting treatment after forming the metal nanowires.
  • the desalting treatment after the formation of the metal nanowire can be performed by a technique such as ultrafiltration, dialysis, gel filtration, decantation, or centrifugation.
  • the metal nanowires contain as little inorganic ions as possible, such as alkali metal ions, alkaline earth metal ions, or halide ions.
  • the electrical conductivity of an aqueous dispersion obtained by dispersing fibrous conductive particles in an aqueous solvent is preferably 1 mS / cm or less, more preferably 0.1 mS / cm or less, and even more preferably 0.05 mS / cm or less.
  • the viscosity of the aqueous dispersion of fibrous conductive particles at 25 ° C.
  • the electrical conductivity and viscosity are measured with the concentration of fibrous conductive particles in the aqueous dispersion as 0.45% by mass. When the concentration of the fibrous conductive particles in the aqueous dispersion is higher than the above concentration, the aqueous dispersion is diluted with distilled water and measured.
  • the average thickness of the conductive particle-containing layer is usually selected in the range of 0.005 ⁇ m to 2 ⁇ m. For example, by setting the average thickness to 0.001 ⁇ m to 0.5 ⁇ m, sufficient durability and film strength can be obtained. In particular, if the average thickness is in the range of 0.01 ⁇ m to 0.1 ⁇ m, it is preferable because an allowable range in manufacturing can be secured.
  • One embodiment of the present invention maintains a high heat insulating property and transparency by using a conductive particle-containing layer that satisfies at least one of the following conditions (i) or (ii), and is derived from a sol-gel cured product. In addition, it is preferable that the fibrous conductive particles are stably fixed and can achieve high strength and durability.
  • the thickness of the conductive particle-containing layer is a thin layer of 0.005 ⁇ m to 0.5 ⁇ m. it can.
  • a heat ray reflective material is used suitably for various uses.
  • the thickness may be 0.005 ⁇ m to 0.5 ⁇ m, more preferably 0.007 ⁇ m to 0.3 ⁇ m, even more preferably 0.008 ⁇ m to 0.2 ⁇ m, and 0.01 ⁇ m to 0.1 ⁇ m is particularly preferable.
  • the transparency of a conductive particle content layer can further improve.
  • the average thickness of the conductive particle-containing layer is calculated as an arithmetic average value by measuring the thickness of the conductive particle-containing layer at five points by directly observing the cross section of the conductive particle-containing layer with an electron microscope.
  • the thickness of the conductive particle-containing layer can be determined by, for example, removing the portion where the conductive particle-containing layer is formed and the conductive particle-containing layer using a stylus type surface shape measuring instrument (Dektak (registered trademark) 150, manufactured by Bruker AXS). It can also be measured as a step with respect to the portion.
  • Dektak registered trademark
  • part of the support may be removed, or an error is likely to occur because the formed conductive particle-containing layer is a thin film. Therefore, in the examples described later, the average thickness measured using an electron microscope is described.
  • At least one layer selected from all the layers including the conductive particle-containing layer arranged on the side having the conductive particle-containing layer of the support contains a specific organic binder.
  • the specific organic binder may be included in the conductive particle-containing layer.
  • the specific organic binder may be included in the layer, or may be included in a plurality of layers. Good.
  • the specific organic binder is formed by polymerizing a monomer composition including a bifunctional or lower polymerizable monomer and a trifunctional or higher functional polymerizable monomer.
  • the mass ratio of the bifunctional or lower polymerizable monomer to the trifunctional or higher functional polymerizable monomer in the monomer composition is 10/90 to 90/10.
  • the heat ray reflective material is excellent in durability such as Wet film strength and suppression of cracks.
  • the polymerization method of the monomer composition that forms the specific organic binder is not particularly limited.
  • the specific organic binder may be one in which the monomer composition is polymerized by light or may be polymerized by heat.
  • bifunctional or less polymerizable monomers examples include a monofunctional polymerizable monomer and a bifunctional polymerizable monomer. From the viewpoint of durability, it is preferable to use at least one monofunctional polymerizable monomer and at least one bifunctional polymerizable monomer.
  • the monofunctional polymerizable monomer can be appropriately selected from monomers having one polymerizable group.
  • the polymerizable group means a group that can be polymerized with other monomers by light or heat, and examples thereof include an unsaturated double bond, a hydroxyl group, and an isocyanate group.
  • Examples of the monofunctional polymerizable monomer include (meth) acrylate, acrylamide, vinyl monomer, unsaturated carboxylic acid, and the like.
  • Examples of the monofunctional (meth) acrylate include (meth) acrylate having a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms).
  • a divalent linking group such as an oxyalkylene group may be contained between the hydrocarbon group and the ester group.
  • Examples of the (meth) acrylate having a hydrocarbon group include (meth) acrylate having a chain aliphatic hydrocarbon group and (meth) acrylate having a cyclic aliphatic hydrocarbon group. More specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) ) Acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth
  • Examples of monofunctional acrylamides include N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N, N-isopropyl (meth) acrylamide, N -T-octyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and diacetone acrylamide.
  • Examples of the monofunctional vinyl monomer include N-vinyl pyrrolidone and N-vinyl caprolactam.
  • Examples of the unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid.
  • (meth) acrylate is preferable, and phenoxyethyl (meth) acrylate, n-dodecyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate are more preferable.
  • the bifunctional polymerizable monomer can be appropriately selected from monomers having two polymerizable groups.
  • Examples of the bifunctional polymerizable monomer include (meth) acrylate, diol, diisocyanate, and the like.
  • the bifunctional (meth) acrylate is selected from monomers containing two (meth) acryloyl groups. Specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol Di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide (EO) modified bisphenol A type di (meth) acrylate, propylene oxide (PO) modified bisphenol A type di (meta ) Acrylate, propylene oxide (PO) modified neopentyl glycol diacrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanedio Di (meth) acrylate, 1,6
  • diol examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, and 2,2-dimethyl-1 , 3-propanediol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 3,3-dimethyl-1,2-butanediol, 2-ethyl-2 -Methyl-1,3-propanediol, 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,2 -Diethyl-1,3-propanediol, 2,4-d
  • diisocyanate examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, hexamethylene diisocyanate, diphenylmethane
  • examples include 4,4-diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate, and 1,5-naphthalene diisocyanate.
