WO2016121933A1 - Insulatingfilm, insulating glass and window - Google Patents

Insulatingfilm, insulating glass and window Download PDF

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Publication number
WO2016121933A1
WO2016121933A1 PCT/JP2016/052673 JP2016052673W WO2016121933A1 WO 2016121933 A1 WO2016121933 A1 WO 2016121933A1 JP 2016052673 W JP2016052673 W JP 2016052673W WO 2016121933 A1 WO2016121933 A1 WO 2016121933A1
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WO
WIPO (PCT)
Prior art keywords
heat insulating
layer
fibrous metal
insulating film
metal particle
Prior art date
Application number
PCT/JP2016/052673
Other languages
French (fr)
Japanese (ja)
Inventor
長谷川　和弘
清都　尚治
Original Assignee
富士フイルム株式会社
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Filing date
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Publication of WO2016121933A1 publication Critical patent/WO2016121933A1/en

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Classifications

    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • 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

  • the present invention relates to a heat insulating film, a heat insulating glass, and a window. More specifically, in the case of using a fibrous metal particle-containing layer containing a fibrous metal particle and a binder containing silver as a main component, a heat insulating film capable of suppressing a change in heat insulation after wet heat aging, heat insulation using this heat insulating film
  • the present invention relates to glass and a window using this heat insulating film.
  • the heat insulating film is a film that delays the heat transfer between the indoor side and the outdoor side by sticking it on a window or the like. By using this film, the amount of air-conditioning used can be reduced, and a power saving effect can be expected. Thermal insulation is defined by the thermal conductivity. According to the solar radiation adjustment film procurement standards for windows in the law on the promotion of the procurement of environmental goods, etc.
  • JIS Joint Industrial Standards
  • a 5759 “Film for architectural window glass”
  • the measurement method requires that the heat transmissivity is less than 5.9 W / (m 2 ⁇ K), and the smaller this number, the higher the heat insulation.
  • the thermal transmissivity can be obtained 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.
  • Patent Document 1 discloses a laminated heat ray reflective film in which a protective layer is formed on the outermost layer of at least one surface of the heat ray reflective film, and the contact angle between the protective layer and water is 90 ° or more, and the protective layer is configured.
  • the laminated heat ray reflective film whose glass transition temperature of resin to perform is 100 degreeC or more and is transparent is disclosed.
  • the laminated heat ray reflective film of the present invention has (b) a metal layer, (c) a metal oxide layer, and (d) a protective layer on at least one surface of the base film. It is a laminated film provided with ".
  • a heat ray reflective layer composed of a resin layer containing aluminum powder and an ultraviolet absorber is provided on at least one surface of a transparent glass substrate, and photocatalyst particles and silicone or amorphous silica and repellent material are disposed on one surface of the glass substrate.
  • a glass plate having a substantially transparent surface layer containing an aqueous fluororesin, the surface layer having a contact angle with water of 90 ° or more and water droplet adhesion prevention and heat ray blocking properties. Yes.
  • the infrared shielding layer includes (A) an ionizing radiation curable resin, (B) an infrared absorber, An antifouling infrared shielding film comprising a cured product of a coating film containing (C) 0.1 to 50 parts by mass of (C) ionizing radiation curable silicone resin per 100 parts by mass of ionizing radiation curable resin is disclosed.
  • Patent Document 4 describes a heat ray shielding film including a transparent film and a far infrared reflective layer provided on the surface thereof, and the far infrared reflective layer includes a fibrous metal particle. Yes. According to Patent Document 4, since the far-infrared reflective layer of the heat ray shielding film contains fibrous metal particles, the heat rays such as heating that are radiated from the inside are not reflected and escaped, and the heat of the outside air is not taken indoors. It is described as being excellent in heat insulation.
  • the heat insulating film used by being attached to the inside of the window glass reflects far infrared rays from the room to prevent heat from escaping through the window glass.
  • the fibrous metal particles mainly containing silver and the binder described in Patent Document 4 are used.
  • a fibrous metal particle-containing layer that contains problems such as the occurrence of condensation on the surface of the heat insulating film arise, water becomes a good absorber of far infrared rays, and heat is released by heat conduction, so the heat insulating film It was found that the performance of can not be demonstrated.
  • Patent Documents 1 to 3 do not describe the use of fibrous metal particles mainly composed of silver in the infrared reflecting layer.
  • the change in heat insulating property when aged in a humid heat environment is not so large. Therefore, when the fibrous metal particle-containing layer containing a fibrous metal particle mainly containing silver and a binder is used, the problem that the heat insulating property change after wet heat aging becomes large is a fiber mainly containing silver. In Patent Documents 1 to 3 that do not use the metal particles, this is a new problem that has not been a problem.
  • the problem to be solved by the present invention is to provide a heat insulating film capable of suppressing a change in heat insulating property after wet heat aging when a fibrous metal particle-containing layer containing fibrous metal particles mainly composed of silver and a binder is used. It is to be.
  • the present inventors have found that the water contact angle of the outermost surface of the heat insulating film is 90 ° when the fibrous metal particle-containing layer containing the fibrous metal particle mainly composed of silver and the binder is used.
  • the heat insulation film which can suppress the heat insulation change after wet heat aging can be provided.
  • the present invention can be achieved by the following specific means.
  • a support A heat insulating film that is disposed on one surface of a support and has a fibrous metal particle-containing layer containing a fibrous metal particle mainly composed of silver and a binder, The heat insulation film whose water contact angle of the outermost surface of a heat insulation film is 90 degrees or more.
  • the outermost surface of the heat insulating film having a water contact angle of 90 ° or more is preferably the outermost surface closer to the fibrous metal particle-containing layer than the support. .
  • the heat insulating film according to [1] or [2] may further include a surface layer having a water contact angle of 90 ° or more on a surface opposite to the support of the fibrous metal particle-containing layer. preferable.
  • the main component of the surface layer is preferably a material containing fluorine or a material containing silicon.
  • the film thickness of the surface layer is preferably 1 ⁇ m or less.
  • the surface layer is preferably a monomolecular film.
  • the main component of the binder of the fibrous metal particle-containing layer is preferably a material containing silicon.
  • the heat insulating film according to any one of [1] to [7] further includes a near-infrared shielding layer on a surface of the support opposite to the surface on which the fibrous metal particle-containing layer is disposed. It is preferable.
  • the water contact angle on the outermost surface of the heat insulating film is preferably 110 ° or more.
  • the support is preferably a transparent film.
  • the average major axis length of the fibrous metal particles is preferably 5 to 50 ⁇ m.
  • the heat insulating film according to any one of [1] to [11] is disposed inside the window, It is preferable that the fibrous metal particle-containing layer is disposed on the surface of the support opposite to the window side.
  • a window comprising the transparent support for windows and the heat insulating film according to any one of [1] to [12] bonded to the transparent support for windows.
  • the heat insulation film which can suppress the heat insulation change after wet heat aging can be provided.
  • FIG. 1 is a schematic view showing a cross section of an example of the heat insulating film of the present invention.
  • FIG. 2 is a schematic view showing a cross section of another example of the heat insulating film of the present invention.
  • FIG. 3 is a schematic view showing a cross section of another example of the heat insulating film of the present invention.
  • FIG. 4 is a schematic view showing a cross section of another example of the heat insulating film of the present invention.
  • FIG. 5 is a schematic view showing a cross section of an example of the heat insulating glass of the present invention.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the main component of a composition means the component contained 50 mass% or more with respect to the whole quantity of a composition.
  • the main component of the binder means a component contained in an amount of 50% by mass or more based on the total amount of the binder.
  • the main component of the surface layer means a component contained by 50% by mass or more with respect to the total amount of the surface layer.
  • the heat-insulating film of the present invention is a heat-insulating film having a support and a fibrous metal particle-containing layer that is disposed on one surface of the support and contains fibrous metal particles mainly containing silver and a binder.
  • the water contact angle on the outermost surface of the heat insulating film is 90 ° or more.
  • the water droplets when water droplets adhere to the surface of the heat insulating film, the water droplets absorb far-infrared rays, and the heat insulating properties are significantly impaired. Without being bound by any theory, it is believed that it is necessary to quickly agglomerate and drop moisture by making the surface of the heat insulating film hydrophobic. According to the present invention, by making the contact angle of the water on the outermost surface of the heat insulating film hydrophobic to 90 ° or more, the condensation itself due to water vapor is suppressed, or the condensed water droplets are easily dropped by their own weight, It is thought that while maintaining the heat insulation efficiency, it is possible to prevent the deterioration of the fibrous metal particle-containing layer due to the long-term retention of water droplets.
  • the fibrous metal particles mainly composed of silver responsible for far-infrared reflection used in the heat insulating film of the present invention are likely to be sulfided with sulfur components dissolved from the air because water droplets stay on the film surface for a long time.
  • Insulation performance deterioration due to disconnection or conductivity decrease is more likely to occur than with Ag sputtered films, etc., so that the heat contact change after wet heat aging due to the water contact angle of the outermost surface of the heat insulation film being 90 ° or more The effect is extremely high.
  • a preferred embodiment of the heat insulating film of the present invention has an effect that the surface of the heat insulating film is hydrophobic, so that it can be easily removed by wiping with water even when dust or oil stains adhere.
  • the heat insulation film which has an example of the preferable aspect of the heat insulation film of this invention and has both the heat insulation / heat insulation function containing a near-infrared shielding layer, the heat ray from sunlight is shielded and it will be in the condition which is easy to dew condensation. Therefore, the effect which can further suppress the heat insulation change after wet heat aging is high.
  • it is excellent in productivity rather than the laminated conductive layer formed by the vacuum film-forming method.
  • the preferable aspect of the heat insulation film of this invention is demonstrated.
  • the water contact angle of the outermost surface of a heat insulation film is 90 degrees or more.
  • the water contact angle of the outermost surface of the heat insulating film is preferably 100 ° or more from the viewpoint of suppressing a change in heat insulation after wet heat aging, more preferably 105 ° or more, and particularly preferably 110 ° or more. preferable.
  • moisture permeation into the fibrous metal-containing layer can be achieved by suppressing condensation itself due to water vapor or by easily dropping the condensed water droplets by their own weight.
  • the method for controlling the water contact angle of the outermost surface of the heat insulating film is not particularly limited, but when the fibrous metal particle-containing layer is the outermost surface, the water contact angle of the fibrous metal particle-containing layer is 90 ° or more.
  • the method of forming a fibrous metal particle content layer using the binder which becomes, and the method of adding an additive to a fibrous metal particle content layer can be mentioned.
  • the heat insulating film of the present invention preferably includes a surface layer having a water contact angle of 90 ° or more on the surface opposite to the support of the fibrous metal particle-containing layer.
  • the heat-insulating film of the present invention has a small rate of change in heat insulating properties (heat transmissivity described later, U value) after wet heat aging.
  • the rate of change after wet heat aging determined by the method described in Examples below is preferably 10% or less, more preferably 9% or less, and 7% or less. Is particularly preferably 5% or less, more preferably 4% or less.
  • the heat insulating film of the present invention is preferably excellent in the initial value of heat insulating properties (heat transmissivity, U value). Insulation film of the present invention preferably has an initial value of the thermal insulation (U value) is less than 5.5W / m 2 ⁇ K, more preferably at most 5.2W / m 2 ⁇ K, 4 . It is particularly preferably 9 W / m 2 ⁇ K or less.
  • the radio wave permeability is further excellent from the viewpoint of enhancing the permeability of useful radio waves emitted from a mobile phone or the like. From the viewpoint of radio wave permeability, it is preferable to increase the surface resistance.
  • the fibrous metal particle-containing layer has a higher surface resistance than the sputtered metal laminate and is preferable. By increasing the surface resistance of the fibrous metal particle-containing layer, the radio wave transmission becomes better.
  • the surface resistance is preferably 1000 ⁇ / ⁇ ( ⁇ per square) or more from the viewpoint of improving radio wave transmission, and more preferably 10000 ⁇ / ⁇ or more.
  • FIG. 1 to 4 are schematic views showing a cross section of an example of the heat insulating film of the present invention.
  • the schematic which shows the cross section of an example of the heat insulation glass of this invention containing the heat insulation film of this invention in FIG. 5 was shown.
  • the heat insulating film of the present invention shown in FIG. 1 includes a support 10 and a fibrous metal particle-containing layer 20.
  • the heat insulation film of this invention shown in FIG. 2 contains the support body 10, the fibrous metal particle content layer 20, and the surface layer 21 in this order.
  • the outermost surface whose water contact angle of a heat insulation film is 90 degrees or more is an outermost surface of the side closer to a fibrous metal particle content layer than a support body.
  • the fibrous metal particle-containing layer 20 is preferably the outermost surface having a water contact angle of 90 ° or more.
  • the surface layer 21 is preferably the outermost surface having a water contact angle of 90 ° or more. That is, as shown in FIG. 2, the heat insulating film of the present invention further includes a surface layer 21 having a water contact angle of 90 ° or more on the surface opposite to the support 10 of the fibrous metal particle-containing layer 20. Is preferred.
  • the heat insulating film of the present invention is preferably a heat insulating film for windows.
  • the heat insulating film of the present invention is preferably arranged inside the window, and the fibrous metal particle-containing layer 20 is arranged on the surface of the support 10 opposite to the window (glass 61 in FIG. 5) side. This is preferable because it is easy to reflect far infrared rays. When there is no heat insulation film, indoor far infrared rays are absorbed by the glass, and heat conduction through the glass causes indoor heat to go out outdoors, but if there is a heat insulation film, the far infrared rays are reflected indoors. Indoor heat is less likely to go out.
  • the fibrous metal particle-containing layer 20 is preferably in a layer as close as possible to the outermost layer on the indoor side, the surface layer 21 is the outermost layer, and the fibrous metal particle-containing layer 20 is in the layer next to the outermost layer. Is preferable from the viewpoint of enhancing heat insulation.
  • the heat insulating film of the present invention shown in FIG. 3 includes an adhesive layer 51, a support 10, a fibrous metal particle-containing layer 20, and a surface layer 21 in this order.
  • the heat insulating film of the present invention preferably has an adhesive layer 51 on the window (glass 61 in FIG. 5) side of the support 10 as shown in FIG. 3 or FIG. 4, and the glass 61 and the adhesive layer 51 are bonded together. It is preferable.
  • the heat insulating film of the present invention preferably further includes a near-infrared shielding layer on the surface of the support opposite to the surface on which the fibrous metal particle-containing layer is disposed.
  • a near-infrared shielding layer on the surface of the support opposite to the surface on which the fibrous metal particle-containing layer is disposed.
  • layer 41 is included.
  • an example of the heat insulation film of this invention has the near-infrared shielding layer 41 containing a near-infrared shielding material.
  • the near-infrared shielding material may be contained in other layers without forming the near-infrared shielding layer 41 alone.
  • the near-infrared shielding material may be included in the fibrous metal particle-containing layer 20, may be included in the first adhesive layer 31 or the second adhesive layer 32, and is included in the adhesive layer 51.
  • the near-infrared shielding material is included in the surface of the support opposite to the surface on which the fibrous metal particle-containing layer is arranged, that is, the layer on the surface of the support 10 on the window (glass 61) side. This is preferable from the viewpoint of shielding infrared light.
  • the heat insulating glass 111 of the present invention shown in FIG. 5 includes the heat insulating film 103 of the present invention and the glass 61.
  • the heat insulating film 103 of the present invention is the inside of the window (indoor side, indoor side, opposite to the sunlight incident side in the daytime, in FIG. (IN side) is preferable.
  • the laminated body in which the support 10, the fibrous metal particle-containing layer 20, and the surface layer 21 are bonded together through an adhesive layer may be referred to as a heat insulating member 102.
  • the adhesive layer may be a single layer or a laminate of two or more layers. In FIG. 5, the adhesive layer is a laminate of the first adhesive layer 31 and the second adhesive layer 32.
  • the laminated body which provided the contact bonding layer (The laminated body of the 1st contact bonding layer 31 and the 2nd contact bonding layer 32 in FIG. 5) on the support body 10 may be called the support body 101 with an contact bonding layer.
  • the preferable aspect of each layer which comprises the heat insulation film of this invention is demonstrated.
  • the support various materials can be used depending on the purpose as long as the support can bear the fibrous metal particle-containing layer. Generally, a plate or sheet is used.
  • the support may be transparent or opaque, but is preferably transparent and more preferably transparent to visible light.
  • the support preferably has a total visible light transmittance of 70% or more, more preferably 85% or more, and still more preferably 90% or more. The total visible light transmittance of the support is measured in accordance with ISO (International Organization for Standardization) 13468-1 (1996).
  • ISO International Organization for Standardization
  • the support is preferably a transparent film.
  • the material constituting the support examples include synthetic resins such as polycarbonate, polyethersulfone, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamideimide, polyimide, polyethylene terephthalate, and polycycloolefin. it can.
  • the surface of the support on which the fibrous metal particle-containing layer is formed is optionally cleaned with an alkaline aqueous solution, chemical treatment such as a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method. Alternatively, pretreatment may be performed by vacuum deposition or the like.
  • the support has a desired thickness depending on the application. Generally, it is selected from the range of 1 ⁇ m to 500 ⁇ m, more preferably 3 ⁇ m to 400 ⁇ m, and even more preferably 5 ⁇ m to 300 ⁇ m.
  • the fibrous metal particle-containing layer is disposed on one surface of the support and includes fibrous metal particles mainly composed of silver and a binder.
  • the fibrous metal particle-containing layer preferably has a small void size for reflecting far infrared rays.
  • the void size of 80% or more voids is 25 ( ⁇ m) 2 or less. The void area is more preferable.
  • fibrous metal particles mainly composed of silver are used.
  • the fibrous metal particles are fibrous, and the fibrous form is synonymous with a wire form or a line form.
  • the fibrous metal particles include metal nanowires and rod-like metal particles.
  • metal nanowires are preferable.
  • metal nanowires may be described as representative examples of the fibrous metal particles, but the description regarding the metal nanowires can be used as a general description of the fibrous metal particles.
  • the fibrous metal particle-containing layer preferably contains metal nanowires having an average minor axis length of 150 nm or less as the fibrous metal particles. 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.
  • the fibrous metal particles such as metal nanowires preferably have a solid structure.
  • the fibrous metal particles such as metal nanowires preferably have an average minor axis length of 1 nm to 150 nm.
  • the average minor axis length (average diameter) of fibrous metal particles such as metal nanowires is preferably 100 nm or less, more preferably 60 nm or less, and 50 nm or less. More preferably, it is particularly preferably 25 nm or less, since 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 major axis length of the fibrous metal particles such as metal nanowires is preferably about the same as the far-infrared reflection band to be reflected from the viewpoint of easily reflecting the far-infrared reflection band to be reflected.
  • the average major axis length of fibrous metal particles such as metal nanowires is preferably 5 ⁇ m to 50 ⁇ m from the viewpoint of easily reflecting far infrared rays having a wavelength of 5 to 50 ⁇ m, more preferably 10 ⁇ m to 40 ⁇ m, and more preferably 15 ⁇ m to More preferably, it is 40 ⁇ m.
  • the average major axis length of the metal nanowires is 40 ⁇ m or less, it becomes easy to synthesize the metal nanowires without generating aggregates, and when the average major axis length is 15 ⁇ m or more, sufficient heat insulation is obtained. Becomes easy.
  • the average minor axis length (average diameter) and the average major axis length of the fibrous metal particles such as metal nanowires are measured using, for example, a transmission electron microscope (TEM) and an optical microscope, and a TEM image or an optical microscope image is obtained. It can be determined by observing.
  • TEM transmission electron microscope
  • optical microscope optical microscope
  • the average minor axis length (average diameter) and the average major axis length of the fibrous metal particles such as metal nanowires were measured using a transmission electron microscope (manufactured by JEOL Ltd., trade name: JEM-2000FX). About 300 randomly selected metal nanowires, the short axis length and the long axis length can be measured, respectively, and the average short axis length and the average long axis length of the fibrous metal particles such as metal nanowires can be obtained from the average value. . In this specification, the value obtained by this method is adopted.