  • (meth) acrylate is preferable, and dipropylene glycol di (meth) acrylate and propylene oxide (PO) -modified neopentyl glycol diacrylate are more preferable.
  • the trifunctional or higher functional polymerizable monomer can be appropriately selected from monomers having three or more polymerizable groups.
  • Examples of the tri- or higher functional polymerizable monomer include (meth) acrylate, polyol, polyisocyanate, and the like.
  • the trifunctional or higher functional (meth) acrylate is selected from monomers containing three or more (meth) acryloyl groups, for example.
  • polystyrene resin examples include glycerin, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol, and sucrose.
  • prepolymer synthesize combined using the above-mentioned bifunctional or less polymerizable monomer and trifunctional or more polymerizable monomer.
  • the prepolymer examples include the above-mentioned monofunctional (meth) acrylate (for example, hydroxyethyl acrylate), bifunctional (meth) acrylate (for example, dipropylene glycol diacrylate), and trifunctional or higher (meth) acrylate.
  • prepolymer formed by polymerizing for example, trimethylolpropane triacrylate).
  • polyisocyanate examples include triphenylmethane triisocyanate, adducts of the aforementioned diisocyanate and polyol compounds such as trimethylolpropane, burettes and isocyanurates.
  • the monomer composition forming the specific organic binder may contain a crosslinking agent and a photopolymerization initiator as a curing agent.
  • photopolymerization initiator any compound suitable for the properties of the above-described bifunctional or lower polymerizable monomer and trifunctional or higher functional polymerizable monomer can be used.
  • the photopolymerization initiator include acetophenone photopolymerization initiators such as 1-hydroxycyclohexyl phenyl ketone, benzoin photopolymerization initiators such as benzyldimethyl ketal, benzophenone photopolymerization initiators such as benzophenone, and thioxanthone photopolymerization initiators.
  • a polymerization initiator etc. are mentioned.
  • an acetophenone-based photopolymerization initiator is preferable, and 1-hydroxycyclohexyl phenyl ketone (for example, IRGACURE 184 manufactured by BASF Japan) is more preferable.
  • the content of the photopolymerization initiator in the monomer composition is not particularly limited, but is 0.1 mass when the total amount of the above-described bifunctional or lower polymerizable monomer and trifunctional or higher functional monomer is 100 parts by mass. Part to 10 parts by weight, preferably 2 parts to 8 parts by weight.
  • These photopolymerization initiators may be used alone or in combination of two or more. When using 2 or more types of photoinitiators, it is preferable that it is contained in said amount as a total amount of a photoinitiator.
  • crosslinking agent examples include an isocyanate crosslinking agent and an epoxy crosslinking agent.
  • an isocyanate type crosslinking agent the above-mentioned diisocyanate and the above-mentioned polyisocyanate are mentioned, for example.
  • epoxy crosslinking agent examples include bisphenol A / epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, Examples include trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl erythritol, diglycerol polyglycidyl ether, and the like.
  • cross-linking agent commercially available ones may be used.
  • Bernock series manufactured by DIC Corporation
  • Duranate series manufactured by Asahi Kasei Corporation
  • Elastron series Daniichi Kogyo Seiyaku Co., Ltd.
  • Manufactured Takenate series (manufactured by Mitsui Chemicals), 7950 and other blocked isocyanate series (manufactured by Baxenden).
  • the content of the isocyanate-based crosslinking agent or the epoxy-based crosslinking agent in the monomer composition is not particularly limited, but the total amount of the aforementioned bifunctional or lower polymerizable monomer and trifunctional or higher functional monomer is 100 parts by mass. In addition, 0.01 to 3 parts by mass is preferable, 0.01 to 2 parts by mass is more preferable, and 0.1 to 1 part by mass is further preferable. However, when diol or diisocyanate is used as the aforementioned bifunctional or lower polymerizable monomer and polyol or polyisocyanate is used as the aforementioned trifunctional or higher polymerizable monomer, the preferred range of the content is not limited to the above. These crosslinking agents may be used alone or in combination of two or more, but are preferably included in the above amount as the total amount of the crosslinking agent.
  • the specific organic binder may be used in the form of a so-called latex in which a monomer composition containing a bifunctional or lower polymerizable monomer and a trifunctional or higher polymerizable monomer is polymerized and dispersed in water. .
  • latex examples include (meth) acrylic latex, polyester latex, polyurethane latex, rubber latex, polyvinyl chloride latex, polyvinylidene chloride latex, polyolefin latex, nylon latex, polyvinyl acetate latex Etc.
  • acrylic latex examples include Nipol LX855, 857 ⁇ 2 (manufactured by Zeon Corporation); Voncoat R3370 (manufactured by DIC Corporation); Jurimer (registered trademark) ET-410 (manufactured by Nippon Pure Chemical Co., Ltd.) AE116, AE119, AE121, AE125, AE134, AE137, AE140, AE173 (manufactured by JSR Corporation); Aron A-104 (manufactured by Toagosei Co., Ltd.) and the like.
  • polyester latex examples include FINITEX ES650, 611, 675, 850 (above, manufactured by DIC Corporation); WD-size, WMS (above, manufactured by Eastman Chemical Co.); A-110, A-115GE, A -120, A-121, A-124GP, A-124S, A-160P, A-210, A-215GE, A-510, A-513E, A-515GE, A-520, A-610, A-613 A-615GE, A-620, WAC-10, WAC-15, WAC-17XC, WAC-20, S-110, S-110EA, S-111SL, S-120, S-140, S-140A, S -250, S-252G, S-250S, S-320, S-680, DNS-63P, NS-122L, NS-122LX, N -244LX, NS-140L, NS-141LX, NS-282LX (above, manufactured by Takamatsu Yushi Co.,
  • polyurethane latex examples include HYDRAN AP10, AP20, AP30, AP40, 101H, Vonic 1320NS, 1610NS (manufactured by DIC Corporation); D-1000, D-2000, D-6000, D-4000, D -9000 (above, manufactured by Daiichi Seika Kogyo Co., Ltd.); NS-155X, NS-310A, NS-310X, NS-311X (above, manufactured by Takamatsu Yushi Co., Ltd.); Elastron (Daiichi Kogyo Seiyaku Co., Ltd.) Manufactured).
  • Examples of rubber latex include LACSTAR 7310K, 3307B, 4700H, 7132C (manufactured by DIC Corporation), Nipol LX416, LX410, LX430, LX435, LX110, LX415A, LX415M, LX438C, 2507H, LX303A, LX407 V1004, MH5055 (above, manufactured by Nippon Zeon Co., Ltd.) and the like.
  • polyvinyl chloride latex examples include G351 and G576 (manufactured by Nippon Zeon Co., Ltd.); VINYBRAN 240, 270, 277, 375, 386, 609, 550, 601, 602, 630, 660, 671, 683.
  • polyvinylidene chloride latex examples include L502 and L513 (manufactured by Asahi Kasei Corporation); D-5071 (manufactured by DIC Corporation), and the like.
  • polyolefin-based latex examples include Chemipearl (registered trademark) S120, SA100, V300 (above, manufactured by Mitsui Chemicals Co., Ltd.); Voncoat 2830, 2210, 2960 (above, manufactured by DIC Corporation), Zyxen, Sephorjon G ( As mentioned above, Sumitomo Seika Co., Ltd.) and the like can be mentioned.
  • nylon latex examples include Sepoljon PA (manufactured by Sumitomo Seika Co., Ltd.).
  • polyvinyl acetate latex examples include, for example, VINYBRAN 1080, 1082, 1085W, 1108W, 1108S, 1563M, 1566, 1570, 1588C, A22J7-F2, 1128C, 1137, 1138, A20J2, A23J1, A23J1, A23K1, A23P2E, A68J1N , 1086A, 1086, 1086D, 1108S, 1187, 1241LT, 1580N, 1083, 1571, 1572, 1581, 4465, 4466, 4468W, 4468S, 4470, 4485LL, 4495LL, 1023, 1042, 1060, 1060S, 1080M, 1084W, 1084S 1096, 1570K, 1050, 1050S, 3290, 1017AD, 1002, 1006, 1008, 1 07L, 1225,1245L, GV-6170, GV-6181,4468W, 4468S (manufactured by Nissin Chemical
  • examples of the latex other than the above-mentioned latex include polylactic acid ester latex, polycarbonate latex, polyacetal latex, styrene-butadiene-rubber (SBR) latex, and the like.
  • SBR styrene-butadiene-rubber
  • latexes may be used alone or in combination of two or more.
  • (meth) acrylic latex, polyester latex, polyurethane latex, and polyvinyl chloride latex are preferable, (meth) acrylic latex and polyurethane latex are more preferable, and polyurethane latex is further preferable.
  • the conductive particle-containing layer may contain a matrix, in addition to the specific organic binder described above.
  • matrix is a general term for resin components that are fixed in a state where fibrous conductive particles are dispersed and that form a layer.
  • the matrix By including the matrix, the dispersion of the fibrous conductive particles in the conductive particle-containing layer is stably maintained, and even when the conductive particle-containing layer is directly formed on the support surface, the support and the conductive particle-containing layer There is a tendency to ensure strong adhesion.
  • the matrix include a sol-gel cured product and a non-photosensitive resin.
  • the conductive particle-containing layer may contain a sol-gel cured product that also has a function as a matrix.
  • a sol-gel cured product that also has a function as a matrix.
  • an alkoxide compound of an element (b) selected from the group consisting of silicon, titanium, zirconium, and aluminum is included. It preferably contains a sol-gel cured product obtained by hydrolysis and polycondensation.
  • the conductive particle-containing layer is a metal nanowire containing a metal element (a) as a fibrous conductive particle and having an average minor axis length of 150 nm or less, and an element (b) selected from the group consisting of silicon, titanium, zirconium and aluminum More preferably, it contains at least a sol-gel cured product obtained by hydrolysis and polycondensation of the alkoxide compound.
  • the conductive particle-containing layer preferably satisfies at least one of the following conditions (i) or (ii), more preferably satisfies at least the following condition (ii), and satisfies the following conditions (i) and (ii): Is particularly preferred.
  • (I) Ratio of the amount of the element (b) contained in the conductive particle-containing layer and the amount of the metal element (a) contained in the conductive particle-containing layer [(number of moles of the element (b)) / ( The number of moles of the metal element (a))] is in the range of 0.10 / 1 to 22/1.
  • Ratio of the mass of the alkoxide compound used for forming the sol-gel cured product in the conductive particle-containing layer and the mass of the metal nanowire contained in the conductive particle-containing layer [(alkoxide compound content) / (metal nanowire] Content))] is in the range of 0.25 / 1 to 30/1.
  • the ratio of the amount of the alkoxide compound to the amount of the metal nanowire used is 0.25 / 1 to 30 /
  • it can be formed in the range of 1.
  • the mass ratio is 0.25 / 1 or more, the heat insulating property (conceived to be due to the high conductivity of the fibrous conductive particles) and the transparency are excellent, and the wear resistance, heat resistance, moist heat resistance and A conductive particle-containing layer having excellent bending resistance can be obtained.
  • the said mass ratio is 30/1 or less, it can become an electroconductive particle content layer excellent in electroconductivity and bending resistance.
  • the mass ratio is more preferably in the range of 0.5 / 1 to 25/1, still more preferably in the range of 1/1 to 20/1, and particularly preferably in the range of 2/1 to 15/1.
  • the obtained conductive particle-containing layer has high heat insulation and high transparency (visible light transmittance and haze), and has high wear resistance, heat resistance, and heat and humidity resistance. It will be excellent and bend-resistant, and a heat ray reflective material having suitable physical properties can be obtained stably.
  • the ratio of the amount of the element (b) to the amount of the metal element (a) [(number of moles of the element (b)) / (of the metal element (a) The number of moles)] is in the range of 0.10 / 1 to 22/1.
  • the molar ratio is more preferably in the range of 0.20 / 1 to 18/1, further preferably 0.45 / 1 to 15/1, still more preferably 0.90 / 1 to 11/1, and particularly preferably.