  • the short-axis length when the short-axis direction cross section of metal nanowire is not circular makes the length of the longest part the short-axis length by the measurement of a short-axis direction. Also. When fibrous metal particles, such as metal nanowires, are bent, a circle having the arc as an arc is taken into consideration, and a value calculated from the radius and the curvature is taken as the major axis length.
  • the minor axis length (diameter) is 150 nm or less and the major axis length is 5 ⁇ m or more and 50 ⁇ m or less with respect to the content of fibrous metal particles such as all-metal nanowires in the fibrous metal particle-containing layer.
  • the content of fibrous metal particles such as metal nanowires is preferably 50% by mass or more in terms of metal amount, more preferably 60% by mass or more, and further preferably 75% by mass or more.
  • the minor axis length (diameter) is 150 nm or less and the ratio of the fibrous metal particles such as metal nanowires having a length of 5 ⁇ m or more and 50 ⁇ m or less is 50% by mass or more, sufficient heat insulation can be obtained.
  • the haze reduction caused by particles having a short axis length and particles having a short length can be suppressed.
  • a decrease in transparency can be avoided even when plasmon absorption is strong.
  • the coefficient of variation of the short axis length (diameter) of fibrous metal particles such as metal nanowires used in the fibrous metal particle-containing layer is preferably 40% or less, more preferably 35% or less, and even more preferably 30% or less.
  • the coefficient of variation is 40% or less, the ratio of metal nanowires that easily reflect far-infrared rays having a wavelength of 5 to 50 ⁇ m increases, which is preferable from the viewpoint of transparency and heat insulation.
  • the coefficient of variation of the short axis length (diameter) of a fibrous metal particle such as a metal nanowire is measured by measuring the short axis length (diameter) of 300 nanowires randomly selected from a transmission electron microscope (TEM) image, for example. It can be obtained by calculating the standard deviation and the arithmetic mean value and dividing the standard deviation by the arithmetic mean value.
  • TEM transmission electron microscope
  • the aspect ratio of fibrous metal particles such as metal nanowires that can be used in the present invention 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 metal particles such as metal nanowires 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. 100 to 100,000 is more preferable.
  • the aspect ratio is 10 or more, a network in which fibrous metal particles such as metal nanowires are uniformly dispersed is easily formed, and a fibrous metal particle-containing layer having high heat insulation is easily obtained.
  • the aspect ratio is 100,000 or less, for example, in a coating solution when a fibrous metal particle-containing layer is provided on a support by coating, fibrous metal particles such as metal nanowires are entangled to form an aggregate.
  • the content of fibrous metal particles such as metal nanowires having an aspect ratio with respect to the mass of the fibrous metal particles such as all metal nanowires contained in the fibrous metal 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 most preferably 80% by mass or more.
  • the shape of the fibrous metal particles such as metal nanowires may be any shape such as a columnar shape, a rectangular parallelepiped shape, or a columnar shape with a polygonal cross section, but for applications that require high transparency, It is preferable that the cross section is a polygon having a pentagon or more and a cross section having no acute angle.
  • the cross-sectional shape of fibrous metal particles such as metal nanowires can be detected by applying an aqueous dispersion of fibrous metal particles such as metal nanowires on a support and observing the cross-section with a transmission electron microscope (TEM). it can.
  • TEM transmission electron microscope
  • the metal which forms a fibrous metal particle has silver as a main component.
  • 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 that forms the fibrous metal particles is at least one selected from the group consisting of the fourth period, the fifth period, and the sixth period of the Long Periodic Table (IUPAC (International Union of Pure and Applied Chemistry) 1991). And at least one metal selected from Groups 2 to 14 is more preferable. Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, Group 13, And at least one metal selected from Group 14 is more preferred, but it contains at least silver 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, palladium, copper, silver, gold, platinum, tin, or any of these
  • the alloy containing 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 silver-based fibrous metal particles are preferably silver nanowires.
  • the content of silver nanowires with respect to the mass of fibrous metal particles such as all metal nanowires contained in the fibrous metal particle-containing layer is not particularly limited as long as the effects of the present invention are not hindered.
  • the content of silver nanowires with respect to the mass of fibrous metal particles such as all metal nanowires contained in the fibrous metal particle-containing layer is preferably 50% by mass or more, more preferably 80% by mass or more, More preferably, the fibrous metal particles such as all metal nanowires are substantially silver nanowires.
  • substantially means that metal atoms other than silver inevitably mixed are allowed.
  • the mass per unit area of the fibrous metal particle-containing layer (the coating amount of the total solid content of the coating liquid during film formation) is the desired range of the heat insulating property, total light transmittance, and haze value of the fibrous metal particle-containing layer. Is selected. If the coating amount is too small, sufficient heat insulating properties cannot be obtained. If the coating amount is too large, haze increases or a failure such as cracking or peeling of the fibrous metal particle-containing layer occurs. Preferably it is in the range of 0.050 to 1.000 g / m 2 , more preferably in the range of 0.100 to 0.600 g / m 2 , and particularly preferably in the range of 0.110 to 0.500 g / m 2. preferable.
  • the amount of the fibrous metal particles relative to the fibrous metal particle-containing layer is preferably selected so that the heat insulating property, the total light transmittance, and the haze value of the fibrous metal particle-containing layer are in a desired range.
  • the amount of the fibrous metal particles relative to the fibrous metal particle-containing layer is preferably 1 to 65% by mass, more preferably 3 to 50% by mass, and particularly preferably 5 to 35% by mass.
  • the fibrous metal particles such as metal nanowires are not particularly limited and may be produced by any method. As described below, it is preferable to produce by reducing metal ions in a solvent in which a halogen compound and a dispersant are dissolved. Moreover, after forming fibrous metal particles such as metal nanowires, it is preferable to perform a desalting treatment by a conventional method from the viewpoints of dispersibility and temporal stability of the fibrous metal particle-containing layer.
  • methods for producing fibrous metal particles such as metal nanowires JP2009-215594A, JP2009-242880A, JP2009-299162A, JP2010-84173A, and JP2010-A. The method described in Japanese Patent No. 86714 can be used.
  • the solvent used for the production of fibrous metal particles such as metal nanowires is preferably a hydrophilic solvent, and examples thereof include water, alcohol solvents, ether solvents, ketone solvents, and these are used alone. You may use 2 or more types together.
  • the alcohol solvent include methanol, ethanol, propanol, isopropanol, butanol, and ethylene glycol.
  • the ether solvent include dioxane and tetrahydrofuran.
  • 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.
  • the temperature may be changed during the grain formation process. Changing the temperature during the process has the effect of controlling nucleation, suppressing renucleation, and improving monodispersity by promoting selective growth. There is.
  • the heat treatment is preferably performed by adding a reducing agent.
  • the reducing agent is not particularly limited and can be appropriately selected from those usually used.
  • reducing sugars, sugar alcohols as derivatives thereof, and 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 fibrous metal particles such as metal nanowires 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 the metal ions or metal halide fine particles. In order to obtain it, it is preferable to divide the addition of the halogen compound into two or more stages because nucleation and growth can be controlled.
  • the step of adding the dispersant is not particularly limited. It may be added before the preparation of fibrous metal particles such as metal nanowires, and may be added in the presence of a dispersing agent, or may be added after the preparation of fibrous metal particles such as metal nanowires. You may add for control.
  • the dispersant include an amino group-containing compound, a thiol group-containing compound, a sulfide group-containing compound, an amino acid or a derivative thereof, a peptide compound, a polysaccharide, a natural polymer derived from a polysaccharide, a synthetic polymer, or a gel derived therefrom. And the like, and the like.
  • various polymer compounds that are preferably used as a dispersant are compounds included in the polymer described below.
  • polymer suitably used as the dispersant examples include gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, polyalkylene amine, polyalkylene amine, partially alkyl ester of polyacrylic acid, polyvinyl pyrrolidone, and polyvinyl pyrrolidone structure, which are protective colloid polymers.
  • a polymer having a hydrophilic group such as a copolymer containing 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) of 3,000 to 300,000, preferably 5,000 to 100,000, as measured by gel permeation chromatography (GPC). Is more preferable.
  • Mw weight average molecular weight
  • GPC gel permeation chromatography
  • the halogen compound is not particularly limited as long as it is a compound containing bromine, chlorine, or iodine, and can be appropriately selected according to the purpose.
  • sodium bromide, sodium chloride, sodium iodide, potassium iodide, odor Preference is given to compounds that can be used in combination with alkali halides such as potassium chloride and potassium chloride and the following dispersion additives.
  • 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 both a halogen compound and silver halide fine particles may be used.
  • 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 a dispersant function 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.
  • HTAB hexadecyl-trimethylammonium bromide
  • HTAC hexadecyl-trimethylammonium chloride
  • desalting is preferably performed after the formation of fibrous metal particles such as metal nanowires.
  • the desalting treatment after formation of fibrous metal particles such as metal nanowires can be performed by techniques such as ultrafiltration, dialysis, gel filtration, decantation, and centrifugation.
  • fibrous metal particles such as metal nanowires contain as little inorganic ions as possible, such as alkali metal ions, alkaline earth metal ions, and halide ions.
  • the electrical conductivity of a dispersion obtained by dispersing metal nanowires 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 aqueous dispersion of fibrous metal particles such as metal nanowires is preferably 0.5 mPa ⁇ s to 100 mPa ⁇ s, and more preferably 1 mPa ⁇ s to 50 mPa ⁇ s. Electrical conductivity and viscosity are measured at a concentration of fibrous metal particles such as metal nanowires in the aqueous dispersion of 0.45% by mass. When the concentration of fibrous metal particles such as metal nanowires in the aqueous dispersion is higher than the above concentration, the aqueous dispersion is diluted with distilled water and measured.
  • the fibrous metal particle-containing layer contains a binder.
  • the binder By containing the binder, the dispersion of the fibrous metal particles such as metal nanowires in the fibrous metal particle-containing layer is stably maintained, and the fibrous metal particle-containing layer is not formed on the support surface without an adhesive layer. Even when it is formed, there is a tendency that strong adhesion between the support and the fibrous metal particle-containing layer is secured.
  • Preferred binders include sol-gel cured products obtained by hydrolysis and polycondensation of an alkoxide compound of element (b) selected from the group consisting of Si, Ti, Zr and Al, conductive polymers, organic polymer polymers (conductivity). (Excluding the conductive polymer).
  • the main component of the binder of the fibrous metal particle-containing layer is preferably a sol-gel cured product.
  • the heat insulating film of the present invention is more preferably a material in which the main component of the binder of the fibrous metal particle-containing layer contains silicon.
  • the silicon-containing material is particularly preferably a sol-gel cured product obtained by hydrolysis and polycondensation of an Si element alkoxide compound or silicone, and obtained by hydrolysis and polycondensation of an Si element alkoxide compound.
  • the sol-gel cured product is particularly preferable.
  • preferred embodiments of the sol-gel cured product, the conductive polymer, and the organic polymer polymer (excluding the conductive polymer) will be described in order.
  • the heat insulating film of the present invention is obtained by hydrolysis and polycondensation of an alkoxide compound of an element (b) selected from the group consisting of Si, Ti, Zr and Al as a main component of the binder of the fibrous metal particle-containing layer.
  • a sol-gel cured product is preferably included, and a sol-gel cured product obtained by hydrolysis and polycondensation of an alkoxide compound of Si element is particularly preferable in terms of production cost and reflectance in the far infrared region.
  • a sol-gel cured product obtained by hydrolysis and polycondensation of an alkoxide compound (hereinafter also referred to as a specific alkoxide compound) of an element (b) selected from the group consisting of Si, Ti, Zr and Al includes silicon oxide, zirconium oxide, It is at least one selected from titanium oxide and aluminum oxide.
  • the main component of the binder of the fibrous metal particle-containing layer is a sol-gel cured product obtained by hydrolysis and polycondensation of an alkoxide compound of the element (b) selected from the group consisting of Si, Ti, Zr and Al
  • the main component of the binder of the fibrous metal particle-containing layer is at least one selected from silicon oxide, zirconium oxide, titanium oxide, and aluminum oxide.
  • the fibrous metal particle-containing layer preferably satisfies at least one of the following conditions (i) and (ii), more preferably satisfies at least the following condition (ii), and satisfies the following conditions (i) and (ii): It is particularly preferable to satisfy it.
  • Ratio of the amount of the element (b) contained in the fibrous metal particle-containing layer to the amount of the metal element (a) contained in the fibrous metal particle-containing layer [(number of moles of the element (b) ) / (Number of moles of 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 fibrous metal particle-containing layer and the mass of the fibrous metal particles such as metal nanowires contained in the fibrous metal particle-containing layer is in the range of 0.25 / 1 to 30/1.
  • the fibrous metal particle-containing layer has a ratio of the usage amount of the specific alkoxide compound to the usage amount of the fibrous metal particles such as the above-described metal nanowire, that is, [(mass of the specific alkoxide compound) / (fibrous metal such as the metal nanowire).
  • the ratio of the mass of particles)] is preferably in the range of 0.25 / 1 to 30/1.
  • the mass ratio is 0.25 / 1 or more, the heat insulation (conceived to be due to the high conductivity of the fibrous metal particles) and the transparency are excellent, and at the same time, the wear resistance, heat resistance, and wet heat durability. It can be a fibrous metal particle-containing layer that is excellent in both properties and bending resistance.
  • the said mass ratio When the said mass ratio is 30/1 or less, it can become a fibrous metal 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 most preferably in the range of 2/1 to 15/1.
  • the obtained fibrous metal particle-containing layer has high heat insulating properties and high transparency (visible light transmittance and haze), as well as wear resistance, heat resistance, and wet heat. It will be excellent in durability and bend resistance, and a heat insulating film having suitable physical properties can be obtained stably.
  • the main component of the binder in the fibrous metal particle-containing layer is preferably a conductive polymer.
  • Conductive polymers also effectively block infrared rays and exhibit heat insulation. This is thought to be because the plasma absorption wavelength due to free electrons of the conductive polymer is shorter than the radiation of an object near the ground temperature, and reflects electromagnetic waves having a wavelength higher than the plasma absorption wavelength.
  • the conductive polymer used as the main component of the binder of the fibrous metal particle-containing layer the conductive polymers described in JP-A-2012-189683, [0038] to [0046] and Examples are preferably used. Can do.
  • the conductive polymer is generally an organic polymer having a conjugated double bond as a basic skeleton, specifically, polythiophene, polypyrrole, polyaniline, polyacetylene, polyparaphenylene, polyfuran, polyfluorene, polyphenylene.
  • Preferable examples include any one kind or a mixture of two or more kinds of conductive polymers selected from vinylene, derivatives thereof, and copolymers of monomers constituting them.
  • polythiophene derivatives that are soluble or dispersible in water or other solvents and exhibit high conductivity and transparency are preferable.
  • formula (I) the following formula (I):
  • R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or R 1 and R 2 may be bonded to each other and optionally substituted
  • a polythiophene derivative containing a repeating unit represented by (forms an alkylene group having 1 to 4 carbon atoms, and n represents an integer of 50 to 1000) is preferable.
  • the optionally substituted alkylene group having 1 to 4 carbon atoms formed by bonding R 1 and R 2 to each other is specifically methylene substituted with an alkyl group.
  • Groups, groups that form ethylene-1,2 groups, propylene-1,3 groups, butene-1,4 groups optionally substituted with alkyl groups having 1 to 12 carbon atoms or phenyl groups.
  • R 1 and R 2 in the formula (I) are preferably a methyl group or an ethyl group, or a methylene group, an ethylene-1, 2 group, or a propylene-1, formed by combining R 1 and R 2 with each other Three groups.
  • Particularly preferred polythiophene derivatives include the following formula (II):
  • p represents an integer of 50 to 1000
  • p represents an integer of 50 to 1000
  • the conductive polymer preferably further contains a dopant (electron donor).
  • a dopant electron donor
  • Preferred examples of the dopant include polystyrene sulfonic acid, polyacrylic acid, polymethacrylic acid, polymaleic acid, and polyvinyl sulfonic acid.
  • polystyrene sulfonic acid is preferable.
  • the number average molecular weight (Mn) of the dopant is preferably 1,000 to 2,000,000, particularly preferably 2,000 to 500,000.
  • the content of the dopant is usually 20 to 2000 parts by mass, preferably 40 to 200 parts by mass with respect to 100 parts by mass of the conductive polymer.
  • a polythiophene derivative of the formula (II) is used as a conductive polymer and polystyrene sulfonic acid is used as a dopant
  • 100 to 200 parts by mass of polystyrene sulfonic acid is preferable with respect to 100 parts by mass of polythiophene, and particularly 120 to 180 parts by mass. Part is preferred.
  • organic polymer used as the main component of the binder of the fibrous metal particle-containing layer include polymethacrylic acid, polymethacrylate (for example, poly (methyl methacrylate)), polyacrylate, and polyacrylonitrile.
  • Acrylic acid polyvinyl alcohol (PVA), polyester (eg, polyethylene terephthalate (PET), polyester naphthalate, and polycarbonate), phenol or cresol-formaldehyde (Novolacs®), polystyrene, polyvinyl toluene, polyvinyl xylene, polyimide, Highly aromatic polymers such as polyamide, polyamideimide, polyetherimide, polysulfide, polysulfone, polyphenylene, and polyphenyl ether, Riurethane (PU; Takelac (registered trademark) WS-4000, manufactured by Mitsui Chemicals, Inc.), epoxy, polyolefin (eg, polypropylene, polymethylpentene, and polycycloolefin), acrylonitrile-butadiene-styrene copolymer (ABS) , Cellulose, silicone and other silicon-containing polymers (eg, polysilsesquioxane and polysilane, SQ
  • the polycycloolefin used as the main component of the binder of the fibrous metal particle-containing layer is preferably polynorbornene. Polynorbornene has little absorption in the infrared region and is excellent in heat insulation and weather resistance.
  • the polynorbornene a commercially available product (for example, ZEONEX (registered trademark) or ZEONOR (registered trademark) manufactured by Nippon Zeon Co., Ltd.) may be used.
  • silicone is preferable from the viewpoint of forming the fibrous metal particle-containing layer using a binder having a water contact angle of 90 ° or more of the fibrous metal particle-containing layer.
  • the water contact angle of the fibrous metal particle-containing layer is not necessarily 90 ° or more. Therefore, the water contact angle is 90 ° or more.
  • a modified silicone for example, acrylic modified silicone
  • the modified silicone having a structure in which the water contact angle is 90 ° or more in the main chain or the side chain include materials described in [0010] of JP-A-10-286900. Are incorporated herein.
  • acrylic modified silicone is preferable.
  • the product name Acrit 8SS-723 manufactured by Taisei Fine Chemical Co., Ltd. can be preferably used.
  • the fibrous metal particle-containing layer may further contain a matrix other than the binder (hereinafter referred to as “other matrix”).
  • the “matrix” is a general term for substances that form a layer containing fibrous metal particles such as metal nanowires.
  • the fibrous metal particle-containing layer containing the other matrix is formed by adding a material capable of forming the other matrix to the liquid composition described later and applying it to the support (for example, by coating). That's fine.
  • the matrix may be non-photosensitive or photosensitive such as a photoresist composition.
  • the fibrous metal particle-containing layer contains other matrix, for example, 0.10% by mass to 20% by mass, preferably 0.15% by mass to 10% by mass, and more preferably 0.20% with respect to the content of the binder. It is advantageous to select from the range of 5% by mass to 5% by mass because a fibrous metal particle-containing layer having excellent heat insulating properties, transparency, film strength, abrasion resistance and bending resistance can be obtained.
  • the water contact angle of the fibrous metal particle-containing layer can be 90 ° or more by a method of adding an additive to the fibrous metal particle-containing layer.
  • an additive for adjusting the water contact angle of the fibrous metal particle-containing layer a filler made of a water repellent material such as a surfactant, a silane coupling agent, or a fluororesin can be used.
  • the surfactant used for the fibrous metal particle-containing layer include materials described in JP-A-2014-697, [0087] to [0090], and the contents of this publication are incorporated herein. .
  • a fluorine-based surfactant is preferable.
  • AGC Seimi Chemical Co., Ltd., a brand name Surflon, etc. can be used preferably.