  • the range is 1.5 / 1 to 10/1.
  • the conductive particle-containing layer has both heat insulation and transparency, and from the viewpoint of physical properties, it has excellent wear resistance, heat resistance, and moist heat resistance, and bend resistance. It can be excellent in properties.
  • the alkoxide compound that can be used in the formation of the conductive particle-containing layer is exhausted by hydrolysis and polycondensation, and there is substantially no alkoxide compound in the conductive particle-containing layer.
  • the element (b) component selected from the group consisting of silicon, titanium, zirconia and aluminum derived from the alkoxide compound in the conductive particle-containing layer and the metal element (a) component derived from the metal nanowire can be analyzed by the following method. That is, by subjecting the conductive particle-containing layer to X-ray photoelectron analysis (ESCA), the substance amount ratio, that is, (element (b) component mole number) / (metal element (a) component mole).
  • the obtained value does not always indicate the molar ratio of the element component. It is possible to create a calibration curve using a conductive particle-containing layer with a known molar ratio, and to calculate the actual mass ratio of the conductive particle-containing layer from the calibration curve. The ratio uses the value calculated by the above method.
  • the heat ray reflective material has high heat insulation and high transparency, and has an effect of being excellent in wear resistance, heat resistance and moist heat resistance and excellent in bending resistance.
  • the conductive particle-containing layer contains a metal nanowire and a matrix that is a sol-gel cured product obtained by hydrolysis and polycondensation of an alkoxide compound. That is, the ratio of the matrix contained in the conductive particle-containing layer is smaller than in the case of the conductive particle-containing layer containing a general organic polymer resin (for example, (meth) acrylic resin, vinyl polymerization resin, etc.) as a matrix.
  • a general organic polymer resin for example, (meth) acrylic resin, vinyl polymerization resin, etc.
  • the molar ratio of the alkoxide compound-derived element (b) / metal nanowire-derived metal element (a) is in the range of 0.10 / 1 to 22/1, and 0.10 / 1 to 22 In relation to the fact that the mass ratio of alkoxide compound / metal nanowire is in the range of 0.25 / 1 to 30/1, the above-mentioned action is achieved. It is presumed that the effect of the increase in the balance and the excellent heat resistance, heat resistance, moist heat resistance and bending resistance is maintained while maintaining the heat insulation and transparency.
  • the non-photosensitive resin includes a polymer.
  • the polymer include polyacrylic acid such as polymethacrylic acid, polymethacrylate (eg, poly (methyl methacrylate)), polyacrylate, and polyacrylonitrile, polyvinyl alcohol, polyester (eg, polyethylene terephthalate (PET), polyester) Naphthalate and polycarbonate), phenol or cresol-formaldehyde (Novolacs®), polystyrene, polyvinyltoluene, polyvinylxylene, polyimide, polyamide, polyamideimide, polyetherimide, polysulfide, polysulfone, polyphenylene, polyphenyl ether, etc.
  • polyacrylic acid such as polymethacrylic acid, polymethacrylate (eg, poly (methyl methacrylate)), polyacrylate, and polyacrylonitrile
  • polyvinyl alcohol polyester (eg, polyethylene terephthalate (PET), polyester) Naphthalate and polycarbonate
  • the conductive particle-containing layer may contain an additive such as a dispersant, a solvent, a metal antioxidant, or other conductive material, if necessary.
  • Dispersant- A dispersing agent is used in order to disperse
  • the dispersant is not particularly limited as long as the fibrous conductive particles can be dispersed, and can be appropriately selected according to the purpose.
  • a commercially available dispersant can be used as the pigment dispersant, and a polymer dispersant having a property of adsorbing to the fibrous conductive particles is particularly preferable.
  • polymer dispersants examples include polyvinylpyrrolidone, BYK (registered trademark) series (manufactured by Big Chemie), Solsperse (registered trademark) series (manufactured by Nippon Lubrizol Co., Ltd.), and Ajisper (registered trademark) series. (Made by Ajinomoto Co., Inc.).
  • the content of the dispersant in the conductive particle-containing layer is preferably 0.1 to 50 parts by weight, and preferably 0.5 to 40 parts by weight with respect to 100 parts by weight of the total solid content of the conductive particle-containing layer. An amount of 1 part by weight to 30 parts by weight is particularly preferred.
  • the coating step Is preferable because a stable liquid film is formed and the occurrence of coating unevenness is suppressed.
  • the solvent is a component used to form a composition (coating liquid) for forming a film on the surface of the support using the composition containing the fibrous conductive particles described above, and is appropriately selected depending on the purpose. You can choose.
  • the solvent include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl lactate, 3-methoxybutanol, water, 1-methoxy-2-propanol, isopropyl
  • examples include acetate, methyl lactate, N-methylpyrrolidone (NMP), ⁇ -butyrolactone (GBL), and propylene carbonate.
  • This solvent may also serve as at least a part of the solvent of the dispersion liquid of the above-mentioned fibrous conductive particles. These may be used alone or in combination of two or more.
  • the solid content concentration of the coating solution containing such a solvent is preferably in the range of 0.1% by mass to 20% by mass.
  • the conductive particle-containing layer preferably contains a metal corrosion inhibitor for fibrous conductive particles.
  • a metal corrosion inhibitor for fibrous conductive particles.
  • a metal corrosion inhibitor for fibrous conductive particles.
  • thiols and azoles are suitable.
  • the metal corrosion inhibitor can be applied to the composition for forming a conductive particle-containing layer by adding it in a state dissolved in a suitable solvent or as a powder.
  • the content in the conductive particle-containing layer is preferably 0.5% by mass to 10% by mass with respect to the content of the fibrous conductive particles.
  • the other matrix it is possible to use, as at least a part of the components constituting the matrix, a polymer compound as a dispersant used in the production of the above-described fibrous conductive particles.
  • the conductive particle-containing layer in addition to the fibrous conductive particles, other conductive materials such as conductive fine particles that are not fibrous may be used in combination as long as the effects of the embodiment of the present invention are not impaired.
  • the content ratio of the fibrous conductive particles preferably, the metal nanowire having an aspect ratio of 10 or more
  • the content ratio of the fibrous conductive particles is 50% or more on a volume basis with respect to the total amount of the conductive material including the fibrous conductive particles.
  • 60% or more is more preferable, and 75% or more is particularly preferable.
  • the conductive particles having a shape other than the fibrous conductive particles may not significantly contribute to the conductivity in the conductive particle-containing layer and may have absorption in the visible light region.
  • the conductive particles are a metal and the shape is not strong in plasmon absorption such as a sphere.
  • the ratio of the fibrous conductive particles can be obtained as follows.
  • the fibrous conductive particles are silver nanowires and the conductive particles are silver particles
  • the silver nanowire aqueous dispersion is filtered to separate the silver nanowires from the other conductive particles and induce Using a coupled plasma (ICP) emission spectrometer, the amount of silver remaining on the filter paper and the amount of silver that has passed through the filter paper can be measured to calculate the ratio of the fibrous conductive particles.
  • the aspect ratio of the fibrous conductive particles is determined by observing the fibrous conductive particles such as the fibrous conductive particles remaining on the filter paper with a TEM and measuring the short axis length and the long axis length of 300 fibrous conductive particles, respectively. Is calculated by The method for measuring the average minor axis length and the average major axis length of the fibrous conductive particles is as described above.
  • the method for forming the conductive particle-containing layer is not particularly limited. At the time of forming the layer of the conductive particle-containing layer, a method of forming the layer by reducing the amount of the fibrous conductive particles as compared with the total solid content is preferable.
  • the method for forming the conductive particle-containing layer on the support includes preparing a dispersion containing the above-mentioned fibrous conductive particles, and further including a monomer composition that forms the above-mentioned specific organic binder. It is preferable to prepare a solution, prepare a coating solution in which both are mixed, and apply the coating solution on a support to form a coating film.
  • the method for applying the above-mentioned coating solution on the support can be performed by a general coating method and can be appropriately selected according to the purpose.
  • a general coating method examples thereof include a roll coating method, a bar coating method, a dip coating method, a spin coating method, a casting method, a die coating method, a blade coating method, a gravure coating method, a curtain coating method, a spray coating method, and a doctor coating method.
  • the monomer composition is polymerized.
  • the polymerization of the monomer composition may be performed by light or may be performed by heat.
  • Polymerization by light can be performed by irradiating the coating film with light using a light source such as a metal halide lamp.
  • polymerization by heat can be performed by heating the coating film.
  • the composition for forming a conductive particle-containing layer may contain an organic solvent as necessary. By containing the organic solvent, a more uniform liquid film can be formed on the support.
  • the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol, chloroform, and methylene chloride.
  • Chlorine solvents aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, and ethylene glycol monomethyl ether and ethylene glycol dimethyl ether And glycol ether solvents such as
  • the organic solvent is preferably in a range of 50% by mass or less, more preferably in a range of 30% by mass or less, based on the total mass of the composition.
  • the heat ray reflective material may be provided as a top layer by further providing a protective layer on the side opposite to the support of the conductive particle-containing layer (that is, the position farthest from the support).
  • the protective layer may contain a specific organic binder.
  • a protective layer contains a specific organic binder.
  • the heat ray reflective material is excellent in durability such as Wet film strength and suppression of cracking.
  • the specific organic binder that can be contained in the protective layer is the same as the specific binder that can be contained in the conductive particle-containing layer described above, and the preferred embodiment is also the same.
  • the protective layer may be formed by preparing an aqueous composition and applying it to the surface of the conductive particle-containing layer.
  • the preparation procedure of the aqueous composition for forming the protective layer is not particularly limited.
  • coating of the aqueous composition for protective layer formation can be performed by a well-known method. For example, a coating method using a spin coater, roll coater, bar coater, curtain coater or the like can be used.
  • a protective layer contains said specific organic binder, superposition
  • the method for polymerizing the monomer composition is as described above.
  • the heat ray reflective material has a support.
  • a support body A well-known support body can be used.
  • an optically transparent support is preferable, and examples thereof include those having a visible light transmittance of 70% or more, preferably 80% or more, and those having a high transmittance in the near infrared region.
  • the support is not particularly limited in its shape, structure, size, and material, and can be appropriately selected according to the purpose.
  • Examples of the shape of the support include a flat plate shape.
  • the structure of the support may be a single layer structure or a laminated structure.
  • the size of the support can be appropriately selected according to the size of the heat ray reflective material.
  • the support material include polyolefin resins such as polyethylene, polypropylene, poly-4-methylpentene-1 and polybutene-1; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate resins and polyvinyl chloride Resin, Polyphenylene sulfide resin, Polyethersulfone resin, Polyethylene sulfide resin, Polyphenylene ether resin, Styrene resin, Acrylic resin, Polyamide resin, Polyimide resin, Cellulose resin such as cellulose acetate Or these laminated
  • multilayer films are mentioned.
  • a polyethylene terephthalate film is particularly preferable.
  • the thickness of the support is usually about 10 ⁇ m to 500 ⁇ m, but is preferably thinner from the viewpoint of thinning.
  • the thickness of the support is preferably 10 ⁇ m to 100 ⁇ m, more preferably 20 ⁇ m to 75 ⁇ m, and particularly preferably 35 ⁇ m to 75 ⁇ m. If the thickness of the support is sufficiently thick, adhesion failure tends to be difficult to occur. Moreover, when the thickness of the support is sufficiently thin, the rigidity as a material is not too high when it is bonded to a building material or an automobile as a heat ray reflective material, and the construction tends to be easy. Furthermore, when the support is sufficiently thin, the visible light transmittance is increased, and the raw material cost tends to be suppressed.
  • the form of the heat ray reflective material of one embodiment of the present invention is not particularly limited as long as it has at least the above-mentioned support and the above-mentioned conductive particle-containing layer.
  • the aspect which is a film from a viewpoint of transparency and productivity to a heat ray reflective material is preferable. That is, the heat ray reflective material of one embodiment of the present invention is preferably a heat ray reflective film.
  • the conductive particle-containing layer 1 and the support 2 are laminated in this order (heat ray reflective material). 10).