  • Dispersant- A dispersing agent is used in order to disperse
  • the dispersant is not particularly limited as long as the metal nanowires can be dispersed, and can be appropriately selected according to the purpose.
  • a commercially available dispersant can be used as a pigment dispersant, and a polymer dispersant having a property of adsorbing to metal nanowires is particularly preferable.
  • polymer dispersants examples include polyvinylpyrrolidone, BYK series (registered trademark, manufactured by Big Chemie), Solsperse series (registered trademark, manufactured by Nihon Lubrizol, etc.), Ajisper series (registered trademark, Ajinomoto Co., Inc.). Manufactured).
  • the content of the dispersant in the fibrous metal particle-containing layer is 0.1 mass relative to 100 mass parts of the binder when the binder described in [0086] to [0095] of JP2013-225461A is used. To 50 parts by mass, preferably 0.5 to 40 parts by mass, more preferably 1 to 30 parts by mass.
  • the content of the dispersant with respect to the binder By setting the content of the dispersant with respect to the binder to 0.1 parts by mass or more, aggregation of fibrous metal particles such as metal nanowires in the dispersion is effectively suppressed, and by setting the content to 50 parts by mass or less. This is preferable because a stable liquid film is formed in the coating process and the occurrence of coating unevenness is suppressed.
  • the solvent is a coating solution for forming a composition containing fibrous metal particles such as the above-described metal nanowires and a binder on the surface of the support or the surface of the adhesive layer of the support with an adhesive layer. It is a component used and can be appropriately selected according to the purpose.
  • the solvent may be anything as long as it can dissolve the binder in an amount of 0.1% by mass or more, and includes water, alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents, aromatic solvents, halogen solvents, and the like. It is done.
  • This solvent may also serve as at least a part of the solvent of the metal nanowire dispersion described above. These may be used individually by 1 type and may use 2 or more types together.
  • 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 fibrous metal particle-containing layer preferably contains a metal corrosion inhibitor for fibrous metal particles such as metal nanowires.
  • a metal corrosion inhibitor for fibrous metal particles such as metal nanowires.
  • thiols, azoles, etc. are suitable.
  • the metal corrosion inhibitor is added to the composition for forming a fibrous metal particle-containing layer in a state dissolved in a suitable solvent, or in powder form, or after forming a conductive film with a conductive layer coating solution described later, It can be applied by soaking in a corrosion inhibitor bath.
  • the content in the fibrous metal particle-containing layer is preferably 0.5% by mass to 10% by mass with respect to the content of the fibrous metal particles such as metal nanowires. .
  • the other matrix it is possible to use a polymer compound as a dispersant used in the production of the fibrous metal particles such as the above-described metal nanowires as at least a part of the components constituting the matrix.
  • conductive materials in addition to fibrous metal particles such as metal nanowires, other conductive materials such as conductive particles can be used in combination as long as the effects of the present invention are not impaired.
  • the conductive particles include metal particles, tin-doped indium oxide (ITO) particles, antimony-doped tin oxide (ATO) particles, and cesium-doped tungsten oxide (CWO) particles.
  • ITO tin-doped indium oxide
  • ATO antimony-doped tin oxide
  • CWO cesium-doped tungsten oxide
  • the conductive oxide particles are listed.
  • ITO is preferable because it increases the infrared reflection of the fibrous metal particle-containing layer.
  • the content ratio of fibrous metal particles such as metal nanowires is based on the total amount of conductive material including fibrous metal particles such as metal nanowires. On a volume basis, it is preferably 50% or more, more preferably 60% or more, and particularly preferably 75% or more.
  • a fibrous metal particle-containing layer having high heat insulating properties can be easily obtained.
  • conductive particles having a shape other than the fibrous metal particles such as metal nanowires may not significantly contribute to the conductivity in the fibrous metal particle-containing layer and may have absorption in the visible light region.
  • the ratio of fibrous metal particles such as metal nanowires can be obtained as follows.
  • the fibrous metal 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
  • the ratio of the metal nanowires can be calculated by measuring the amount of silver remaining on the filter paper and the amount of silver transmitted through the filter paper using an coupled plasma (Inductively Coupled Plasma; ICP) emission spectrometer.
  • ICP Inductively Coupled Plasma
  • the aspect ratio of fibrous metal particles such as metal nanowires is determined by observing the fibrous metal particles such as metal nanowires remaining on the filter paper with a TEM, and the short axis length and long axis of the fibrous metal particles such as 300 metal nanowires. Calculated by measuring each length.
  • the average film thickness of the fibrous metal particle-containing layer is usually selected in the range of 0.005 ⁇ m to 2 ⁇ m. For example, by setting the average film thickness to 0.001 ⁇ m or more and 0.5 ⁇ m or less, sufficient durability and film strength can be obtained. In particular, if the average film thickness is in the range of 0.01 ⁇ m to 0.1 ⁇ m, an acceptable range in manufacturing can be secured, which is preferable.
  • the fibrous metal particle-containing layer satisfying at least one of the above-mentioned conditions (i) and (ii), it is possible to maintain high heat insulating properties and transparency, and due to the sol-gel cured product, metal nanowires It is preferable that fibrous metal particles such as can be stably fixed and can achieve high strength and durability. For example, even if the thickness of the fibrous metal particle-containing layer is a thin layer of 0.005 ⁇ m to 0.5 ⁇ m, the fibrous metal particles have wear resistance, heat resistance, wet heat durability, and bending resistance that do not cause any practical problems. A containing layer can be obtained. For this reason, the heat insulation film which is one Embodiment of this invention is used suitably for various uses.
  • the film thickness may be 0.005 ⁇ m to 0.5 ⁇ m, more preferably 0.007 ⁇ m to 0.3 ⁇ m, more preferably 0.008 ⁇ m to 0.2 ⁇ m, and more preferably 0.01 ⁇ m to 0.2 ⁇ m. 0.1 ⁇ m is most preferable.
  • the fibrous metal particle-containing layer thinner, the transparency of the fibrous metal particle-containing layer can be further improved.
  • the average film thickness of the fibrous metal particle-containing layer is calculated as an arithmetic average value by measuring the thickness of the fibrous metal particle-containing layer at five points by directly observing the cross section of the fibrous metal particle-containing layer with an electron microscope. .
  • the film thickness of the fibrous metal particle-containing layer is, for example, a portion of the fibrous metal particle-containing layer formed using a stylus type surface shape measuring instrument (Dektak (registered trademark) 150, manufactured by Bruker AXS) and a fibrous shape. It can also be measured as a step in the portion from which the metal particle-containing layer has been removed.
  • the heat insulation film of this invention contains the surface layer whose water contact angle is 90 degrees or more further on the surface opposite to the support body of a fibrous metal particle content layer.
  • the surface layer composition Although there is no restriction
  • a fluorine-containing material or a silicon-containing material is preferable, and a fluorine-containing material is more preferable.
  • the main component of the surface layer is preferably a material containing fluorine or a material containing silicon from the viewpoint of improving the abrasion resistance.
  • the fluorine-containing material for forming the surface layer having a water contact angle of 90 ° or more include a fluororesin and a fluorine-containing monomolecular film.
  • fluororesin used for the surface layer examples include the fluororesins described in JP-A-2002-127310, [0021] to [0022], and the contents of this gazette are incorporated herein.
  • fluororesins include fluorocarbon polymers (eg, polyvinylidene fluoride, polytetrafluoroethylene (TFE), or polyhexafluoropropylene), fluoro-olefin copolymers (eg, manufactured by Asahi Glass Co., Ltd.).
  • fluorocarbon polymers eg, polyvinylidene fluoride, polytetrafluoroethylene (TFE), or polyhexafluoropropylene
  • fluoro-olefin copolymers eg, manufactured by Asahi Glass Co., Ltd.
  • "LUMIFLON” registered trademark
  • amorphous fluorocarbon polymer or copolymer for example, "CYTOP” (registered trademark) manufactured by Asahi
  • the surface layer is preferably a monomolecular film from the viewpoint of improving heat insulating properties (initial U value).
  • the silicon-containing material for forming a surface layer having a water contact angle of 90 ° or more include hydrophobized silica and modified silicone. Hydrophobized silica improves heat insulation (initial U value). It is more preferable from the viewpoint of.
  • the hydrophobized silica used for the surface layer include materials described in JP-A-2013-123660, [0040] to [0043], and the contents of this publication are incorporated herein. As the hydrophobized silica, hydrophobic fumed silica is preferable.
  • the modified silicone used for the surface layer include materials described in JP-A-10-286900, [0010], and the contents of this publication are incorporated herein.
  • acrylic modified silicone is preferable.
  • the product name Acrit 8SS-723 manufactured by Taisei Fine Chemical Co., Ltd. can be preferably used.
  • the surface layer preferably has a low moisture permeability from the viewpoint of improving heat-insulating wet heat durability. As the moisture permeability of the surface layer, the product of the water vapor transmission rate and the film thickness can be used as an index.
  • Examples of the material having a low water vapor transmission rate that can be preferably used for the surface layer in the present invention include silicon-containing materials.
  • the film thickness of the surface layer is preferably 1 ⁇ m or less from the viewpoint of improving the initial value of heat insulating properties, more preferably 0.5 ⁇ m or less, and 0.3 ⁇ m or less. It is particularly preferred.
  • the surface layer may contain oxide particles for the purpose of adjusting the refractive index or increasing the surface hardness.
  • oxide particles include silicon oxide, titanium oxide, and zirconium oxide. Since the surface layer is the outermost layer of the heat insulating film, it is preferable to use silicon oxide having a low refractive index from the viewpoint of antireflection, and it is particularly preferable to use silicon oxide of hollow particles.
  • the particle size of the oxide particles is preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 200 nm.
  • the amount of oxide particles added is preferably in the range of 1 to 50% by mass, and more preferably in the range of 10 to 40% by mass.
  • the heat insulating film preferably has at least one intermediate layer between the support and the fibrous metal particle-containing layer.
  • the intermediate layer By providing an intermediate layer between the support and the fibrous metal particle-containing layer, the adhesion between the support and the fibrous metal particle-containing layer, the total light transmittance of the fibrous metal particle-containing layer, and the fibrous metal particles It is possible to improve at least one of the haze of the containing layer and the film strength of the fibrous metal particle-containing layer.
  • an adhesive layer for improving the adhesive force between the support and the fibrous metal particle-containing layer, and a functional layer that improves functionality by interaction with the components contained in the fibrous metal particle-containing layer Etc. are appropriately provided depending on the purpose.
  • the fibrous metal particle-containing layer 20 is provided on a support 101 with an adhesive layer having an intermediate layer (first adhesive layer 31 and second adhesive layer) on the support. Yes. Between the support 10 and the fibrous metal particle-containing layer 20, the first adhesive layer 31 excellent in affinity with the support 10 and the second excellent in affinity between the fibrous metal particle-containing layer 20.
  • the intermediate layer including the adhesive layer 32 is provided.
  • An intermediate layer having a configuration other than that in FIG. 5 may be included.
  • the first adhesive layer 31 and the first adhesive layer 31 similar to those in the embodiment in FIG. 5 are provided between the support 10 and the fibrous metal particle-containing layer 20.
  • ⁇ Near-infrared shielding layer> Furthermore, by using a near-infrared shielding material, the shielding property of near-infrared light can be improved.
  • a near-infrared shielding material flat metal particles (for example, silver nanodisks), organic multilayer films, spherical metal oxide particles (for example, tin-doped indium oxide (ITO) particles, antimony-doped tin oxide (ATO) particles, Cesium-doped tungsten oxide (CWO) particles).
  • a near-infrared shielding material is contained in a near-infrared shielding layer, and it is more preferable that it is a material which forms a near-infrared shielding layer independently.
  • the near-infrared shielding layer is divided into a heat ray reflection type near infrared reflection layer and a heat ray absorption type near infrared absorption layer depending on the material contained therein.
  • Near-infrared reflective layer using flat metal particles From the viewpoint of heat ray shielding (acquisition rate of solar heat), a heat ray reflection type with no re-radiation is desirable rather than a heat ray absorption type with re-radiation of absorbed light into the room (about 1/3 of the absorbed solar energy). . From the viewpoint of reflecting near-infrared light, it is preferable to use flat metal particles as the near-infrared shielding material.
  • a near-infrared reflective layer using such flat metal particles is disclosed in JP 2013-228694 A [0019] to [0046], JP 2013-083974 A, JP 2013-080222 A, JP
  • the near-infrared shielding materials described in JP2013-080221A, JP2013-077007A, JP2013-068945A, and the like can be used, and the descriptions of these publications are incorporated in this specification.
  • the near-infrared reflective layer is a layer containing at least one kind of metal particles, and the metal particles have 60% by number or more of hexagonal or circular plate-like metal particles, and the hexagonal or circular shape.
  • the main plane of the shaped flat metal particles is plane-oriented in an average range of 0 ° to ⁇ 30 ° with respect to one surface of the near-infrared reflective layer.
  • the material of the metal particles is not particularly limited and can be appropriately selected according to the purpose. However, silver, gold, aluminum, copper, rhodium, nickel, platinum are preferred because of the high heat ray (near infrared) reflectance. Etc. are preferable.
  • a near-infrared absorbing layer of a heat ray absorption type that easily generates heat on the heat insulating film is preferable among the near-infrared shielding layers.
  • the near-infrared absorption layer [0033] of Japanese Patent Application Laid-Open No. 2014-240907, [0011] to [0022] of Japanese Patent Application Laid-Open No. 2014-214299, and [0013] to [0017] of Japanese Patent Application Laid-Open No. 2014-148567.
  • JP-A-2014-139617, [0010] to [0034], JP-A-2014-80466, [0022] to [0035] can be preferably used. Incorporated in the description.
  • the heat insulating film of the present invention preferably has an adhesive layer.
  • the adhesive layer can contain 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.
  • you may add an antistatic agent, a lubricant, an antiblocking agent, etc. to the adhesion layer.
  • the thickness of the adhesive layer is preferably 0.1 ⁇ m to 10 ⁇ m.
  • the method for producing a heat insulating film is a step of forming a fibrous metal particle-containing layer by applying a coating solution for forming a fibrous metal particle-containing layer containing fibrous metal particles mainly composed of silver and a binder onto a support. It is preferable to contain. It is also preferable to include a step of forming a surface layer by applying a coating solution for forming a surface layer having a water contact angle of 90 ° or more on the fibrous metal particle-containing layer.
  • the coating liquid for forming the fibrous metal particle-containing layer is prepared by preparing an aqueous dispersion of fibrous metal particles such as metal nanowires, and a material other than the metal oxide derived from the specific alkoxide compound described above ( For example, it may be prepared by mixing a binder mainly composed of the aforementioned conductive polymer).
  • the coating for forming the fibrous metal particle-containing layer is used as a method of forming the fibrous metal particle-containing layer on the support.
  • a liquid hereinafter also referred to as “sol-gel coating liquid” is applied onto a support to form a liquid film, and a hydrolysis and polycondensation reaction of a specific alkoxide compound in the liquid film (hereinafter referred to as this The reaction of hydrolysis and polycondensation is also referred to as “sol-gel reaction.”) To form a fibrous metal particle-containing layer by causing a reaction.
  • the sol-gel coating solution may be prepared by preparing an aqueous dispersion of fibrous metal particles such as metal nanowires and mixing this with a specific alkoxide compound.
  • an aqueous solution containing a specific alkoxide compound is prepared, and the aqueous solution is heated to hydrolyze and polycondensate at least a part of the specific alkoxide compound to form a sol state.
  • a sol-gel coating solution may be prepared by mixing with an aqueous dispersion of fibrous metal particles. In order to promote the sol-gel reaction, it is practically preferable to use an acidic catalyst or a basic catalyst in combination because the reaction efficiency can be increased.
  • the coating film After coating, it can be dried by any method, and is preferably dried by heating.
  • the binder mainly composed of the metal oxide derived from the specific alkoxide compound hydrolysis and condensation reaction of the specific alkoxide compound occurs in the coating film of the sol-gel coating liquid formed on the support.
  • the coating film is preferably heated and dried.
  • the heating temperature for promoting the sol-gel reaction is suitably in the range of 30 ° C. to 200 ° C., more preferably in the range of 50 ° C. to 180 ° C.
  • the heating and drying time is preferably 10 seconds to 300 minutes, more preferably 1 minute to 120 minutes.
  • the coating method in each step described above there is no particular limitation on the coating method in each step described above, and it can be performed by a general coating method and can be appropriately selected according to the purpose. 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 coating liquid for forming the surface layer can form a uniform liquid film on the fibrous metal particle-containing layer by using the same solvent as the fibrous metal particle-containing layer.
  • the coating liquid for forming the surface layer can form a uniform liquid film on the fibrous metal particle-containing layer by using the same solvent as the fibrous metal particle-containing layer.
  • the heat insulation glass of this invention is the heat insulation glass which laminated
  • the window of this invention is a window containing the heat insulating film of this invention bonded together to the transparent support body for windows, and the transparent support body for windows.
  • the transparent support for windows is preferably a transparent support for windows having a thickness of 0.5 mm or more, more preferably a transparent support for windows having a thickness of 1 mm or more, and is caused by the thickness of the transparent support for windows. From the viewpoint of suppressing heat conduction and increasing warmth, a transparent support for windows having a thickness of 2 mm or more is particularly preferable.
  • the transparent support for windows is generally a plate or sheet.
  • transparent support for windows 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. Examples thereof include a resin plate of resin.
  • the transparent support body for windows is a transparent glass or a resin board, and it is more preferable that it is transparent glass.
  • Transparent glass such as white plate glass, blue plate glass, silica coat blue plate glass, can be used as glass and window glass, for example.
  • the glass used in the present invention preferably has a smooth surface, and is preferably float glass.
  • the heat insulation film of this invention is affixed on the inner side of a window, ie, the indoor side of a window glass.
  • the fibrous metal particle-containing layer of the heat insulating film of the present invention is disposed on the surface of the support opposite to the surface on the window (glass) side.
  • the fibrous metal particle-containing layer depends on the thickness of the layer
  • the distance between the fibrous metal particle-containing layer and the outermost surface on the indoor side is preferably within 5 ⁇ m from the viewpoint of enhancing the heat insulating property. It is particularly preferably 1 to 5 ⁇ m or less, and particularly preferably 2 to 4 ⁇ m or less.
  • the fibrous metal particle-containing layer of the heat insulating film of the present invention is preferably in the layer next to the outermost layer on the indoor side from the viewpoint of improving heat insulating properties.
  • the near infrared shielding layer is installed on the sunlight side as much as possible because it can reflect the infrared rays entering the indoor in advance.
  • the near infrared shielding layer It is preferable to laminate the adhesive layer so that is placed on the sunlight incident side. Specifically, an adhesive layer is provided on the near-infrared shielding layer or a functional layer such as an overcoat layer provided on the near-infrared shielding layer, and is bonded to the window glass through the adhesive layer. It is preferable.
  • the heat insulating film of the present invention When the heat insulating film of the present invention is applied to the window glass, the heat insulating film of the present invention prepared by coating or laminating the adhesive layer is prepared, and the interface between the window glass surface and the adhesive layer surface of the heat insulating film of the present invention is prepared in advance. After spraying an aqueous solution containing an activator (mainly anionic), the heat insulating film of the present invention may be installed on the window glass through an adhesive layer. Until the moisture evaporates, the adhesive force of the adhesive layer decreases, and therefore the position of the heat insulating film of the present invention can be adjusted on the glass surface.
  • an activator mainly anionic
  • the window glass is swept away from the glass center toward the edge by using a squeegee or the like to leave moisture remaining between the window glass and the heat insulating film of the present invention.
  • the heat insulation film of this invention can be fixed to the surface. Thus, it is possible to install the heat insulation film of this invention in a window glass.
  • a building material is a building material containing the heat insulation film of this invention or the heat insulation glass of this invention.
  • the building is a building including the heat insulating film of the present invention, the heat insulating glass of the present invention, the building material of the present invention, or the window of the present invention.
  • buildings include houses, buildings, and warehouses.
  • the vehicle is a vehicle including the heat insulating film of the present invention, the heat insulating glass of the present invention or the window of the present invention. Examples of the vehicle include an automobile, a railway vehicle, and a ship.