  • the protective layer 3 As an example of the layer configuration of the heat ray reflective material according to the embodiment of the present invention, as shown in FIG. 2, the protective layer 3, the conductive particle-containing layer 1, and the support 2 are laminated in this order. A mode (heat ray reflective material 10) is mentioned.
  • the conductive particle-containing layer is preferably the uppermost layer disposed at the position farthest from the support or the layer adjacent to the uppermost layer on the support side. From the same viewpoint as described above, the conductive particle-containing layer is more preferably the uppermost layer disposed at the position farthest from the support.
  • a heat ray reflective material can be manufactured by forming the above-mentioned electroconductive particle content layer on the above-mentioned support.
  • the method for forming the conductive particle-containing layer is as described above.
  • a heat ray reflective material has a protective layer, you may form on the surface of an electroconductive particle content layer.
  • the heat ray reflective material may be manufactured in a roll shape or a sheet shape. After forming the conductive particle-containing layer, the conductive particle-containing layer may be wound into a roll shape or cut into a sheet shape.
  • the window of one Embodiment of this invention is equipped with the above-mentioned heat ray reflective material, an adhesive layer, and a transparent base material.
  • the heat ray reflective material is disposed on the indoor side of the transparent substrate.
  • the heat ray reflective material in the window is preferably arranged with the side having the support facing the pressure-sensitive adhesive layer.
  • the transparent substrate is preferably 0.5 mm or more in thickness, more preferably 1 mm or more, and 2 mm or more in thickness from the viewpoint of suppressing heat conduction due to the thickness of the transparent substrate and increasing warmth.
  • the transparent substrate is particularly preferable.
  • a transparent substrate is generally used in the form of a plate.
  • transparent glass such as white plate glass, blue plate glass, silica coated blue plate glass; synthesis of polycarbonate, polyethersulfone, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamideimide, polyimide, etc. Resins; metals such as aluminum, copper, nickel, and stainless steel; ceramics, silicon wafers used for semiconductor substrates, and the like.
  • a transparent base material is glass or a resin board, and it is more preferable that it is glass.
  • a component which comprises glass For example, transparent glass, such as white plate glass, blue plate glass, a silica coat blue plate glass, can be used as glass.
  • transparent glass such as white plate glass, blue plate glass, a silica coat blue plate glass, can be used as glass.
  • the surface of a transparent base material is smooth, and it is especially preferable that it is float glass.
  • the visible light transmittance it is preferable to measure the heat ray reflective material of the present invention by bonding it to 3 mm blue glass. About 3 mm blue plate glass, it is preferable to use the glass described in JIS A5759: 2008.
  • the visible light transmittance of the heat ray reflective material according to JIS A5759: 2008 is preferably 70% or more.
  • the window has an adhesive layer.
  • the pressure-sensitive adhesive layer in the window is preferably disposed in contact with the support of the heat ray reflective material described above.
  • the pressure-sensitive adhesive layer made of these materials can be formed by coating. Furthermore, you may add an antistatic agent, a lubricant, an antiblocking agent, etc. to an adhesive layer.
  • the thickness of the pressure-sensitive adhesive layer is preferably 0.1 ⁇ m to 30 ⁇ m.
  • the adhesive layer a commercially available double-sided tape may be used.
  • An example of the double-sided tape is Panaclean PD-S1 (manufactured by Panac Co., Ltd.).
  • a heat ray reflective material is affixed on the indoor side of the transparent base material in a window glass from a viewpoint of the efficiency of heat insulation.
  • the conductive particle-containing layer is preferably the uppermost layer on the indoor side.
  • the heat ray reflective material further has a layer on the indoor side of the conductive particle containing layer, and the layer is the uppermost layer, the thickness of the uppermost layer (when the uppermost layer is formed by laminating a plurality of layers) , The total thickness) is 5 ⁇ m or less, preferably from the viewpoint of enhancing the heat insulation, more preferably 4 ⁇ m or less, and even more preferably 3 ⁇ m or less.
  • an adhesive layer is coated on the support of the heat ray reflective material or an adhesive layer is provided by lamination, and the interface between the transparent substrate surface and the adhesive layer surface is previously provided.
  • an aqueous solution containing an activator mainly anionic
  • a heat ray reflective material is placed on the transparent substrate via the adhesive layer.
  • the adhesive force of the adhesive layer is low, and the position of the heat ray reflective material of the present invention can be adjusted on the surface of the transparent substrate.
  • the heat ray reflective material is attached to the transparent substrate, the surface of the transparent substrate is swept away from the glass center toward the edge using the squeegee.
  • a heat ray reflective material can be fixed to the surface.
  • an aqueous dispersion containing silver nanowires was prepared as follows. 410 mL of pure water was placed in a three-necked flask, and 82.5 mL of additive solution H and 206 mL of additive solution G were added using a funnel while stirring at 20 ° C. To this solution, 206 mL of additive solution A was added at a flow rate of 2.0 mL / min and at a stirring speed of 800 rpm. Ten minutes later, 82.5 mL of additive solution H was added. Thereafter, the internal temperature was raised to 73 ° C. at 3 ° C./min.
  • the stirring rotation speed was reduced to 200 rpm and heated for 4 hours to obtain an aqueous dispersion in which silver nanowires 1 were dispersed.
  • the resulting aqueous dispersion was cooled.
  • an ultrafiltration module SIP1013 (trade name, manufactured by Asahi Kasei Co., Ltd., molecular weight cut off: 6,000), a magnet pump, and a stainless steel cup were connected with a silicone tube to prepare an ultrafiltration device.
  • the aqueous dispersion after cooling was put into a stainless cup of an ultrafiltration device, and ultrafiltration was performed by driving a pump.
  • the filtrate from the ultrafiltration module reached 50 mL, 950 mL of distilled water was added to the stainless steel cup to wash the filtrate.
  • the expression “silver nanowire aqueous dispersion 1” indicates an aqueous dispersion of silver nanowires obtained by the above method.
  • the aqueous dispersion was centrifuged to remove the supernatant water, and then propylene glycol monomethyl ether was added so that the silver nanowire content was 0.84% by mass, whereby the silver nanowire solvent dispersion 1 was added.
  • the silver nanowire solvent dispersion 1 was added.