  • additive liquid G 1 g of glucose powder was dissolved in 280 mL of pure water to prepare additive solution G.
  • additive solution H was prepared by dissolving 4 g of HTAB (hexadecyl-trimethylammonium bromide) powder in 220 mL of pure water.
  • a silver nanowire aqueous dispersion (1) 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 through a funnel while stirring at 20 ° C. (first stage). To this solution, 206 mL of additive solution A was added at a flow rate of 2.0 mL / min and at a stirring rotation speed of 800 rpm (round per minutes) (second stage). Ten minutes later, 82.5 mL of additive liquid H was added (third stage). Thereafter, the internal temperature was raised to 73 ° C. at 3 ° C./min.
  • the above washing was repeated until the electric conductivity (measured with CM-25R manufactured by Toa DKK Co., Ltd.) was 50 ⁇ S / cm or less, followed by concentration to obtain a 0.84% silver nanowire aqueous dispersion (1). It was.
  • the obtained silver nanowire aqueous dispersion (1) was used as the silver nanowire aqueous dispersion of Preparation Example 1.
  • the average minor axis length, the average major axis length, and the minor axis length of the fibrous metal particles were as described above. The coefficient of variation was measured.
  • silver nanowire aqueous dispersion (1) indicates the silver nanowire aqueous dispersion obtained by the above method.
  • a bonding solution 1 was prepared with the following composition.
  • Adhesive solution 1 -Takelac (registered trademark) WS-4000 5.0 parts by mass (polyurethane for coating, solid content concentration 30%, manufactured by Mitsui Chemicals, Inc.) ⁇ Surfactant 0.3 part by mass (Brand name: NAROACTY HN-100, manufactured by Sanyo Chemical Industries, Ltd.) ⁇ Surfactant 0.3 part by mass (Sandet (registered trademark) BL, solid content concentration 43%, manufactured by Sanyo Chemical Industries, Ltd.) ⁇ 94.4 parts by mass of water
  • One surface of a 75 ⁇ m-thick PET film (reference numeral 10 in FIG. 5) used as a support is subjected to corona discharge treatment, and the adhesive solution 1 is applied to the surface subjected to the corona discharge treatment, and the temperature is 120 ° C. And dried for 2 minutes to form a first adhesive layer (reference numeral 31 in FIG. 5) having a thickness of 0.11 ⁇ m.
  • An adhesive solution 2 was prepared with the following composition.
  • Adhesive solution 2 was prepared by the following method. While the aqueous acetic acid solution was vigorously stirred, 3-glycidoxypropyltrimethoxysilane was dropped into the aqueous acetic acid solution over 3 minutes. Next, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was added to the aqueous acetic acid solution over 3 minutes with vigorous stirring. Next, tetraethoxysilane was added to the acetic acid aqueous solution over 5 minutes with vigorous stirring, and then stirring was continued for 2 hours. Next, colloidal silica, a curing agent, and a surfactant were sequentially added to prepare an adhesive solution 2.
  • the adhesive solution 2 is applied to the surface by a bar coating method and heated at 170 ° C. for 1 minute. It dried and formed the 2nd contact bonding layer (code
  • Example 1 ⁇ Formation by application of fibrous metal particle-containing layer> The solution of the alkoxide compound having the following composition was stirred at 60 ° C. for 1 hour to confirm that the solution became uniform. The prepared solution was used as a sol-gel solution.
  • a sol-gel coating liquid which is a coating liquid for use, was obtained.
  • the surface of the second adhesive layer of the above support with an adhesive layer is subjected to a corona discharge treatment, and the surface is coated with a silver amount of 0.040 g / m 2 and the total solid content applied amount is 0.120 g / m.
  • the sol-gel coating solution was applied so as to be 2 . After that, it was dried at 175 ° C. for 1 minute to cause a sol-gel reaction to form a fibrous metal particle-containing layer.
  • the mass ratio of tetraethoxysilane (alkoxide compound) / silver nanowire in the fibrous metal particle-containing layer was 2/1.
  • the above surface layer composition is applied using an applicator so that the film thickness after drying is 0.2 ⁇ m, and dried by heating at 170 ° C. for 1 minute. A surface layer was formed to obtain a heat insulating film of Example 1.
  • Example 2 In Example 1, the heat insulation film of Example 2 was obtained like Example 1 except having apply
  • Example 3 In Example 1, the heat insulation film of Example 3 was obtained like Example 1 except having apply
  • Example 4 ⁇ Surface layer composition> A solution obtained by diluting a fluororesin (trade name: OPTOOL DSX, manufactured by Daikin Industries, Ltd.) used as a surface layer material to 0.1% by mass with perfluorohexane was prepared as a surface layer composition.
  • a fluororesin trade name: OPTOOL DSX, manufactured by Daikin Industries, Ltd.
  • the above surface layer composition was dip-coated at a lifting speed of 1 cm / min, and the environment was 60 ° C. and relative humidity 90% for 1 hour. After leaving, the surface layer was formed by wiping with a non-woven fabric soaked with perfluorohexane until the surface unevenness was eliminated, and the heat insulating film of Example 4 was obtained. The obtained surface layer was confirmed to be a monomolecular film by X-ray reflectivity measurement.
  • Example 5 ⁇ Hydrophobic silica dispersion> Hydrophobic fumed silica particles (trade name AEROSIL R 202, manufactured by Nippon Aerosil Co., Ltd.) as a surface layer material were added to 200 parts by mass of ethanol to prepare a hydrophobic silica dispersion.
  • Hydrophobic fumed silica particles (trade name AEROSIL R 202, manufactured by Nippon Aerosil Co., Ltd.) as a surface layer material were added to 200 parts by mass of ethanol to prepare a hydrophobic silica dispersion.
  • an acrylic silicone-based hydrophobic composition (trade name Acryt 8SS-723, manufactured by Taisei Fine Chemical Co., Ltd.), which is an acrylic silicone polymer methoxypropanol having UV (Ultraviolet) reactive groups, was prepared.
  • Example 7 ⁇ Formation by application of fibrous metal particle-containing layer> 2.09 parts by mass of the sol-gel solution obtained in Example 1, 32.70 parts by mass of the silver nanowire aqueous dispersion (1) obtained in Preparation Example 1, and a fluorosurfactant (trade name Surflon, AGC Seimi Chemical Co., Ltd.) 0.1 parts by mass was mixed and further diluted with distilled water to obtain a sol-gel coating solution which is a coating solution for forming a fibrous metal particle-containing layer.
  • a fluorosurfactant trade name Surflon, AGC Seimi Chemical Co., Ltd.
  • the surface of the second adhesive layer of the above support with an adhesive layer is subjected to a corona discharge treatment, and the surface is coated with a silver amount of 0.040 g / m 2 and the total solid content applied amount is 0.120 g / m.
  • the sol-gel coating solution was applied so as to be 2 . After that, it was dried at 175 ° C. for 1 minute to cause a sol-gel reaction to form a fibrous metal particle-containing layer.
  • the mass ratio of tetraethoxysilane (alkoxide compound) / silver nanowire in the fibrous metal particle-containing layer was 2/1.
  • the obtained laminated body was used as the heat insulating film of Example 7.
  • Example 8 ⁇ Formation of fibrous metal particle-containing layer using PEDOT / PSS binder> A poly (3,4-ethylenedioxythiophene) (PEDOT) solution doped with polystyrene sulfonic acid (PSS) having the following composition was prepared. -Poly (3,4-ethylenedioxythiophene) aqueous dispersion 50.0 parts by mass (CleviosP AI 4083, manufactured by Heraeus Co., Ltd.) -2.0 parts by mass of distilled water-8.0 parts by mass of ethanol 18.0 parts by mass of the obtained PEDOT solution and 32.70 parts by mass of the silver nanowire aqueous dispersion (1) obtained in Preparation Example 1 were mixed.
  • PEDOT poly (3,4-ethylenedioxythiophene)
  • PSS polystyrene sulfonic acid
  • distribution PEDOT coating liquid which is a coating liquid for fibrous metal particle content layer formation.
  • the surface of the second adhesive layer of the above support with an adhesive layer is subjected to a corona discharge treatment, and the surface is coated with a silver amount of 0.040 g / m 2 and the total solid content applied amount is 0.120 g / m.
  • the silver nanowire-dispersed PEDOT coating solution was applied so as to be 2 . After that, it was dried at 100 ° C. for 2 minutes to form a fibrous metal particle-containing layer using a PEDOT / PSS binder.
  • the mass ratio of binder / silver nanowire in the fibrous metal particle-containing layer using the PEDOT / PSS binder was 2/1.
  • a surface layer was formed in the same manner as in Example 2 to obtain a heat insulating film of Example 8.
  • Example 9 ⁇ Formation of fibrous metal particle-containing layer using COP binder>
  • the silver nanowire aqueous dispersion obtained in Preparation Example 1 was subjected to solvent substitution with n-propanol without changing the silver nanowire concentration of the dispersion, and then further with 1-isopropyl-4-methylcyclohexane.
  • a cycloolefin polymer (COP) solution having the following composition was prepared.
  • the above COP solution 3.50 parts by mass and the above-mentioned solvent-substituted silver nanowire aqueous dispersion 32.70 parts by mass are mixed and silver nanowire-dispersed COP coating is performed.
  • a liquid was obtained.
  • the surface of the second adhesive layer of the above support with an adhesive layer is subjected to a corona discharge treatment, and the surface is coated with a silver amount of 0.040 g / m 2 and the total solid content applied amount is 0.120 g / m.
  • the silver nanowire-dispersed COP coating solution was applied so as to be 2 . After that, it was dried at 100 ° C. for 2 minutes to form a fibrous metal particle-containing layer using a COP binder.
  • the mass ratio of COP / silver nanowire in the fibrous metal particle-containing layer using the COP binder was 2/1.
  • a surface layer was formed in the same manner as in Example 2 to obtain a heat insulating film of Example 9.
  • Example 10 ⁇ Formation of fibrous metal particle-containing layer using PU binder> A polyurethane (PU) solution having the following composition was prepared. -Polyurethane aqueous dispersion 5.0 parts by mass (trade name, Takerak (registered trademark) WS-4000, manufactured by Mitsui Chemicals, Inc.) -95.0 parts by mass of distilled water 15.0 parts by mass of the obtained PU solution and 32.70 parts by mass of the silver nanowire aqueous dispersion (1) obtained in Preparation Example 1 were mixed and further diluted with distilled water. Thus, a silver nanowire-dispersed PU coating solution was obtained.
  • PU polyurethane
  • the surface of the second adhesive layer of the above support with an adhesive layer is subjected to a corona discharge treatment, and the surface is coated with a silver amount of 0.040 g / m 2 and the total solid content applied amount is 0.120 g / m.
  • the silver nanowire-dispersed PU coating solution was applied so as to be 2 . Thereafter, it was dried at 120 ° C. for 2 minutes to form a fibrous metal particle-containing layer using a PU binder.
  • the mass ratio of PU / silver nanowires in the fibrous metal particle-containing layer using the PU binder was 2/1.
  • a surface layer was formed in the same manner as in Example 2 to obtain a heat insulating film of Example 10.
  • Example 11 ⁇ Formation of fibrous metal particle-containing layer using silicone binder> A silicone solution having the following composition was prepared. ⁇ Silicone-modified acrylic resin (trade name SQ100, solid content 50%, Co., Ltd. 5.0 parts by mass / isocyanate curing agent (trade name UAX-615, manufactured by Tokushi Co., Ltd.) 1.0 part by mass / tin-based catalyst (trade name UA-38, manufactured by Tokiki Co., Ltd.) 0.2 part by mass / 93.8 parts by mass of methyl ethyl ketone The silver nanowire aqueous dispersion obtained in Preparation Example 1 was used as a dispersion.
  • the solvent was replaced with n-propanol, and the solvent was further replaced with methyl ethyl ketone.
  • 4.4 parts by mass of the obtained silicone solution and 32.70 parts by mass of the silver nanowire aqueous dispersion subjected to the solvent replacement were mixed to obtain a silver nanowire-dispersed silicone coating liquid.
  • the surface of the second adhesive layer of the above support with an adhesive layer is subjected to a corona discharge treatment, and the surface is coated with a silver amount of 0.040 g / m 2 and the total solid content applied amount is 0.120 g / m.
  • the silver nanowire-dispersed silicone coating solution was applied so as to be 2 . After that, it was dried at 100 ° C.
  • Example 11 A surface layer was formed in the same manner as in Example 2 on the surface of the fibrous metal particle-containing layer using the above silicone binder to obtain a heat insulating film of Example 11.
  • Example 12 A near-infrared reflective layer was provided on the heat insulating film by the following method.
  • Preparation of silver tabular grain dispersion B1> (Preparation of silver tabular grain dispersion A1) Agitator with 13L of ion-exchanged water measured in a reaction vessel of NTKR-4 (manufactured by Nippon Metal Industry Co., Ltd.) and four NTKR-4 propellers and four NTKR-4 paddles attached to a SUS316L shaft While stirring using a chamber equipped with 1.0 g of 10 g / L trisodium citrate (anhydrous) aqueous solution, 1.0 L was added and kept at 35 ° C.
  • the stirring was increased to 1200 rpm, and the silver sulfite white precipitate mixture prepared by the method described later was further added to the reaction vessel.
  • 5.0 L of 1 mol / L NaOH aqueous solution was further added to the reaction vessel at 0.33 L / min.
  • an additional 2.0 g / L of 1- (meta-sulfophenyl) -5-mercaptotetrazole sodium aqueous solution NaOH and citric acid (anhydride) was added to the reaction vessel to a pH of 7.0 ⁇ 1.0.
  • the obtained silver tabular grain dispersion liquid A1 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.
  • the silver tabular grain dispersion liquid A1 was subjected to a desalting treatment and a redispersion treatment to prepare a silver tabular grain dispersion liquid B1.
  • a coating liquid M1 for a near-infrared reflective layer was prepared with the following composition.
  • -Coating liquid M1- Aqueous urethane resin Hydran HW350 (Dic Co., Ltd., solid content: 30% by mass) 0.27 parts by mass
  • Silver tabular grain dispersion B1 10.24 parts by mass 1- (methylureidophenyl) -5-mercaptotetrazole (Wako Pure Chemical Industries, Ltd.) Manufactured, prepared 2% by mass of alkaline aqueous solution) 0.61 part by mass
  • Surfactant A Lipal 870P (Manufactured by Lion Co., Ltd., diluted with ion exchange water at a solid content of 1% by mass) 0.96 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
  • Rate of change after wet heat aging 100 ⁇
  • Rate of change after wet heat aging 100 ⁇
  • the heat insulating film of the present invention can suppress a change in heat insulating property after aging with wet heat when using a fibrous metal particle-containing layer containing fibrous metal particles mainly composed of silver and a binder.
  • Comparative Examples 1 to 4 it was found that when the water contact angle on the outermost surface of the heat insulating film was less than 90 °, the change in heat insulating property after wet heat aging was large.
  • Comparative Example 4 even when the layer using a silicon resin binder (silicone binder) described in [0048] of JP2012-252172A is the outermost surface, the contact angle is 90. It was found that when the fibrous metal particle-containing layer using a silicone binder having a temperature of less than 0 ° was used, the heat insulating property change after wet heat aging was large.
  • the heat insulation film of this invention it turned out that abrasion resistance, a dirt wiping test result, and the initial value of heat insulation can also be improved.
  • the consumption of the air conditioner was reduced by 10% on average in the winter compared with the case where it was not used.
  • the consumption of the air conditioner was reduced by 15% on average in winter.
  • Example 12 of the lamination with the near-infrared reflective layer the consumption of the air conditioner in summer was further suppressed.
  • the heat insulating film of the present invention when the water contact angle is 110 ° or more, even if the heat insulating film is disposed in a high humidity environment having a relative humidity of 90% or more, the cloudiness of the surface due to water droplets is clearly visible Therefore, it is considered that the heat insulation change after wet heat aging could be suppressed.
  • the material having a water contact angle of 110 ° or more (Cytop CTX-109M) has a lower water absorption rate or water vapor transmission rate than the other binder and the material used for the surface layer. Therefore, it is considered that the penetration of moisture could be suppressed.
  • the heat insulating glass of the present invention using the heat insulating film of the present invention can suppress the heat insulating change after the aging of wet heat, the heat insulating property after the aging of the wet heat is suppressed when the heat insulating film of the present invention is arranged inside the window.
  • Such a heat insulating film of the present invention can provide a building or vehicle including a window that can achieve both low haze and high heat insulating properties.
  • the heat insulation film of this invention is a window which can suppress the heat insulation change after time-lapse

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Abstract

Provided is an insulating film having a support body and a fiber-like metal particle-containing layer that is disposed on one surface of the support body and comprises a binder and fiber-like metal particles with silver as the main component, wherein the water contact angle of the outermost surface of the insulating film is at least 90°. The insulating film is capable of suppressing changes in thermal insulation properties after being subjected to heat and humidity over time when the fiber-like metal particle-containing layer comprising the binder and fiber-like metal particles with silver as the main component is used. Further provided are an insulating glass and a window.

Description

断熱フィルム、断熱ガラスおよび窓Insulation film, insulation glass and window
　本発明は、断熱フィルム、断熱ガラスおよび窓に関する。より詳しくは、銀を主成分とする繊維状金属粒子およびバインダーを含む繊維状金属粒子含有層を用いた場合に、湿熱経時後の断熱性変化を抑制できる断熱フィルム、この断熱フィルムを用いた断熱ガラスおよびこの断熱フィルムを用いた窓に関する。 The present invention relates to a heat insulating film, a heat insulating glass, and a window. More specifically, in the case of using a fibrous metal particle-containing layer containing a fibrous metal particle and a binder containing silver as a main component, a heat insulating film capable of suppressing a change in heat insulation after wet heat aging, heat insulation using this heat insulating film The present invention relates to glass and a window using this heat insulating film.
　近年、二酸化炭素削減のための省エネルギー施策の一つとして環境負荷の少ない商品、いわゆるエコな商品が求められており、自動車や建物等の窓に対する日射調整フィルムや断熱フィルムが注目されている。断熱フィルムとは窓などに貼ることで屋内側と屋外側の熱の行き来を遅くさせるフィルムのことであり、これを使用することにより冷暖房の使用量が減り、節電効果が期待できる。断熱性は、熱貫流率で定義される。国等による環境物品等の調達の推進等に関する法律（いわゆるグリーン購入法）における窓用日射調整フィルム調達基準では、断熱性については、ＪＩＳ（Ｊａｐａｎｅｓｅ　Ｉｎｄｕｓｔｒｉａｌ　Ｓｔａｎｄａｒｄｓ）　Ａ　５７５９「建築窓ガラス用フィルム」による計測方法で、熱貫流率５．９Ｗ／（ｍ２・Ｋ）未満であることが求められており、この数字が小さいほど断熱性が高いことになる。ＪＩＳ　Ａ　５７５９によれば、熱貫流率は波長５μｍ～５０μｍの遠赤外線の反射スペクトルから求めることができる。すなわち、熱貫流率を下げるには波長５μｍ～５０μｍの遠赤外線の反射率を上げることが好ましい。 In recent years, as an energy-saving measure for reducing carbon dioxide, products with less environmental impact, so-called eco-products, have been demanded, and solar radiation adjustment films and heat insulation films for windows of automobiles and buildings have attracted attention. The heat insulating film is a film that delays the heat transfer between the indoor side and the outdoor side by sticking it on a window or the like. By using this film, the amount of air-conditioning used can be reduced, and a power saving effect can be expected. Thermal insulation is defined by the thermal conductivity. According to the solar radiation adjustment film procurement standards for windows in the law on the promotion of the procurement of environmental goods, etc. by the national government (so-called green purchasing law), JIS (Japan Industrial Standards) A 5759 “Film for architectural window glass” The measurement method requires that the heat transmissivity is less than 5.9 W / (m 2 · K), and the smaller this number, the higher the heat insulation. According to JIS A 5759, the thermal transmissivity can be obtained from the reflection spectrum of far infrared rays having a wavelength of 5 μm to 50 μm. That is, it is preferable to increase the reflectivity of far-infrared rays having a wavelength of 5 μm to 50 μm in order to reduce the heat transmissivity.