  • ⁇ Measurement method of coefficient of variation of minor axis length of metal nanowires The short axis length (diameter) of 300 silver nanowires randomly selected from the transmission electron microscope (TEM) image is measured, and the standard deviation and the arithmetic average value are calculated for the short axis length of 300 silver nanowires. It was obtained by dividing the standard deviation by the arithmetic mean value.
  • Example 1 ⁇ Production of heat ray reflective material> -Preparation of monomer composition 1- Each component is mixed so that it may become the following composition, it stirs for 60 minutes, and the solution-like monomer composition 1 whose mass ratio of the polymerizable monomer more than trifunctional with respect to the polymerizable monomer less than bifunctional is 50/50 is obtained. Prepared.
  • conductive particle containing layer- 20 parts of the obtained monomer composition 1 and 119 parts of the silver nanowire solvent dispersion liquid 1 were mixed to obtain a coating liquid for forming a conductive particle-containing layer.
  • the surface of the support (polyethylene terephthalate (PET) substrate, A4300 manufactured by Toyobo Co., Ltd.) is subjected to corona discharge treatment, and the amount of silver nanowires is 0.040 g / m 2 by a bar coating method on the corona-treated surface.
  • the coating solution was applied so that Then, after drying at 120 ° C.
  • Example 1 the heat ray reflective material of Example 1 was produced.
  • Example 2 to Example 5 Example 16 to Example 20, Comparative Example 3 and Comparative Example 4
  • Example 1 except that the monomer composition 1 used in Example 1 was changed to the following monomer composition 2 to monomer composition 10 and comparative composition 2 to comparative composition 3 as shown in Tables 1 and 2.
  • the heat ray reflective material of each Example and the comparative example was produced.
  • the bifunctional or lower polymerizable monomer and trifunctional or higher polymerizable monomer in the solution are changed to the polymerizable monomers shown in Table 1. It was produced in the same manner as the monomer composition 1 except that.
  • the monomer composition 2 to the monomer composition 10 are polymerized to form the organic binder 2 to the organic binder 10, respectively, and the comparative example composition 2 to the comparative composition 3 are polymerized to compare the comparative binder 2 to the comparative binder 3. Is formed.
  • Comparative Example 1 (polyvinyl alcohol solution having a solid content of 1% by mass) shown in Table 1 below, 1 part of silver nanowire aqueous dispersion 1 and 10 parts of water were mixed to obtain a coating solution. The obtained coating solution was applied to the surface of the PET substrate with a bar coater and dried at 120 ° C. for 1 minute to form a conductive particle-containing layer. Thus, the heat ray reflective material of Comparative Example 1 was produced.
  • Comparative Example 2 On the conductive particle-containing layer of the heat ray reflective material of Comparative Example 1, Comparative Composition 1 was further applied using a bar coater and dried at 120 ° C. for 2 minutes to form a protective layer. Thus, the heat ray reflective material of Comparative Example 2 was produced.
  • Example 6 In Example 1, the monomer composition 1 is changed to the monomer composition A shown below, and a conductive particle-containing layer is formed on a polyethylene terephthalate (PET) substrate in the same manner as in Example 1, and further contains conductive particles.
  • a heat ray reflective material was produced in the same manner as in Example 1, except that the monomer composition 1 was applied on the layer to form a protective layer.
  • the protective layer was formed by drying the monomer composition 1 at 120 ° C. for 2 minutes, and irradiating a metal halide lamp (manufactured by Mario Network, Handy 250) for 5 minutes in a nitrogen-substituted atmosphere. The procedure of polymerizing composition 1 to form organic binder 1 was performed.
  • the mass ratio of the fibrous conductive particles to the organic binder in the heat ray reflective material of Example 6 was 1/10.
  • the monomer composition A does not contain a polymerization initiator, the polymerization reaction does not proceed and an organic binder is not formed. That is, the amount of organic binder is the amount of organic binder in the protective layer.
  • Examples 7 to 11, Comparative Example 5 The same as Example 1 except that the monomer composition 1 and the silver nanowire solvent dispersion liquid 1 used in Example 1 were prepared and used so as to have a mass ratio of fibrous conductive particles / organic binder shown in Table 2 below. Thus, the heat ray reflective materials of the respective examples and comparative examples were produced.
  • Example 12 to Example 15 The heat ray reflective materials of the respective examples and comparative examples were produced in the same manner as in Example 1 except that the coating amount of the silver nanowires in Example 1 was changed to the amount shown in Table 2 below.
  • Example 21 A heat ray reflective material was produced in the same manner as in Example 1 except that the silver nanowire solvent dispersion 1 in Example 1 was changed to the silver nanowire solvent dispersion 2 described above.
  • Example 22 Preparation of composition for polyol synthesis- Each component was stirred for 60 minutes so that it might become the following composition, and after preparing the composition for a polyol synthesis
  • composition of composition for polyol synthesis Dipropylene glycol diacrylate (DPGDA) 7.0 parts (bifunctional polymerizable monomer) ⁇ Hydroxyethyl acrylate (HEA): 3.0 parts (monofunctional polymerizable monomer) Trimethylolpropane triacrylate (TMPTA) 2.0 parts (trifunctional polymerizable monomer) ⁇ Polymerization initiator: 0.2 parts (IRGACURE184, manufactured by BASF) ⁇ Propylene glycol monomethyl ether: 12 parts (solvent)
  • monomer composition 11 solution 15 parts of the above polyol solution (trifunctional or higher functional polymerizable monomer, solid content 49.6% by mass) and 2.5 parts of tolylene diisocyanate (bifunctional or lower polymerizable monomer) are stirred for 60 minutes, A monomer composition 11 solution having a mass ratio of a bifunctional or higher polymerizable monomer to a trifunctional or lower polymerizable monomer of 25/75 was prepared.
  • ⁇ Formation of conductive particle-containing layer 17.5 parts of the obtained monomer composition 11 solution and 119 parts of the silver nanowire solvent dispersion 1 were mixed to obtain a coating liquid for forming a conductive particle-containing layer.
  • the surface of the support (PET substrate, A4300 manufactured by Toyobo Co., Ltd.) is subjected to corona discharge treatment, and the surface of the corona treatment is subjected to bar coating so that the amount of silver nanowires is 0.040 g / m 2.