　断熱フィルムとして、断熱フィルムとしてスパッタ法などの蒸着により形成した金属薄膜と高屈折率膜の積層体を用い、表面の物性を改良する観点から表面層を設けた構成が知られている。
　例えば、特許文献１には、熱線反射フィルムの少なくとも片面の最表層に保護層を形成した積層熱線反射フィルムであって、保護層と水との接触角が９０°以上であり、保護層を構成する樹脂のガラス転移温度が１００℃以上でありかつ透明である積層熱線反射フィルムが開示されている。特許文献１の［０００５］段落には「本発明の積層熱線反射フィルムは、（イ）基材フィルムの少なくとも片面に、（ロ）金属層、（ハ）金属酸化物層及び（ニ）保護層を設けた積層フィルムである」と記載されている。 As a heat insulating film, a structure in which a laminated body of a metal thin film and a high refractive index film formed by vapor deposition such as a sputtering method is used as a heat insulating film and a surface layer is provided from the viewpoint of improving surface properties.
For example, Patent Document 1 discloses a laminated heat ray reflective film in which a protective layer is formed on the outermost layer of at least one surface of the heat ray reflective film, and the contact angle between the protective layer and water is 90 ° or more, and the protective layer is configured. The laminated heat ray reflective film whose glass transition temperature of resin to perform is 100 degreeC or more and is transparent is disclosed. In paragraph [0005] of Patent Document 1, “the laminated heat ray reflective film of the present invention has (b) a metal layer, (c) a metal oxide layer, and (d) a protective layer on at least one surface of the base film. It is a laminated film provided with ".
　特許文献２には、透明なガラス基材の少なくとも片面にアルミ粉末及び紫外線吸収剤を含む樹脂層からなる熱線反射性層を設け、ガラス基材の片面に光触媒粒子とシリコーン又は無定形シリカと撥水性フッ素樹脂とを含有する実質的に透明な表面層を積層し、表面層の表面は水との接触角が９０°以上である水滴付着防止性及び熱線遮断性を有するガラス板が開示されている。 In Patent Document 2, a heat ray reflective layer composed of a resin layer containing aluminum powder and an ultraviolet absorber is provided on at least one surface of a transparent glass substrate, and photocatalyst particles and silicone or amorphous silica and repellent material are disposed on one surface of the glass substrate. Disclosed is a glass plate having a substantially transparent surface layer containing an aqueous fluororesin, the surface layer having a contact angle with water of 90 ° or more and water droplet adhesion prevention and heat ray blocking properties. Yes.
　特許文献３には、透明基材フィルムの一方の面に、少なくとも赤外線遮蔽層を設けたフィルムにおいて、上記赤外線遮蔽層が、（Ａ）電離放射線硬化型樹脂と、（Ｂ）赤外線吸収剤と、電離放射線硬化型樹脂１００質量部当たり、（Ｃ）電離放射線硬化型シリコーン樹脂０．１～５０質量部とを含む塗膜の硬化物からなる防汚性赤外線遮蔽フィルムが開示されている。 In Patent Document 3, in a film in which at least an infrared shielding layer is provided on one surface of a transparent substrate film, the infrared shielding layer includes (A) an ionizing radiation curable resin, (B) an infrared absorber, An antifouling infrared shielding film comprising a cured product of a coating film containing (C) 0.1 to 50 parts by mass of (C) ionizing radiation curable silicone resin per 100 parts by mass of ionizing radiation curable resin is disclosed.
　また、断熱フィルムの材料に繊維状金属粒子を用い、塗布方法により製造する方法が知られている。例えば、特許文献４には、透明フィルム、およびその表面に設けられた遠赤外線反射層を含む熱線遮蔽フィルムであって、遠赤外線反射層が、繊維状金属粒子を含む熱線遮蔽フィルムが記載されている。特許文献４によれば、熱線遮蔽フィルムの遠赤外線反射層が繊維状金属粒子を含んでいるので、屋内から放射される暖房等の熱線を反射して逃がさず、外気の熱を屋内に取り込まない断熱性に優れる等と記載されている。 In addition, a method is known in which fibrous metal particles are used as the material of the heat insulating film, and manufacturing is performed by a coating method. For example, Patent Document 4 describes a heat ray shielding film including a transparent film and a far infrared reflective layer provided on the surface thereof, and the far infrared reflective layer includes a fibrous metal particle. Yes. According to Patent Document 4, since the far-infrared reflective layer of the heat ray shielding film contains fibrous metal particles, the heat rays such as heating that are radiated from the inside are not reflected and escaped, and the heat of the outside air is not taken indoors. It is described as being excellent in heat insulation.
特開平１０－２８６９００号公報JP-A-10-286900 特開２００２－１２７３１０号公報JP 2002-127310 A 特開２０００－２１１０６３号公報JP 2000-211063 A 特開２０１２－２５２１７２号公報JP 2012-252172 A
　窓ガラスの内側に貼付されて使用される断熱フィルムは、室内からの遠赤外線を反射して熱が窓ガラスを通して逃げることを防止する。 The heat insulating film used by being attached to the inside of the window glass reflects far infrared rays from the room to prevent heat from escaping through the window glass.
　本発明者らが断熱フィルムを湿熱環境下で経時させる（例えば冬期に温かい室内で使用する）ことを検討したところ、特許文献４などに記載の銀を主成分とする繊維状金属粒子およびバインダーを含む繊維状金属粒子含有層を用いた場合に、断熱フィルム表面に結露が発生するなどの問題が生じ、水が遠赤外線の良好な吸収体となり、熱伝導により熱を逃がしてしまうため、断熱フィルムの性能を発揮できなくなることがわかった。いかなる理論に拘泥するものでもないが、銀を主成分とする繊維状金属粒子とバインダーとを有する繊維状金属粒子含有層を用いた遠赤外線反射層の場合は、湿熱経時後の断熱性変化が生じやすい。銀が金属酸化物でバリアされておらず、比表面積が大きく、端面以外の膜のどこからでも腐食開始されるために銀が腐食されやすい点と、銀を主成分とする繊維状金属粒子が切断され長さが変わると遠赤外線反射性能の劣化に直結する点などに起因すると考えられる。特許文献４はフィルム表面が結露することの課題を見いだせていないため、結露による断熱効率の顕著な低下が発生するものであった。また、特許文献４の構成ではフィルム表面に長時間水滴が滞留することで、繊維状金属粒子含有層の経時劣化も発生してしまうと予想される。なお、特許文献４では結露から反射層を保護するため２重ガラス窓の中空内部に断熱フィルムを配置する構成をとっており、断熱フィルム上に直接、結露防止層を配置することの記載はない。 When the present inventors examined that the heat insulating film is aged in a humid heat environment (for example, used in a warm room in winter), the fibrous metal particles mainly containing silver and the binder described in Patent Document 4 are used. When using a fibrous metal particle-containing layer that contains, problems such as the occurrence of condensation on the surface of the heat insulating film arise, water becomes a good absorber of far infrared rays, and heat is released by heat conduction, so the heat insulating film It was found that the performance of can not be demonstrated. Although not bound by any theory, in the case of a far-infrared reflective layer using a fibrous metal particle-containing layer having fibrous metal particles mainly composed of silver and a binder, the heat insulation change after aging with wet heat Prone to occur. Silver is not barriered by metal oxide, has a large specific surface area, and since corrosion starts from anywhere on the film other than the end face, silver is easily corroded, and fibrous metal particles based on silver are cut However, it is thought that this is due to the fact that if the length is changed, it directly leads to the deterioration of the far-infrared reflection performance. Since patent document 4 has not found the subject that the film surface dew condensation, the remarkable fall of the heat insulation efficiency by dew condensation generate | occur | produced. Moreover, in the structure of patent document 4, it is estimated that a time-dependent deterioration of a fibrous metal particle content layer will also generate | occur | produce because a water droplet stays on the film surface for a long time. In addition, in patent document 4, in order to protect a reflection layer from dew condensation, the structure which has arrange | positioned the heat insulation film in the hollow inside of a double glass window is taken, and there is no description of arrange | positioning a dew condensation prevention layer directly on a heat insulation film. .
　これに対し、特許文献１～３では、赤外線反射層において、銀を主成分とする繊維状金属粒子を使用することの記載はない。また、特許文献１～３の熱線遮蔽フィルムや断熱ガラスでは、湿熱環境下で経時させた場合の断熱性変化はあまり大きくなかった。そのため、銀を主成分とする繊維状金属粒子およびバインダーを含む繊維状金属粒子含有層を用いた場合に湿熱経時後の断熱性変化が大きくなってしまうという課題は、銀を主成分とする繊維状金属粒子を使用していない特許文献１～３ではあまり問題とならなかった新規課題であった。 On the other hand, Patent Documents 1 to 3 do not describe the use of fibrous metal particles mainly composed of silver in the infrared reflecting layer. In addition, in the heat ray shielding films and the heat insulating glasses of Patent Documents 1 to 3, the change in heat insulating property when aged in a humid heat environment is not so large. Therefore, when the fibrous metal particle-containing layer containing a fibrous metal particle mainly containing silver and a binder is used, the problem that the heat insulating property change after wet heat aging becomes large is a fiber mainly containing silver. In Patent Documents 1 to 3 that do not use the metal particles, this is a new problem that has not been a problem.
　したがって、特許文献１～４に記載の方法を含め、銀を主成分とする繊維状金属粒子およびバインダーを含む繊維状金属粒子含有層を用いた場合に、湿熱経時後の断熱性変化を抑制できる断熱フィルムについては知られていないのが実情であった。 Therefore, including the methods described in Patent Documents 1 to 4, when a fibrous metal particle-containing layer containing fibrous metal particles containing silver as a main component and a binder can be used, it is possible to suppress a change in heat insulation after wet heat aging. The fact is that the heat insulation film is not known.
　本発明が解決しようとする課題は、銀を主成分とする繊維状金属粒子およびバインダーを含む繊維状金属粒子含有層を用いた場合に、湿熱経時後の断熱性変化を抑制できる断熱フィルムを提供することである。 The problem to be solved by the present invention is to provide a heat insulating film capable of suppressing a change in heat insulating property after wet heat aging when a fibrous metal particle-containing layer containing fibrous metal particles mainly composed of silver and a binder is used. It is to be.
　本発明者らは鋭意検討を行った結果、銀を主成分とする繊維状金属粒子およびバインダーを含む繊維状金属粒子含有層を用いた場合に、断熱フィルムの最表面の水接触角が９０°以上であることで、湿熱経時後の断熱性変化を抑制できる断熱フィルムを提供できることを見出した。 As a result of intensive studies, the present inventors have found that the water contact angle of the outermost surface of the heat insulating film is 90 ° when the fibrous metal particle-containing layer containing the fibrous metal particle mainly composed of silver and the binder is used. By the above, it discovered that the heat insulation film which can suppress the heat insulation change after wet heat aging can be provided.
　即ち、本発明は、以下の具体的手段により達成できる。
［１］　支持体と、
　支持体の一方の面上に配置され、銀を主成分とする繊維状金属粒子およびバインダーを含む繊維状金属粒子含有層とを有する断熱フィルムであって、
　断熱フィルムの最表面の水接触角が９０°以上である、断熱フィルム。
［２］　［１］に記載の断熱フィルムは、断熱フィルムの水接触角が９０°以上である最表面が、支持体よりも繊維状金属粒子含有層に近い側の最表面であることが好ましい。
［３］　［１］または［２］に記載の断熱フィルムは、繊維状金属粒子含有層の支持体とは反対の面上に、さらに水接触角が９０°以上である表面層を含むことが好ましい。
［４］　［３］に記載の断熱フィルムは、表面層の主成分が、フッ素を含有する材料またはケイ素を含有する材料であることが好ましい。
［５］　［３］または［４］に記載の断熱フィルムは、表面層の膜厚が、１μｍ以下であることが好ましい。
［６］　［３］～［５］のいずれか一つに記載の断熱フィルムは、表面層が、単分子膜であることが好ましい。
［７］　［１］～［６］のいずれか一つに記載の断熱フィルムは、繊維状金属粒子含有層のバインダーの主成分が、ケイ素を含有する材料であることが好ましい。
［８］　［１］～［７］のいずれか一つに記載の断熱フィルムは、支持体の繊維状金属粒子含有層が配置された面とは反対の面に、さらに近赤外線遮蔽層を含むことが好ましい。
［９］　［１］～［８］のいずれか一つに記載の断熱フィルムは、断熱フィルムの最表面の水接触角が１１０°以上であることが好ましい。
［１０］　［１］～［９］のいずれか一つに記載の断熱フィルムは、支持体が、透明フィルムであることが好ましい。
［１１］　［１］～［１０］のいずれか一つに記載の断熱フィルムは、繊維状金属粒子の平均長軸長が５～５０μｍであることが好ましい。
［１２］　［１］～［１１］のいずれか一つに記載の断熱フィルムは、窓の内側に配置され、
　繊維状金属粒子含有層が、支持体の窓側の面とは反対側の面上に配置されることが好ましい。
［１３］　［１］～［１２］のいずれか一つに記載の断熱フィルムと、ガラスとを積層した断熱ガラス。
［１４］　窓用透明支持体と、窓用透明支持体に貼り合わせた［１］～［１２］のいずれか一つに記載の断熱フィルムを含む、窓。 That is, the present invention can be achieved by the following specific means.
[1] a support;
A heat insulating film that is disposed on one surface of a support and has a fibrous metal particle-containing layer containing a fibrous metal particle mainly composed of silver and a binder,
The heat insulation film whose water contact angle of the outermost surface of a heat insulation film is 90 degrees or more.
[2] In the heat insulating film according to [1], the outermost surface of the heat insulating film having a water contact angle of 90 ° or more is preferably the outermost surface closer to the fibrous metal particle-containing layer than the support. .
[3] The heat insulating film according to [1] or [2] may further include a surface layer having a water contact angle of 90 ° or more on a surface opposite to the support of the fibrous metal particle-containing layer. preferable.
[4] In the heat insulating film according to [3], the main component of the surface layer is preferably a material containing fluorine or a material containing silicon.
[5] In the heat insulating film according to [3] or [4], the film thickness of the surface layer is preferably 1 μm or less.
[6] In the heat insulating film according to any one of [3] to [5], the surface layer is preferably a monomolecular film.
[7] In the heat-insulating film according to any one of [1] to [6], the main component of the binder of the fibrous metal particle-containing layer is preferably a material containing silicon.
[8] The heat insulating film according to any one of [1] to [7] further includes a near-infrared shielding layer on a surface of the support opposite to the surface on which the fibrous metal particle-containing layer is disposed. It is preferable.
[9] In the heat insulating film according to any one of [1] to [8], the water contact angle on the outermost surface of the heat insulating film is preferably 110 ° or more.
[10] In the heat insulating film according to any one of [1] to [9], the support is preferably a transparent film.
[11] In the heat insulating film according to any one of [1] to [10], the average major axis length of the fibrous metal particles is preferably 5 to 50 μm.
[12] The heat insulating film according to any one of [1] to [11] is disposed inside the window,
It is preferable that the fibrous metal particle-containing layer is disposed on the surface of the support opposite to the window side.
[13] A heat insulating glass in which the heat insulating film according to any one of [1] to [12] and glass are laminated.
[14] A window comprising the transparent support for windows and the heat insulating film according to any one of [1] to [12] bonded to the transparent support for windows.
　本発明によれば、銀を主成分とする繊維状金属粒子およびバインダーを含む繊維状金属粒子含有層を用いた場合に、湿熱経時後の断熱性変化を抑制できる断熱フィルムを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, when the fibrous metal particle content layer containing the fibrous metal particle which has silver as a main component, and a binder is used, the heat insulation film which can suppress the heat insulation change after wet heat aging can be provided. .
図１は、本発明の断熱フィルムの一例の断面を示す概略図である。FIG. 1 is a schematic view showing a cross section of an example of the heat insulating film of the present invention. 図２は、本発明の断熱フィルムの他の一例の断面を示す概略図である。FIG. 2 is a schematic view showing a cross section of another example of the heat insulating film of the present invention. 図３は、本発明の断熱フィルムの他の一例の断面を示す概略図である。FIG. 3 is a schematic view showing a cross section of another example of the heat insulating film of the present invention. 図４は、本発明の断熱フィルムの他の一例の断面を示す概略図である。FIG. 4 is a schematic view showing a cross section of another example of the heat insulating film of the present invention. 図５は、本発明の断熱ガラスの一例の断面を示す概略図である。FIG. 5 is a schematic view showing a cross section of an example of the heat insulating glass of the present invention.
　以下において、本発明について詳細に説明する。以下に記載する構成要件の説明は、代表的な実施形態や具体例に基づいてなされることがあるが、本発明はそのような実施形態に限定されるものではない。なお、本明細書において「～」を用いて表される数値範囲は「～」前後に記載される数値を下限値および上限値として含む範囲を意味する。
　本明細書中、組成物の主成分とは、組成物の全量に対して５０質量％以上含まれる成分のことを言う。例えば、バインダーの主成分とは、バインダーの全量に対して５０質量％以上含まれる成分のことを意味する。表面層の主成分とは、表面層の全量に対して５０質量％以上含まれる成分のことを意味する。 Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, the main component of a composition means the component contained 50 mass% or more with respect to the whole quantity of a composition. For example, the main component of the binder means a component contained in an amount of 50% by mass or more based on the total amount of the binder. The main component of the surface layer means a component contained by 50% by mass or more with respect to the total amount of the surface layer.
［断熱フィルム］
　本発明の断熱フィルムは、支持体と、支持体の一方の面上に配置され、銀を主成分とする繊維状金属粒子およびバインダーを含む繊維状金属粒子含有層とを有する断熱フィルムであって、断熱フィルムの最表面の水接触角が９０°以上である。
　このような構成により、銀を主成分とする繊維状金属粒子およびバインダーを含む繊維状金属粒子含有層を用いた場合に、湿熱経時後の断熱性変化を抑制できる断熱フィルムを提供できる。ここで、断熱フィルムの表面に水滴が付着すると、水滴が遠赤外線を吸収し、断熱性が顕著に損なわれる。いかなる理論に拘泥するものでもないが、断熱フィルムの表面を疎水性にすることによって、水分を素早く凝集落下することが必要であると考えられる。本発明によれば、断熱フィルムの最表面の水の接触角を９０°以上の疎水性とすることにより、水蒸気による結露自体を抑制するか、あるいは、結露した水滴を自重で落としやすくして、断熱効率を維持するとともに、水滴の長期滞留による繊維状金属粒子含有層の劣化を防止することができると考えられる。また、水蒸気による結露自体を抑制するか、あるいは、結露した水滴を自重で落としやすくして、水滴を通して侵入する硫黄成分によって銀が腐食される時間を短くして、湿熱経時後の断熱性変化を抑制できると考えられる。本発明の断熱フィルムに用いている遠赤外線反射を担う銀を主成分とする繊維状金属粒子は、水滴がフィルム表面に長期に留まることで、空気中から溶け込んだ硫黄成分で硫化してしまいやすく、断線や導電性低下による断熱性能の劣化が、Ａｇスパッタ膜等よりも発生しやすいため、断熱フィルムの最表面の水接触角が９０°以上であることによる湿熱経時後の断熱性変化の抑制効果が極めて高い。 [Insulation film]
The heat-insulating film of the present invention is a heat-insulating film having a support and a fibrous metal particle-containing layer that is disposed on one surface of the support and contains fibrous metal particles mainly containing silver and a binder. The water contact angle on the outermost surface of the heat insulating film is 90 ° or more.
With such a configuration, when a fibrous metal particle-containing layer containing fibrous metal particles mainly containing silver and a binder is used, it is possible to provide a heat insulating film that can suppress a heat insulating change after wet heat aging. Here, when water droplets adhere to the surface of the heat insulating film, the water droplets absorb far-infrared rays, and the heat insulating properties are significantly impaired. Without being bound by any theory, it is believed that it is necessary to quickly agglomerate and drop moisture by making the surface of the heat insulating film hydrophobic. According to the present invention, by making the contact angle of the water on the outermost surface of the heat insulating film hydrophobic to 90 ° or more, the condensation itself due to water vapor is suppressed, or the condensed water droplets are easily dropped by their own weight, It is thought that while maintaining the heat insulation efficiency, it is possible to prevent the deterioration of the fibrous metal particle-containing layer due to the long-term retention of water droplets. In addition, it suppresses the condensation itself due to water vapor, or makes it easy to drop condensed water droplets by its own weight, shortens the time that silver is corroded by the sulfur component that penetrates through the water droplets, and changes the heat insulation after aging It can be suppressed. The fibrous metal particles mainly composed of silver responsible for far-infrared reflection used in the heat insulating film of the present invention are likely to be sulfided with sulfur components dissolved from the air because water droplets stay on the film surface for a long time. Insulation performance deterioration due to disconnection or conductivity decrease is more likely to occur than with Ag sputtered films, etc., so that the heat contact change after wet heat aging due to the water contact angle of the outermost surface of the heat insulation film being 90 ° or more The effect is extremely high.
　本発明の断熱フィルムの好ましい態様は、断熱フィルム表面が疎水性であるため、埃や油汚れ等が付着した場合でも、水拭きにより簡単に除去できる効果を有する。
　また、本発明の断熱フィルムの好ましい態様の一例である、さらに近赤外線遮蔽層を含む遮熱／断熱の両機能を有する断熱フィルムでは、太陽光からの熱線が遮蔽され、結露しやすい状況になるため、さらに湿熱経時後の断熱性変化を抑制できる効果が高い。
　本発明の断熱フィルムの好ましい態様では、真空成膜法で形成された積層導電層よりも製造性に優れる。
　以下、本発明の断熱フィルムの好ましい態様を説明する。 A preferred embodiment of the heat insulating film of the present invention has an effect that the surface of the heat insulating film is hydrophobic, so that it can be easily removed by wiping with water even when dust or oil stains adhere.
Moreover, in the heat insulation film which has an example of the preferable aspect of the heat insulation film of this invention and has both the heat insulation / heat insulation function containing a near-infrared shielding layer, the heat ray from sunlight is shielded and it will be in the condition which is easy to dew condensation. Therefore, the effect which can further suppress the heat insulation change after wet heat aging is high.
In the preferable aspect of the heat insulation film of this invention, it is excellent in productivity rather than the laminated conductive layer formed by the vacuum film-forming method.
Hereinafter, the preferable aspect of the heat insulation film of this invention is demonstrated.
＜特性＞
（最表面の水接触角）
　本発明の断熱フィルムは、断熱フィルムの最表面の水接触角が９０°以上である。断熱フィルムの最表面の水接触角は、１００°以上であることが湿熱経時後の断熱性変化を抑制する観点から好ましく、１０５°以上であることがより好ましく、１１０°以上であることが特に好ましい。
　特に断熱フィルムの最表面の水接触角が１１０°以上であると、水蒸気による結露自体を抑制するか、あるいは、結露した水滴を自重で落としやすくことで、繊維状金属含有層への水分の浸透を抑制して湿熱経時後の断熱性変化を抑制できるようになる。さらに、水接触角が大きい材料は吸水率や水蒸気透過率が低く、繊維状金属粒子含有層への水分の侵入を抑制することで、湿熱経時後の断熱性変化を抑制できる。
　断熱フィルムの最表面の水接触角を制御する方法としては特に制限はないが、繊維状金属粒子含有層が最表面である場合は、繊維状金属粒子含有層の水接触角が９０°以上となるバインダーを用いて繊維状金属粒子含有層を形成する方法や、繊維状金属粒子含有層に添加剤を添加する方法を挙げることができる。表面層が最表面である場合は、水接触角が大きい表面を形成できる材料を表面層の主成分として用いる方法を挙げることができる。耐擦性の観点からは、本発明の断熱フィルムは、繊維状金属粒子含有層の支持体とは反対の面上に、さらに水接触角が９０°以上である表面層を含むことが好ましい。 <Characteristic>
(Surface water contact angle)
As for the heat insulation film of this invention, the water contact angle of the outermost surface of a heat insulation film is 90 degrees or more. The water contact angle of the outermost surface of the heat insulating film is preferably 100 ° or more from the viewpoint of suppressing a change in heat insulation after wet heat aging, more preferably 105 ° or more, and particularly preferably 110 ° or more. preferable.
In particular, when the water contact angle of the outermost surface of the heat insulating film is 110 ° or more, moisture permeation into the fibrous metal-containing layer can be achieved by suppressing condensation itself due to water vapor or by easily dropping the condensed water droplets by their own weight. It becomes possible to suppress the heat insulation change after wet heat aging. Furthermore, a material having a large water contact angle has a low water absorption rate and water vapor transmission rate, and by suppressing the intrusion of moisture into the fibrous metal particle-containing layer, it is possible to suppress a change in heat insulating properties after aging with moisture.
The method for controlling the water contact angle of the outermost surface of the heat insulating film is not particularly limited, but when the fibrous metal particle-containing layer is the outermost surface, the water contact angle of the fibrous metal particle-containing layer is 90 ° or more. The method of forming a fibrous metal particle content layer using the binder which becomes, and the method of adding an additive to a fibrous metal particle content layer can be mentioned. In the case where the surface layer is the outermost surface, a method using a material capable of forming a surface having a large water contact angle as a main component of the surface layer can be mentioned. From the viewpoint of abrasion resistance, the heat insulating film of the present invention preferably includes a surface layer having a water contact angle of 90 ° or more on the surface opposite to the support of the fibrous metal particle-containing layer.
（断熱性の湿熱経時後変化率）
　本発明の断熱フィルムは、断熱性（後述の熱貫流率、Ｕ値）の湿熱経時後変化率が小さい。本発明の断熱フィルムは、後述の実施例に記載の方法で求められる湿熱経時後変化率が、１０％以下であることが好ましく、９％以下であることがより好ましく、７％以下であることが特に好ましく、５％以下であることがより特に好ましく、４％以下であることがさらにより特に好ましい。 (The rate of change in heat-insulating wet heat over time)
The heat-insulating film of the present invention has a small rate of change in heat insulating properties (heat transmissivity described later, U value) after wet heat aging. In the heat insulating film of the present invention, the rate of change after wet heat aging determined by the method described in Examples below is preferably 10% or less, more preferably 9% or less, and 7% or less. Is particularly preferably 5% or less, more preferably 4% or less.
（断熱性）
　本発明の断熱フィルムは、断熱性（熱貫流率、Ｕ値）の初期値が優れることが好ましい。本発明の断熱フィルムは、断熱性（Ｕ値）の初期値が５．５Ｗ／ｍ２・Ｋ以下であることが好ましく、５．２Ｗ／ｍ２・Ｋ以下であることがより好ましく、４．９Ｗ／ｍ２・Ｋ以下であることが特に好ましい。 (Thermal insulation properties)
The heat insulating film of the present invention is preferably excellent in the initial value of heat insulating properties (heat transmissivity, U value). Insulation film of the present invention preferably has an initial value of the thermal insulation (U value) is less than 5.5W / m 2 · K, more preferably at most 5.2W / m 2 · K, 4 . It is particularly preferably 9 W / m 2 · K or less.
　本発明の断熱フィルムの好ましい態様では、さらに電波透過性にも優れることが、携帯電話等の発する有用電波の透過性を高める観点から好ましい。電波透過性の観点では表面抵抗を高くすることが好ましい。一般に繊維状金属粒子含有層は、スパッタ金属積層体よりも表面抵抗が高く、好ましい。繊維状金属粒子含有層の表面抵抗を高くすることで、電波透過性はより良好となる。表面抵抗が１０００Ω／□（Ω毎スクエア）以上であることが、電波透過性を高める観点から好ましく、１００００Ω／□以上がより好ましい。 In a preferred embodiment of the heat insulating film of the present invention, it is preferable that the radio wave permeability is further excellent from the viewpoint of enhancing the permeability of useful radio waves emitted from a mobile phone or the like. From the viewpoint of radio wave permeability, it is preferable to increase the surface resistance. In general, the fibrous metal particle-containing layer has a higher surface resistance than the sputtered metal laminate and is preferable. By increasing the surface resistance of the fibrous metal particle-containing layer, the radio wave transmission becomes better. The surface resistance is preferably 1000 Ω / □ (Ω per square) or more from the viewpoint of improving radio wave transmission, and more preferably 10000 Ω / □ or more.
＜構成＞
　本発明の断熱フィルムの構成について、説明する。
　図１～図４に本発明の断熱フィルムの一例の断面を示す概略図を示した。図５に本発明の断熱フィルムを含む、本発明の断熱ガラスの一例の断面を示す概略図を示した。
　図１に示した本発明の断熱フィルムは、支持体１０と、繊維状金属粒子含有層２０とを含む。図２に示した本発明の断熱フィルムは、支持体１０と、繊維状金属粒子含有層２０と、表面層２１とをこの順で含む。ここで、本発明の断熱フィルムは、断熱フィルムの水接触角が９０°以上である最表面が、支持体よりも繊維状金属粒子含有層に近い側の最表面であることが好ましい。図１に示した断熱フィルムの一例では、繊維状金属粒子含有層２０が、水接触角が９０°以上である最表面であることが好ましい。一方、図２に示した断熱フィルムの一例では、表面層２１が、水接触角が９０°以上である最表面であることが好ましい。すなわち、本発明の断熱フィルムは、図２に示すとおり、繊維状金属粒子含有層２０の支持体１０とは反対の面上に、さらに水接触角が９０°以上である表面層２１を含むことが好ましい。 <Configuration>
The structure of the heat insulation film of this invention is demonstrated.
1 to 4 are schematic views showing a cross section of an example of the heat insulating film of the present invention. The schematic which shows the cross section of an example of the heat insulation glass of this invention containing the heat insulation film of this invention in FIG. 5 was shown.
The heat insulating film of the present invention shown in FIG. 1 includes a support 10 and a fibrous metal particle-containing layer 20. The heat insulation film of this invention shown in FIG. 2 contains the support body 10, the fibrous metal particle content layer 20, and the surface layer 21 in this order. Here, as for the heat insulation film of this invention, it is preferable that the outermost surface whose water contact angle of a heat insulation film is 90 degrees or more is an outermost surface of the side closer to a fibrous metal particle content layer than a support body. In the example of the heat insulating film shown in FIG. 1, the fibrous metal particle-containing layer 20 is preferably the outermost surface having a water contact angle of 90 ° or more. On the other hand, in the example of the heat insulating film shown in FIG. 2, the surface layer 21 is preferably the outermost surface having a water contact angle of 90 ° or more. That is, as shown in FIG. 2, the heat insulating film of the present invention further includes a surface layer 21 having a water contact angle of 90 ° or more on the surface opposite to the support 10 of the fibrous metal particle-containing layer 20. Is preferred.
　本発明の断熱フィルムは窓用の断熱フィルムであることが好ましい。本発明の断熱フィルムは、窓の内側に配置されることが好ましく、繊維状金属粒子含有層２０が支持体１０の窓（図５におけるガラス６１）側の面とは反対側の面上に配置されることが遠赤外線を反射しやすいために好ましい。断熱フィルムがないときは屋内の遠赤外線がガラスに吸収されて、ガラス中を熱伝導することにより、屋内の熱が屋外に出てしまうが、断熱フィルムがあると遠赤外線を屋内に反射するため屋内の熱が屋外に出にくくなる。繊維状金属粒子含有層２０は、できるだけ屋内側の最外層に近い層にあることが好ましく、表面層２１が最外層であり、繊維状金属粒子含有層２０が最外層の次の層にあることが断熱性を高める観点から好ましい。 The heat insulating film of the present invention is preferably a heat insulating film for windows. The heat insulating film of the present invention is preferably arranged inside the window, and the fibrous metal particle-containing layer 20 is arranged on the surface of the support 10 opposite to the window (glass 61 in FIG. 5) side. This is preferable because it is easy to reflect far infrared rays. When there is no heat insulation film, indoor far infrared rays are absorbed by the glass, and heat conduction through the glass causes indoor heat to go out outdoors, but if there is a heat insulation film, the far infrared rays are reflected indoors. Indoor heat is less likely to go out. The fibrous metal particle-containing layer 20 is preferably in a layer as close as possible to the outermost layer on the indoor side, the surface layer 21 is the outermost layer, and the fibrous metal particle-containing layer 20 is in the layer next to the outermost layer. Is preferable from the viewpoint of enhancing heat insulation.
　図３に示した本発明の断熱フィルムは、粘着層５１と、支持体１０と、繊維状金属粒子含有層２０と、表面層２１とをこの順で含む。
　本発明の断熱フィルムは図３または図４に示すように粘着層５１を支持体１０の窓（図５におけるガラス６１）側の面に有することが好ましく、ガラス６１と粘着層５１を貼り合わせられることが好ましい。 The heat insulating film of the present invention shown in FIG. 3 includes an adhesive layer 51, a support 10, a fibrous metal particle-containing layer 20, and a surface layer 21 in this order.
The heat insulating film of the present invention preferably has an adhesive layer 51 on the window (glass 61 in FIG. 5) side of the support 10 as shown in FIG. 3 or FIG. 4, and the glass 61 and the adhesive layer 51 are bonded together. It is preferable.
　本発明の断熱フィルムは、支持体の繊維状金属粒子含有層が配置された面とは反対の面に、さらに近赤外線遮蔽層を含むことが好ましく、例えば図４に示す層構成で近赤外線遮蔽層４１を含むことが好ましい。図４では、本発明の断熱フィルムの一例は、近赤外遮蔽材料を含む近赤外線遮蔽層４１を有する。近赤外遮蔽材料は、近赤外線遮蔽層４１を単独で形成せずに、その他の層に含まれていてもよい。例えば、近赤外遮蔽材料が、繊維状金属粒子含有層２０に含まれていてもよく、第１の接着層３１や第２の接着層３２に含まれていてもよく、粘着層５１に含まれていてもよい。近赤外遮蔽材料は、支持体の繊維状金属粒子含有層が配置された面とは反対の面、すなわち支持体１０の窓（ガラス６１）側の面側の層に含まれることが、近赤外光を遮蔽する観点から好ましい。 The heat insulating film of the present invention preferably further includes a near-infrared shielding layer on the surface of the support opposite to the surface on which the fibrous metal particle-containing layer is disposed. For example, the layer structure shown in FIG. Preferably, layer 41 is included. In FIG. 4, an example of the heat insulation film of this invention has the near-infrared shielding layer 41 containing a near-infrared shielding material. The near-infrared shielding material may be contained in other layers without forming the near-infrared shielding layer 41 alone. For example, the near-infrared shielding material may be included in the fibrous metal particle-containing layer 20, may be included in the first adhesive layer 31 or the second adhesive layer 32, and is included in the adhesive layer 51. It may be. The near-infrared shielding material is included in the surface of the support opposite to the surface on which the fibrous metal particle-containing layer is arranged, that is, the layer on the surface of the support 10 on the window (glass 61) side. This is preferable from the viewpoint of shielding infrared light.
　図５に示した本発明の断熱ガラス１１１は、本発明の断熱フィルム１０３と、ガラス６１を含む。本発明の断熱フィルム１０３は、ガラス６１が窓の一部（窓ガラス）である場合に、窓の内側（屋内側、室内側、日中における太陽光入射側とは反対側、図５中のＩＮ側）に配置されることが好ましい。
　支持体１０と、繊維状金属粒子含有層２０と、表面層２１が、接着層を介して貼り合わせられた積層体を断熱部材１０２と言うことがある。接着層は単層でも２層以上の積層体でもよく、図５では接着層は第１の接着層３１および第２の接着層３２の積層体である。また、支持体１０上に、接着層（図５では第１の接着層３１および第２の接着層３２の積層体）を設けた積層体を、接着層付きの支持体１０１と言うことがある。
　以下、本発明の断熱フィルムを構成する各層の好ましい態様を説明する。 The heat insulating glass 111 of the present invention shown in FIG. 5 includes the heat insulating film 103 of the present invention and the glass 61. When the glass 61 is a part of the window (window glass), the heat insulating film 103 of the present invention is the inside of the window (indoor side, indoor side, opposite to the sunlight incident side in the daytime, in FIG. (IN side) is preferable.
The laminated body in which the support 10, the fibrous metal particle-containing layer 20, and the surface layer 21 are bonded together through an adhesive layer may be referred to as a heat insulating member 102. The adhesive layer may be a single layer or a laminate of two or more layers. In FIG. 5, the adhesive layer is a laminate of the first adhesive layer 31 and the second adhesive layer 32. Moreover, the laminated body which provided the contact bonding layer (The laminated body of the 1st contact bonding layer 31 and the 2nd contact bonding layer 32 in FIG. 5) on the support body 10 may be called the support body 101 with an contact bonding layer. .
Hereinafter, the preferable aspect of each layer which comprises the heat insulation film of this invention is demonstrated.
＜支持体＞
　上記支持体としては、繊維状金属粒子含有層を担うことができるものである限り、目的に応じて種々のものを使用することができる。一般的には、板状またはシート状のものが使用される。
　支持体は、透明であっても、不透明であってもよいが、透明であることが好ましく、可視光に透明であることがより好ましい。支持体は全可視光透過率が７０％以上であることが好ましく、８５％以上であることがより好ましく、９０％以上であることが更に好ましい。なお、支持体の全可視光透過率は、ＩＳＯ（Ｉｎｔｅｒｎａｔｉｏｎａｌ　Ｏｒｇａｎｉｚａｔｉｏｎ　ｆｏｒ　Ｓｔａｎｄａｒｄｉｚａｔｉｏｎ）　１３４６８－１（１９９６）に準拠して測定される。
　本発明の断熱フィルムは、支持体が、透明フィルムであることが好ましい。
　支持体を構成する素材としては、例えば、ポリカーボネート、ポリエーテルスルホン、ポリエステル、アクリル樹脂、塩化ビニル樹脂、芳香族ポリアミド樹脂、ポリアミドイミド、ポリイミド、ポリエチレンテレフタレート、ポリシクロオレフィン等の合成樹脂を挙げることができる。これらの支持体の繊維状金属粒子含有層が形成される表面は、所望により、アルカリ性水溶液による清浄化処理、シランカップリング剤などの薬品処理、プラズマ処理、イオンプレーティング、スパッタリング、気相反応法、真空蒸着などにより前処理がされていてもよい。
　支持体の厚さは、用途に応じて所望の範囲のものが使用される。一般的には、１μｍ～５００μｍの範囲から選択され、３μｍ～４００μｍがより好ましく、５μｍ～３００μｍが更に好ましい。 <Support>
As the support, various materials can be used depending on the purpose as long as the support can bear the fibrous metal particle-containing layer. Generally, a plate or sheet is used.
The support may be transparent or opaque, but is preferably transparent and more preferably transparent to visible light. The support preferably has a total visible light transmittance of 70% or more, more preferably 85% or more, and still more preferably 90% or more. The total visible light transmittance of the support is measured in accordance with ISO (International Organization for Standardization) 13468-1 (1996).
In the heat insulating film of the present invention, the support is preferably a transparent film.
Examples of the material constituting the support include synthetic resins such as polycarbonate, polyethersulfone, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamideimide, polyimide, polyethylene terephthalate, and polycycloolefin. it can. The surface of the support on which the fibrous metal particle-containing layer is formed is optionally cleaned with an alkaline aqueous solution, chemical treatment such as a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method. Alternatively, pretreatment may be performed by vacuum deposition or the like.
The support has a desired thickness depending on the application. Generally, it is selected from the range of 1 μm to 500 μm, more preferably 3 μm to 400 μm, and even more preferably 5 μm to 300 μm.
＜繊維状金属粒子含有層＞
　本発明では、繊維状金属粒子含有層は、支持体の一方の面上に配置され、銀を主成分とする繊維状金属粒子およびバインダーを含む。
　繊維状金属粒子含有層は、遠赤外線を反射させるには空隙サイズが小さいことが好ましく、例えば繊維状金属粒子含有層の断面写真において、８０％以上の空隙の空隙サイズが２５（μｍ）２以下の空隙面積であることがより好ましい。 <Fibrous metal particle-containing layer>
In the present invention, the fibrous metal particle-containing layer is disposed on one surface of the support and includes fibrous metal particles mainly composed of silver and a binder.