  • a coating solution was applied. Then, it dried at 120 degreeC for 2 minute (s), and formed the electrically conductive particle content layer.
  • the mass ratio of silver nanowire / organic binder in the conductive particle-containing layer was 1/10. In this way, a heat ray reflective material was obtained.
  • Visible light transmittance (%) was measured in accordance with JIS A 5759: 2008 for the heat ray reflective materials of the examples and comparative examples.
  • the visible light transmittance was measured using an ultraviolet-visible near-infrared spectrometer (manufactured by JASCO Corporation, V-670, using integrating sphere unit ISN-723).
  • a sample for measurement was a Panaclean PD-S1 manufactured by Panac Co., Ltd., using a float plate glass specified in JIS R 3202: 2011 and the surface on the support side of the heat ray reflective material of each example and comparative example as an adhesive. (Adhesive layer 25 ⁇ m) was used for bonding.
  • the heat transmissivity (W / m 2 ⁇ K) was calculated in accordance with JIS A 5759: 2008 for the heat ray reflective materials of each Example and Comparative Example.
  • the heat transmissivity was calculated by measuring the reflectivity of a heat ray reflective material at a wavelength of 5 ⁇ m to 50 ⁇ m using an infrared spectrometer (manufactured by Bruker Optics, IFS 66v / S). The sample for measurement was produced by the same method as the measurement of the visible light transmittance.
  • the heat ray reflective materials of the examples are all good in heat insulation, wet film strength, and cracking evaluation results. This shows that the heat ray reflective material of an Example is excellent in heat insulation and durability.
  • ⁇ Preparation of window with heat ray reflective material> Using the heat ray reflective material of Example 1 to Example 22, it was attached to the surface of the window glass attached to the window of the building by the following procedure to produce a window provided with the heat ray reflective material.
  • a pressure-sensitive adhesive layer was formed by bonding a pressure-sensitive adhesive to the surface of the heat ray reflective material of Examples 1 to 22 on the support side.
  • the PANACL PD-S1 manufactured by Panac Co., Ltd. (adhesive layer thickness of 25 ⁇ m, light release separator on one side of the adhesive layer and heavy release separator on the other side) was used as the pressure sensitive adhesive. Silicone-coated PET) was peeled off and bonded to the support surface.
  • the heavy release separator of the pressure-sensitive adhesive layer was peeled off.
  • a 0.1% by mass aqueous solution of a surfactant polyoxyethylene lauryl ether sodium sulfate
  • a surfactant polyoxyethylene lauryl ether sodium sulfate
  • the glass surface was moved to adjust the position of the heat ray reflective material.
  • the surface of the heat ray reflective material is rubbed with a squeegee and the moisture remaining between the window glass and the heat ray reflective material is directed from the glass center toward the edge. Sweeped out and fixed a heat ray reflective material on the window glass surface.
  • the window provided with the heat ray reflective material was produced.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Laminated Bodies (AREA)
  • Special Wing (AREA)
  • Optical Filters (AREA)

Abstract

L'invention concerne un matériau de réflexion de rayon de chaleur et une fenêtre, le matériau de réflexion de rayon de chaleur ayant un support et une couche contenant des particules électroconductrices comprenant des particules électroconductrices fibreuses, la résistance superficielle de la surface de la couche contenant des particules électroconductrices sur le côté inverse de cette dernière depuis le côté sur lequel se trouve le support étant 1000 Ω/carré ou plus, et au moins une couche disposée sur le côté du support ayant la couche contenant des particules électroconductrices et sélectionnée parmi toutes les couches y compris la couche contenant des particules électroconductrices comprenant un liant organique qui est un polymère d'une composition de monomère comprenant un monomère polymérisable bifonctionnel au maximum et un monomère polymérisable trifonctionnel ou plus, le rapport de masse du monomère polymérisable trifonctionnel ou plus et du monomère polymérisable bifonctionnel au maximum étant de 10/90 à 90/10.
PCT/JP2016/071932 2015-07-31 2016-07-26 Matériau de réflexion de rayon de chaleur et fenêtre WO2017022579A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010131525A (ja) * 2008-12-04 2010-06-17 Toyota Central R&D Labs Inc ポリマーで固定化されたコロイド結晶及びその製造方法
JP2012208169A (ja) * 2011-03-29 2012-10-25 Konica Minolta Holdings Inc ハードコートフィルムと、それを用いた熱線遮断フィルム及び有機素子デバイス
JP2012252172A (ja) * 2011-06-03 2012-12-20 Bridgestone Corp 熱線遮蔽フィルム、これを用いた熱線遮蔽ウィンドウ
US20140302326A1 (en) * 2011-12-21 2014-10-09 Dong Myeong SHIN Conductive film composition, conductive film fabricated using the same, and optical display apparatus including the same
JP2014224921A (ja) * 2013-05-16 2014-12-04 日本化薬株式会社 赤外線遮蔽シート及びその製造方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005275225A (ja) * 2004-03-26 2005-10-06 Konica Minolta Opto Inc 反射防止フィルム、偏光板及び画像表示装置
WO2006082944A1 (fr) * 2005-02-07 2006-08-10 Teijin Dupont Films Japan Limited Film multicouche conducteur
US20150177433A1 (en) * 2012-07-13 2015-06-25 Konica Minolta, Inc. Infrared shielding film

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010131525A (ja) * 2008-12-04 2010-06-17 Toyota Central R&D Labs Inc ポリマーで固定化されたコロイド結晶及びその製造方法
JP2012208169A (ja) * 2011-03-29 2012-10-25 Konica Minolta Holdings Inc ハードコートフィルムと、それを用いた熱線遮断フィルム及び有機素子デバイス
JP2012252172A (ja) * 2011-06-03 2012-12-20 Bridgestone Corp 熱線遮蔽フィルム、これを用いた熱線遮蔽ウィンドウ
US20140302326A1 (en) * 2011-12-21 2014-10-09 Dong Myeong SHIN Conductive film composition, conductive film fabricated using the same, and optical display apparatus including the same
JP2014224921A (ja) * 2013-05-16 2014-12-04 日本化薬株式会社 赤外線遮蔽シート及びその製造方法

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