The fibrous metal particle-containing layer preferably has a small void size for reflecting far infrared rays. For example, in a cross-sectional photograph of the fibrous metal particle-containing layer, the void size of 80% or more voids is 25 (μm) 2 or less. The void area is more preferable.
（繊維状金属粒子）
　本発明では、銀を主成分とする繊維状金属粒子を用いる。
　繊維状金属粒子は繊維状であり、繊維状は、ワイヤ状や線状と同義である。
　繊維状金属粒子としては、金属ナノワイヤ、棒状金属粒子を挙げることができる。繊維状金属粒子としては、金属ナノワイヤが好ましい。以下、金属ナノワイヤを繊維状金属粒子の代表例として説明することがあるが、金属ナノワイヤに関する説明は繊維状金属粒子の一般的な説明として用いることができる。 (Fibrous metal particles)
In the present invention, fibrous metal particles mainly composed of silver are used.
The fibrous metal particles are fibrous, and the fibrous form is synonymous with a wire form or a line form.
Examples of the fibrous metal particles include metal nanowires and rod-like metal particles. As the fibrous metal particles, metal nanowires are preferable. Hereinafter, metal nanowires may be described as representative examples of the fibrous metal particles, but the description regarding the metal nanowires can be used as a general description of the fibrous metal particles.
　繊維状金属粒子含有層は、繊維状金属粒子として、平均短軸長１５０ｎｍ以下の金属ナノワイヤを含有することが好ましい。平均短軸長が１５０ｎｍ以下であると、断熱性が向上し、光散乱等による光学特性の悪化が生じにくくなるため、好ましい。金属ナノワイヤなどの繊維状金属粒子は、中実構造であることが好ましい。 The fibrous metal particle-containing layer preferably contains metal nanowires having an average minor axis length of 150 nm or less as the fibrous metal particles. 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. The fibrous metal particles such as metal nanowires preferably have a solid structure.
　より透明な繊維状金属粒子含有層を形成しやすいという観点からは、例えば、金属ナノワイヤなどの繊維状金属粒子は、平均短軸長が１ｎｍ～１５０ｎｍのものが好ましい。
　製造時の扱い易さから、金属ナノワイヤなどの繊維状金属粒子の平均短軸長（平均直径）は、１００ｎｍ以下であることが好ましく、６０ｎｍ以下であることがより好ましく、５０ｎｍ以下であることが更に好ましく、特に２５ｎｍ以下であることがヘイズに関して一段と優れるものが得られるので好ましい。平均短軸長を１ｎｍ以上とすることにより、耐酸化性が良好で、耐候性に優れる繊維状金属粒子含有層が容易に得られる。平均短軸長は５ｎｍ以上であることがより好ましく、１０ｎｍ以上であることが更に好ましく、１５ｎｍ以上であることが特に好ましい。 From the viewpoint of easily forming a more transparent fibrous metal particle-containing layer, for example, the fibrous metal particles such as metal nanowires preferably have an average minor axis length of 1 nm to 150 nm.
From the viewpoint of ease of handling during production, the average minor axis length (average diameter) of fibrous metal particles such as metal nanowires is preferably 100 nm or less, more preferably 60 nm or less, and 50 nm or less. More preferably, it is particularly preferably 25 nm or less, since a further excellent haze can be obtained. By setting the average minor axis length to 1 nm or more, a fibrous metal particle-containing layer having good oxidation resistance and excellent weather resistance can be easily 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.
　金属ナノワイヤなどの繊維状金属粒子の平均長軸長は、反射したい遠赤外線の反射帯域と同じ程度であることが、その反射したい遠赤外線の反射帯域を反射しやすい観点から好ましい。本発明では、金属ナノワイヤなどの繊維状金属粒子の平均長軸長は、５μｍ～５０μｍであることが波長５～５０μｍの遠赤外線を反射しやすい観点から好ましく、１０μｍ～４０μｍがより好ましく、１５μｍ～４０μｍが更に好ましい。特に、金属ナノワイヤの平均長軸長が４０μｍ以下であると、金属ナノワイヤを凝集物が生じることなく合成することが容易となり、平均長軸長が１５μｍ以上であると、十分な断熱性を得ることが容易となる。
　金属ナノワイヤなどの繊維状金属粒子の平均短軸長（平均直径）および平均長軸長は、例えば、透過型電子顕微鏡（Ｔｒａｎｓｍｉｓｓｉｏｎ　Ｅｌｅｃｔｒｏｎ　Ｍｉｃｒｏｓｃｏｐｅ；ＴＥＭ）と光学顕微鏡を用い、ＴＥＭ像や光学顕微鏡像を観察することにより求めることができる。具体的には、金属ナノワイヤなどの繊維状金属粒子の平均短軸長（平均直径）および平均長軸長は、透過型電子顕微鏡（日本電子株式会社製、商品名：ＪＥＭ－２０００ＦＸ）を用い、ランダムに選択した３００個の金属ナノワイヤについて、各々短軸長と長軸長を測定し、その平均値から金属ナノワイヤなどの繊維状金属粒子の平均短軸長と平均長軸長を求めることができる。本明細書ではこの方法で求めた値を採用している。なお、金属ナノワイヤの短軸方向断面が円形でない場合の短軸長は、短軸方向の測定で最も長い箇所の長さを短軸長とする。また。金属ナノワイヤなどの繊維状金属粒子が曲がっている場合、それを弧とする円を考慮し、その半径、および曲率から算出される値を長軸長とする。 The average major axis length of the fibrous metal particles such as metal nanowires is preferably about the same as the far-infrared reflection band to be reflected from the viewpoint of easily reflecting the far-infrared reflection band to be reflected. In the present invention, the average major axis length of fibrous metal particles such as metal nanowires is preferably 5 μm to 50 μm from the viewpoint of easily reflecting far infrared rays having a wavelength of 5 to 50 μm, more preferably 10 μm to 40 μm, and more preferably 15 μm to More preferably, it is 40 μm. In particular, when the average major axis length of the metal nanowires is 40 μm or less, it becomes easy to synthesize the metal nanowires without generating aggregates, and when the average major axis length is 15 μm or more, sufficient heat insulation is obtained. Becomes easy.
The average minor axis length (average diameter) and the average major axis length of the fibrous metal particles such as metal nanowires are measured using, for example, a transmission electron microscope (TEM) and an optical microscope, and a TEM image or an optical microscope image is obtained. It can be determined by observing. Specifically, the average minor axis length (average diameter) and the average major axis length of the fibrous metal particles such as metal nanowires were measured using a transmission electron microscope (manufactured by JEOL Ltd., trade name: JEM-2000FX). About 300 randomly selected metal nanowires, the short axis length and the long axis length can be measured, respectively, and the average short axis length and the average long axis length of the fibrous metal particles such as metal nanowires can be obtained from the average value. . In this specification, the value obtained by this method is adopted. In addition, the short-axis length when the short-axis direction cross section of metal nanowire is not circular makes the length of the longest part the short-axis length by the measurement of a short-axis direction. Also. When fibrous metal particles, such as metal nanowires, are bent, a circle having the arc as an arc is taken into consideration, and a value calculated from the radius and the curvature is taken as the major axis length.
　ある実施態様においては、繊維状金属粒子含有層における全金属ナノワイヤなどの繊維状金属粒子の含有量に対する、短軸長（直径）が１５０ｎｍ以下であり、かつ長軸長が５μｍ以上５０μｍ以下である金属ナノワイヤなどの繊維状金属粒子の含有量が、金属量で５０質量％以上であることが好ましく、６０質量％以上であることがより好ましく、７５質量％以上であることが更に好ましい。
　短軸長（直径）が１５０ｎｍ以下であり、長さが５μｍ以上５０μｍ以下である金属ナノワイヤなどの繊維状金属粒子の割合が、５０質量％以上であることで、十分な断熱性が得られるとともに、短軸長の大きい粒子や長さの短い粒子に起因するヘイズの低下を抑制しうるため好ましい。繊維状金属粒子以外の導電性粒子が繊維状金属粒子含有層に実質的に含まれない構成では、プラズモン吸収が強い場合にも透明度の低下を避け得る。 In one embodiment, the minor axis length (diameter) is 150 nm or less and the major axis length is 5 μm or more and 50 μm or less with respect to the content of fibrous metal particles such as all-metal nanowires in the fibrous metal particle-containing layer. The content of fibrous metal particles such as metal nanowires is preferably 50% by mass or more in terms of metal amount, more preferably 60% by mass or more, and further preferably 75% by mass or more.
When the minor axis length (diameter) is 150 nm or less and the ratio of the fibrous metal particles such as metal nanowires having a length of 5 μm or more and 50 μm or less is 50% by mass or more, sufficient heat insulation can be obtained. It is preferable because the haze reduction caused by particles having a short axis length and particles having a short length can be suppressed. In a configuration in which conductive particles other than the fibrous metal particles are not substantially contained in the fibrous metal particle-containing layer, a decrease in transparency can be avoided even when plasmon absorption is strong.
　繊維状金属粒子含有層に用いられる金属ナノワイヤなどの繊維状金属粒子の短軸長（直径）の変動係数は、４０％以下が好ましく、３５％以下がより好ましく、３０％以下が更に好ましい。
　変動係数が４０％以下であると、波長５～５０μｍの遠赤外線を反射しやすい金属ナノワイヤの比率が増えて、透明性と断熱性の観点で好ましい。
　金属ナノワイヤなどの繊維状金属粒子の短軸長（直径）の変動係数は、例えば透過型電子顕微鏡（ＴＥＭ）像からランダムに選択した３００個のナノワイヤの短軸長（直径）を計測し、その標準偏差と算術平均値を算出し、標準偏差を算術平均値で除することにより、求めることができる。 The coefficient of variation of the short axis length (diameter) of fibrous metal particles such as metal nanowires used in the fibrous metal particle-containing layer is preferably 40% or less, more preferably 35% or less, and even more preferably 30% or less.
When the coefficient of variation is 40% or less, the ratio of metal nanowires that easily reflect far-infrared rays having a wavelength of 5 to 50 μm increases, which is preferable from the viewpoint of transparency and heat insulation.
The coefficient of variation of the short axis length (diameter) of a fibrous metal particle such as a metal nanowire is measured by measuring the short axis length (diameter) of 300 nanowires randomly selected from a transmission electron microscope (TEM) image, for example. It can be obtained by calculating the standard deviation and the arithmetic mean value and dividing the standard deviation by the arithmetic mean value.
　本発明に用いうる金属ナノワイヤなどの繊維状金属粒子のアスペクト比は、１０以上であることが好ましい。ここで、アスペクト比とは、平均短軸長に対する平均長軸長の比（平均長軸長／平均短軸長）を意味する。前述の方法により算出した平均長軸長と平均短軸長から、アスペクト比を算出することができる。 The aspect ratio of fibrous metal particles such as metal nanowires that can be used in the present invention is preferably 10 or more. Here, 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.
　金属ナノワイヤなどの繊維状金属粒子のアスペクト比は、１０以上であれば特に制限はなく、目的に応じて適宜選択することができるが、１０～１００，０００が好ましく、５０～１００，０００がさらに好ましく、１００～１００，０００がより好ましい。
　アスペクト比が１０以上であると、金属ナノワイヤなどの繊維状金属粒子同士が均一に分散したネットワークが容易に形成され、高い断熱性を有する繊維状金属粒子含有層が容易に得られる。また、アスペクト比が１００，０００以下であると、例えば支持体上に繊維状金属粒子含有層を塗布により設ける際の塗布液において、金属ナノワイヤなどの繊維状金属粒子同士が絡まって凝集物を形成することが抑制され、安定な塗布液が得られるので、繊維状金属粒子含有層の製造が容易となる。
　繊維状金属粒子含有層に含まれる全金属ナノワイヤなどの繊維状金属粒子の質量に対するアスペクト比が１０以上の金属ナノワイヤなどの繊維状金属粒子の含有量は特に制限されない。例えば、７０質量％以上であることが好ましく、７５質量％以上であることがより好ましく、８０質量％以上であることが最も好ましい。 The aspect ratio of the fibrous metal particles such as metal nanowires 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. 100 to 100,000 is more preferable.
When the aspect ratio is 10 or more, a network in which fibrous metal particles such as metal nanowires are uniformly dispersed is easily formed, and a fibrous metal particle-containing layer having high heat insulation is easily obtained. Further, when the aspect ratio is 100,000 or less, for example, in a coating solution when a fibrous metal particle-containing layer is provided on a support by coating, fibrous metal particles such as metal nanowires are entangled to form an aggregate. Since it is suppressed and a stable coating liquid is obtained, manufacture of a fibrous metal particle content layer becomes easy.
The content of fibrous metal particles such as metal nanowires having an aspect ratio with respect to the mass of the fibrous metal particles such as all metal nanowires contained in the fibrous metal 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 most preferably 80% by mass or more.
　金属ナノワイヤなどの繊維状金属粒子の形状としては、例えば円柱状、直方体状、断面が多角形となる柱状など任意の形状であり得るが、高い透明性が必要とされる用途では、円柱状や断面が５角形以上の多角形であって鋭角的な角が存在しない断面形状であるものが好ましい。
　金属ナノワイヤなどの繊維状金属粒子の断面形状は、支持体上に金属ナノワイヤなどの繊維状金属粒子水分散液を塗布し、断面を透過型電子顕微鏡（ＴＥＭ）で観察することにより検知することができる。 The shape of the fibrous metal particles such as metal nanowires may be any shape such as a columnar shape, a rectangular parallelepiped shape, or a columnar shape with a polygonal cross section, but for applications that require high transparency, It is preferable that the cross section is a polygon having a pentagon or more and a cross section having no acute angle.
The cross-sectional shape of fibrous metal particles such as metal nanowires can be detected by applying an aqueous dispersion of fibrous metal particles such as metal nanowires on a support and observing the cross-section with a transmission electron microscope (TEM). it can.
　本発明では、繊維状金属粒子を形成する金属は銀を主成分とすること以外は特に制限がない。１種の金属以外にも２種以上の金属を組み合わせて用いてもよく、合金を用いることも可能である。これらの中でも、金属単体又は金属化合物から形成されるものが好ましく、金属単体から形成されるものがより好ましい。
　繊維状金属粒子を形成する金属としては、長周期律表（ＩＵＰＡＣ（Ｉｎｔｅｒｎａｔｉｏｎａｌ　Ｕｎｉｏｎ　ｏｆ　Ｐｕｒｅ　ａｎｄ　Ａｐｐｌｉｅｄ　Ｃｈｅｍｉｓｔｒｙ）１９９１）の第４周期、第５周期、および第６周期からなる群から選ばれる少なくとも１種の金属が好ましく、第２～１４族から選ばれる少なくとも１種の金属がより好ましく、第２族、第８族、第９族、第１０族、第１１族、第１２族、第１３族、および第１４族から選ばれる少なくとも１種の金属が更に好ましいが、少なくとも銀を主成分として含む。 In this invention, there is no restriction | limiting in particular except that the metal which forms a fibrous metal particle has silver as a main component. 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 that forms the fibrous metal particles is at least one selected from the group consisting of the fourth period, the fifth period, and the sixth period of the Long Periodic Table (IUPAC (International Union of Pure and Applied Chemistry) 1991). And at least one metal selected from Groups 2 to 14 is more preferable. Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, Group 13, And at least one metal selected from Group 14 is more preferred, but it contains at least silver as a main component.
　金属としては、具体的には銅、銀、金、白金、パラジウム、ニッケル、錫、コバルト、ロジウム、イリジウム、鉄、ルテニウム、オスミウム、マンガン、モリブデン、タングステン、ニオブ、タンタル、チタン、ビスマス、アンチモン、鉛、および、これらのうちいずれかを含む合金などが挙げられる。これらの中でも、銅、銀、金、白金、パラジウム、ニッケル、錫、コバルト、ロジウム、イリジウム又はこれらの合金が好ましく、パラジウム、銅、銀、金、白金、錫、又は、これらのうちいずれかを含む合金がより好ましく、銀又は銀を含有する合金が特に好ましい。ここで銀を含有する合金における銀の含有量は合金の全量に対して５０モル％以上であることが好ましく、６０モル％以上であることがより好ましく、８０モル％以上であることがさらに好ましい。 Specific examples of 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. Among these, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium or alloys thereof are preferable, palladium, copper, silver, gold, platinum, tin, or any of these The alloy containing is more preferable, and silver or an alloy containing silver is particularly preferable. Here, 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. .
　銀を主成分繊維状金属粒子は、銀ナノワイヤであることが好ましい。
　繊維状金属粒子含有層に含まれる全金属ナノワイヤなどの繊維状金属粒子の質量に対する銀ナノワイヤの含有量は、本発明の効果を妨げない限り特に制限されない。例えば、繊維状金属粒子含有層に含まれる全金属ナノワイヤなどの繊維状金属粒子の質量に対する銀ナノワイヤの含有量は５０質量％以上であることが好ましく、８０質量％以上であることがより好ましく、全金属ナノワイヤなどの繊維状金属粒子が実質的に銀ナノワイヤであることが更に好ましい。ここで「実質的に」とは、不可避的に混入する銀以外の金属原子を許容することを意味する。 The silver-based fibrous metal particles are preferably silver nanowires.
The content of silver nanowires with respect to the mass of fibrous metal particles such as all metal nanowires contained in the fibrous metal particle-containing layer is not particularly limited as long as the effects of the present invention are not hindered. For example, the content of silver nanowires with respect to the mass of fibrous metal particles such as all metal nanowires contained in the fibrous metal particle-containing layer is preferably 50% by mass or more, more preferably 80% by mass or more, More preferably, the fibrous metal particles such as all metal nanowires are substantially silver nanowires. Here, “substantially” means that metal atoms other than silver inevitably mixed are allowed.
　繊維状金属粒子含有層の単位面積当たりの質量（製膜時の塗布液の全固形分の塗布量）は、繊維状金属粒子含有層の断熱性、全光透過率およびヘイズ値が所望の範囲となるよう選択される。塗布量が少なすぎると十分な断熱性を得られなくなり、多すぎるとヘイズ増加の原因となったり、繊維状金属粒子含有層の割れや剥がれなどの故障の原因となる。好ましくは０．０５０～１．０００ｇ／ｍ２の範囲であり、より好ましくは０．１００～０．６００ｇ／ｍ２の範囲であり、０．１１０～０．５００ｇ／ｍ２であることが特に好ましい。 The mass per unit area of the fibrous metal particle-containing layer (the coating amount of the total solid content of the coating liquid during film formation) is the desired range of the heat insulating property, total light transmittance, and haze value of the fibrous metal particle-containing layer. Is selected. If the coating amount is too small, sufficient heat insulating properties cannot be obtained. If the coating amount is too large, haze increases or a failure such as cracking or peeling of the fibrous metal particle-containing layer occurs. Preferably it is in the range of 0.050 to 1.000 g / m 2 , more preferably in the range of 0.100 to 0.600 g / m 2 , and particularly preferably in the range of 0.110 to 0.500 g / m 2. preferable.
　繊維状金属粒子含有層に対する繊維状金属粒子の量は、繊維状金属粒子含有層の断熱性、全光透過率およびヘイズ値が所望の範囲となるよう選択されることが好ましい。繊維状金属粒子の量が十分に多いと良好な断熱性を得られ、十分に少ないとヘイズ増加の原因とならず、繊維状金属粒子含有層の電波透過性が低下する原因とならなくなる。繊維状金属粒子含有層に対する繊維状金属粒子の量は、１～６５質量％であることが好ましく、３～５０質量％であることがより好ましく、５～３５質量％であることが特に好ましい。 The amount of the fibrous metal particles relative to the fibrous metal particle-containing layer is preferably selected so that the heat insulating property, the total light transmittance, and the haze value of the fibrous metal particle-containing layer are in a desired range. When the amount of the fibrous metal particles is sufficiently large, good heat insulating properties can be obtained, and when the amount is sufficiently small, the haze increase is not caused, and the radio wave permeability of the fibrous metal particle-containing layer is not lowered. The amount of the fibrous metal particles relative to the fibrous metal particle-containing layer is preferably 1 to 65% by mass, more preferably 3 to 50% by mass, and particularly preferably 5 to 35% by mass.
－繊維状金属粒子の製造方法－
　金属ナノワイヤなどの繊維状金属粒子は、特に制限はなく、いかなる方法で作製されたものであってもよい。以下のように、ハロゲン化合物と分散剤を溶解した溶媒中で金属イオンを還元することによって製造することが好ましい。また、金属ナノワイヤなどの繊維状金属粒子を形成した後は、常法により脱塩処理を行うことが、分散性、繊維状金属粒子含有層の経時安定性の観点から好ましい。
　金属ナノワイヤなどの繊維状金属粒子の製造方法としては、特開２００９－２１５５９４号公報、特開２００９－２４２８８０号公報、特開２００９－２９９１６２号公報、特開２０１０－８４１７３号公報、特開２０１０－８６７１４号公報などに記載の方法を用いることができる。 -Manufacturing method of fibrous metal particles-
The fibrous metal particles such as metal nanowires are not particularly limited and may be produced by any method. As described below, it is preferable to produce by reducing metal ions in a solvent in which a halogen compound and a dispersant are dissolved. Moreover, after forming fibrous metal particles such as metal nanowires, it is preferable to perform a desalting treatment by a conventional method from the viewpoints of dispersibility and temporal stability of the fibrous metal particle-containing layer.
As methods for producing fibrous metal particles such as metal nanowires, JP2009-215594A, JP2009-242880A, JP2009-299162A, JP2010-84173A, and JP2010-A. The method described in Japanese Patent No. 86714 can be used.
　金属ナノワイヤなどの繊維状金属粒子の製造に用いられる溶媒としては、親水性溶媒が好ましく、例えば、水、アルコール系溶媒、エーテル系溶媒、ケトン系溶媒などが挙げられ、これらは１種単独で使用してもよく、２種以上を併用してもよい。
　アルコール系溶媒としては、例えば、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、エチレングリコールなどが挙げられる。
　エーテル系溶媒としては、例えば、ジオキサン、テトラヒドロフランなどが挙げられる。
　ケトン系溶媒としては、例えば、アセトンなどが挙げられる。
　加熱する場合、その加熱温度は、２５０℃以下が好ましく、２０℃以上２００℃以下がより好ましく、３０℃以上１８０℃以下が更に好ましく、４０℃以上１７０℃以下が特に好ましい。上記温度を２０℃以上とすることで、形成される金属ナノワイヤなどの繊維状金属粒子の長さが分散安定性を確保しうる好ましい範囲となり、且つ、２５０℃以下とすることで、金属ナノワイヤの断面外周が鋭角を有しない、なめらかな形状となるため、金属粒子の表面プラズモン吸収による着色が抑えられ、透明性の観点から好適である。
　なお、必要に応じて、粒子形成過程で温度を変更してもよく、途中での温度変更は核形成の制御や再核発生の抑制、選択成長の促進による単分散性向上の効果があることがある。 The solvent used for the production of fibrous metal particles such as metal nanowires is preferably a hydrophilic solvent, and examples thereof include water, alcohol solvents, ether solvents, ketone solvents, and these are used alone. You may use 2 or more types together.
Examples of the alcohol solvent include methanol, ethanol, propanol, isopropanol, butanol, and ethylene glycol.
Examples of the ether solvent include dioxane and tetrahydrofuran.
Examples of the ketone solvent include acetone.
In the case of heating, 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 particularly preferably 40 ° C. or higher and 170 ° C. or lower. By setting the temperature to 20 ° C. or higher, the length of the fibrous metal particles such as metal nanowires to be formed is in a preferable range that can ensure dispersion stability, and by setting the temperature to 250 ° C. or lower, Since the outer periphery of the cross section has a smooth shape without an acute angle, the coloring due to surface plasmon absorption of the metal particles is suppressed, which is preferable from the viewpoint of transparency.
If necessary, the temperature may be changed during the grain formation process. Changing the temperature during the process has the effect of controlling nucleation, suppressing renucleation, and improving monodispersity by promoting selective growth. There is.
　加熱処理は、還元剤を添加して行うことが好ましい。
　還元剤としては、特に制限はなく、通常使用されるものの中から適宜選択することができ、例えば、水素化ホウ素金属塩、水素化アルミニウム塩、アルカノールアミン、脂肪族アミン、ヘテロ環式アミン、芳香族アミン、アラルキルアミン、アルコール、有機酸類、還元糖類、糖アルコール類、亜硫酸ナトリウム、ヒドラジン化合物、デキストリン、ハイドロキノン、ヒドロキシルアミン、エチレングリコール、グルタチオンなどが挙げられる。これらの中でも、還元糖類、その誘導体としての糖アルコール類、エチレングリコールが特に好ましい。
　還元剤によっては、機能として分散剤や溶媒としても機能する化合物があり、同様に好ましく用いることができる。 The heat treatment is preferably performed by adding a reducing agent.
The reducing agent is not particularly limited and can be appropriately selected from those usually used. For example, borohydride metal salt, aluminum hydride salt, alkanolamine, aliphatic amine, heterocyclic amine, aromatic Group amines, aralkylamines, alcohols, organic acids, reducing sugars, sugar alcohols, sodium sulfite, hydrazine compounds, dextrin, hydroquinone, hydroxylamine, ethylene glycol, glutathione and the like. Among these, reducing sugars, sugar alcohols as derivatives thereof, and ethylene glycol are particularly preferable.
Depending on the reducing agent, there is a compound that functions as a dispersant or a solvent as a function, and can be preferably used in the same manner.
　金属ナノワイヤなどの繊維状金属粒子の製造は分散剤と、ハロゲン化合物又はハロゲン化金属微粒子を添加して行うことが好ましい。
　分散剤とハロゲン化合物の添加のタイミングは、還元剤の添加前でも添加後でもよく、金属イオンあるいはハロゲン化金属微粒子の添加前でも添加後でもよいが、単分散性のよりよい繊維状金属粒子を得るためには、核形成と成長を制御できるため、ハロゲン化合物の添加を２段階以上に分けることが好ましい。 The production of fibrous metal particles such as metal nanowires 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 the metal ions or metal halide fine particles. In order to obtain it, it is preferable to divide the addition of the halogen compound into two or more stages because nucleation and growth can be controlled.
　分散剤を添加する段階は特に制限されない。金属ナノワイヤなどの繊維状金属粒子を調製する前に添加し、分散剤存在下で金属ナノワイヤなどの繊維状金属粒子を添加してもよいし、金属ナノワイヤなどの繊維状金属粒子調製後に分散状態の制御のために添加しても構わない。
　分散剤としては、例えばアミノ基含有化合物、チオール基含有化合物、スルフィド基含有化合物、アミノ酸又はその誘導体、ペプチド化合物、多糖類、多糖類由来の天然高分子、合成高分子、又はこれらに由来するゲル等の高分子化合物類、などが挙げられる。これらのうち分散剤として好ましく用いられる各種高分子化合物類は、後述するポリマーに包含される化合物である。 The step of adding the dispersant is not particularly limited. It may be added before the preparation of fibrous metal particles such as metal nanowires, and may be added in the presence of a dispersing agent, or may be added after the preparation of fibrous metal particles such as metal nanowires. You may add for control.
Examples of the dispersant include an amino group-containing compound, a thiol group-containing compound, a sulfide group-containing compound, an amino acid or a derivative thereof, a peptide compound, a polysaccharide, a natural polymer derived from a polysaccharide, a synthetic polymer, or a gel derived therefrom. And the like, and the like. Among these, various polymer compounds that are preferably used as a dispersant are compounds included in the polymer described below.
　分散剤として好適に用いられるポリマーとしては、例えば保護コロイド性のあるポリマーであるゼラチン、ポリビニルアルコール、メチルセルロース、ヒドロキシプルピルセルロース、ポリアルキレンアミン、ポリアクリル酸の部分アルキルエステル、ポリビニルピロリドン、ポリビニルピロリドン構造を含む共重合体、アミノ基やチオール基を有するポリアクリル酸、等の親水性基を有するポリマーが好ましく挙げられる。
　分散剤として用いるポリマーはゲル浸透クロマトグラフィー（ｇｅｌ　ｐｅｒｍｅａｔｉｏｎ　ｃｈｒｏｍａｔｏｇｒａｐｈｙ；ＧＰＣ）により測定した重量平均分子量（ｗｅｉｇｈｔ　ａｖｅｒａｇｅ　ｍｏｌｅｃｕｌａｒ　ｗｅｉｇｈｔ；Ｍｗ）が、３０００以上３０００００以下であることが好ましく、５０００以上１０００００以下であることがより好ましい。
　分散剤として使用可能な化合物の構造については、例えば「顔料の事典」（伊藤征司郎編、株式会社朝倉書店発行、２０００年）の記載を参照できる。
　使用する分散剤の種類によって得られる金属ナノワイヤの形状を変化させることができる。 Examples of the polymer suitably used as the dispersant include gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, polyalkylene amine, polyalkylene amine, partially alkyl ester of polyacrylic acid, polyvinyl pyrrolidone, and polyvinyl pyrrolidone structure, which are protective colloid polymers. Preferably, a polymer having a hydrophilic group such as a copolymer containing 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) of 3,000 to 300,000, preferably 5,000 to 100,000, as measured by gel permeation chromatography (GPC). Is more preferable.
For the structure of the compound that can be used as the dispersant, for example, the description of “Encyclopedia of Pigments” (edited by Seijiro Ito, published by Asakura Shoten Co., Ltd., 2000) can be referred to.
The shape of the metal nanowire obtained can be changed depending on the type of the dispersant used.
　ハロゲン化合物は、臭素、塩素、ヨウ素を含有する化合物であれば特に制限はなく、目的に応じて適宜選択することができ、例えば、臭化ナトリウム、塩化ナトリウム、ヨウ化ナトリウム、ヨウ化カリウム、臭化カリウム、塩化カリウム等のアルカリハライドや下記の分散添加剤と併用できる化合物が好ましい。
　ハロゲン化合物は、分散添加剤として機能するものがありうるが、同様に好ましく用いることができる。
　ハロゲン化合物の代替としてハロゲン化銀微粒子を使用してもよいし、ハロゲン化合物とハロゲン化銀微粒子を共に使用してもよい。 The halogen compound is not particularly limited as long as it is a compound containing bromine, chlorine, or iodine, and can be appropriately selected according to the purpose. For example, sodium bromide, sodium chloride, sodium iodide, potassium iodide, odor Preference is given to compounds that can be used in combination with alkali halides such as potassium chloride and potassium chloride and the following dispersion additives.
Although the halogen compound may function as a dispersion additive, it can be preferably used in the same manner.
As an alternative to the halogen compound, silver halide fine particles may be used, or both a halogen compound and silver halide fine particles may be used.
　また、分散剤の機能とハロゲン化合物の機能との双方を有する単一の物質を用いてもよい。即ち、分散剤としての機能を有するハロゲン化合物を用いることで、１つの化合物で、分散剤とハロゲン化合物の双方の機能を発現する。
　分散剤の機能を有するハロゲン化合物としては、例えば、アミノ基と臭化物イオンを含むヘキサデシル－トリメチルアンモニウムブロミド（ＨＴＡＢ）、アミノ基と塩化物イオンを含むヘキサデシル－トリメチルアンモニウムクロライド（ＨＴＡＣ）、アミノ基と臭化物イオン又は塩化物イオンを含むドデシルトリメチルアンモニウムブロミド、ドデシルトリメチルアンモニウムクロリド、ステアリルトリメチルアンモニウムブロミド、ステアリルトリメチルアンモニウムクロリド、デシルトリメチルアンモニウムブロミド、デシルトリメチルアンモニウムクロリド、ジメチルジステアリルアンモニウムブロミド、ジメチルジステアリルアンモニウムクロリド、ジラウリルジメチルアンモニウムブロミド、ジラウリルジメチルアンモニウムクロリド、ジメチルジパルミチルアンモニウムブロミド、ジメチルジパルミチルアンモニウムクロリド、などが挙げられる。
　金属ナノワイヤなどの繊維状金属粒子の製造方法においては、金属ナノワイヤなどの繊維状金属粒子形成後に脱塩処理を行うことが好ましい。金属ナノワイヤなどの繊維状金属粒子形成後の脱塩処理は、限外ろ過、透析、ゲルろ過、デカンテーション、遠心分離などの手法により行うことができる。 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.
Examples of the halogen compound having a dispersant function 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. Dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, stearyl trimethyl ammonium chloride, decyl trimethyl ammonium bromide, decyl trimethyl ammonium chloride, dimethyl distearyl ammonium bromide, dimethyl distearyl ammonium chloride, di Lauryldimethylammonium bromide, dilauryldimethylammonium chloride Chloride, dimethyl dipalmityl ammonium bromide, dimethyl dipalmityl ammonium chloride, and the like.
In the method for producing fibrous metal particles such as metal nanowires, desalting is preferably performed after the formation of fibrous metal particles such as metal nanowires. The desalting treatment after formation of fibrous metal particles such as metal nanowires can be performed by techniques such as ultrafiltration, dialysis, gel filtration, decantation, and centrifugation.
　金属ナノワイヤなどの繊維状金属粒子は、アルカリ金属イオン、アルカリ土類金属イオン、ハロゲン化物イオン等の無機イオンをなるべく含まないことが好ましい。金属ナノワイヤを水性溶媒に分散させてなる分散物の電気伝導度は１ｍＳ／ｃｍ以下が好ましく、０．１ｍＳ／ｃｍ以下がより好ましく、０．０５ｍＳ／ｃｍ以下が更に好ましい。
　金属ナノワイヤなどの繊維状金属粒子の水分散物の２５℃における粘度は、０．５ｍＰａ・ｓ～１００ｍＰａ・ｓが好ましく、１ｍＰａ・ｓ～５０ｍＰａ・ｓがより好ましい。
　電気伝導度および粘度は、水分散物における金属ナノワイヤなどの繊維状金属粒子の濃度を０．４５質量％として測定される。水分散物における金属ナノワイヤなどの繊維状金属粒子の濃度が上記濃度より高い場合には、水分散物を蒸留水にて希釈して測定する。 It is preferable that fibrous metal particles such as metal nanowires contain as little inorganic ions as possible, such as alkali metal ions, alkaline earth metal ions, and halide ions. The electrical conductivity of a dispersion obtained by dispersing metal nanowires 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 at 25 ° C. of the aqueous dispersion of fibrous metal particles such as metal nanowires is preferably 0.5 mPa · s to 100 mPa · s, and more preferably 1 mPa · s to 50 mPa · s.
Electrical conductivity and viscosity are measured at a concentration of fibrous metal particles such as metal nanowires in the aqueous dispersion of 0.45% by mass. When the concentration of fibrous metal particles such as metal nanowires in the aqueous dispersion is higher than the above concentration, the aqueous dispersion is diluted with distilled water and measured.
（バインダー）
　繊維状金属粒子含有層は、バインダーを含む。
　上記バインダーを含むことにより、繊維状金属粒子含有層における金属ナノワイヤなどの繊維状金属粒子の分散が安定に維持される上、支持体表面に繊維状金属粒子含有層を、接着層を介することなく形成した場合においても支持体と繊維状金属粒子含有層との強固な接着が確保される傾向がある。 (binder)
The fibrous metal particle-containing layer contains a binder.
By containing the binder, the dispersion of the fibrous metal particles such as metal nanowires in the fibrous metal particle-containing layer is stably maintained, and the fibrous metal particle-containing layer is not formed on the support surface without an adhesive layer. Even when it is formed, there is a tendency that strong adhesion between the support and the fibrous metal particle-containing layer is secured.
　好ましいバインダーとしては、Ｓｉ、Ｔｉ、ＺｒおよびＡｌからなる群より選ばれる元素（ｂ）のアルコキシド化合物を加水分解および重縮合して得られるゾルゲル硬化物、導電性高分子、有機高分子ポリマー（導電性高分子を除く）を挙げることができる。繊維状金属粒子含有層のバインダーの主成分が、ゾルゲル硬化物であることが好ましい。
　また、本発明の断熱フィルムは、繊維状金属粒子含有層のバインダーの主成分がケイ素を含有する材料であることがより好ましい。ケイ素を含有する材料としては、Ｓｉ元素のアルコキシド化合物を加水分解および重縮合して得られるゾルゲル硬化物、またはシリコーンであることが特に好ましく、Ｓｉ元素のアルコキシド化合物を加水分解および重縮合して得られるゾルゲル硬化物であることがより特に好ましい。
　以下、上記のゾルゲル硬化物、導電性高分子、有機高分子ポリマー（導電性高分子を除く）の好ましい態様を順に説明する。 Preferred binders include sol-gel cured products obtained by hydrolysis and polycondensation of an alkoxide compound of element (b) selected from the group consisting of Si, Ti, Zr and Al, conductive polymers, organic polymer polymers (conductivity). (Excluding the conductive polymer). The main component of the binder of the fibrous metal particle-containing layer is preferably a sol-gel cured product.
The heat insulating film of the present invention is more preferably a material in which the main component of the binder of the fibrous metal particle-containing layer contains silicon. The silicon-containing material is particularly preferably a sol-gel cured product obtained by hydrolysis and polycondensation of an Si element alkoxide compound or silicone, and obtained by hydrolysis and polycondensation of an Si element alkoxide compound. The sol-gel cured product is particularly preferable.
Hereinafter, preferred embodiments of the sol-gel cured product, the conductive polymer, and the organic polymer polymer (excluding the conductive polymer) will be described in order.
－ゾルゲル硬化物－
　本発明の断熱フィルムは、繊維状金属粒子含有層のバインダーの主成分が、Ｓｉ、Ｔｉ、ＺｒおよびＡｌからなる群より選ばれる元素（ｂ）のアルコキシド化合物を加水分解および重縮合して得られるゾルゲル硬化物を含むことが好ましく、製造コストや遠赤外線領域の反射率の点で、Ｓｉ元素のアルコキシド化合物を加水分解および重縮合して得られるゾルゲル硬化物が特に好ましい。
　Ｓｉ、Ｔｉ、ＺｒおよびＡｌからなる群より選ばれる元素（ｂ）のアルコキシド化合物（以下、特定アルコキシド化合物とも言う）を加水分解および重縮合して得られるゾルゲル硬化物は、酸化ケイ素、酸化ジルコニウム、酸化チタン、および酸化アルミニウムから選ばれる少なくとも１種である。前述の繊維状金属粒子含有層のバインダーの主成分がＳｉ、Ｔｉ、ＺｒおよびＡｌからなる群より選ばれる元素（ｂ）のアルコキシド化合物を加水分解および重縮合して得られるゾルゲル硬化物である場合、当然ながら前述の繊維状金属粒子含有層のバインダーの主成分は酸化ケイ素、酸化ジルコニウム、酸化チタン、および酸化アルミニウムから選ばれる少なくとも１種である。 -Hardened sol-gel-
The heat insulating film of the present invention is obtained by hydrolysis and polycondensation of an alkoxide compound of an element (b) selected from the group consisting of Si, Ti, Zr and Al as a main component of the binder of the fibrous metal particle-containing layer. A sol-gel cured product is preferably included, and a sol-gel cured product obtained by hydrolysis and polycondensation of an alkoxide compound of Si element is particularly preferable in terms of production cost and reflectance in the far infrared region.
A sol-gel cured product obtained by hydrolysis and polycondensation of an alkoxide compound (hereinafter also referred to as a specific alkoxide compound) of an element (b) selected from the group consisting of Si, Ti, Zr and Al includes silicon oxide, zirconium oxide, It is at least one selected from titanium oxide and aluminum oxide. When the main component of the binder of the fibrous metal particle-containing layer is a sol-gel cured product obtained by hydrolysis and polycondensation of an alkoxide compound of the element (b) selected from the group consisting of Si, Ti, Zr and Al Of course, the main component of the binder of the fibrous metal particle-containing layer is at least one selected from silicon oxide, zirconium oxide, titanium oxide, and aluminum oxide.
　繊維状金属粒子含有層は、下記条件（ｉ）および（ｉｉ）の少なくとも一つを満たすことが好ましく、下記条件（ｉｉ）を少なくとも満たすことがより好ましく、下記条件（ｉ）および（ｉｉ）を満たすことが特に好ましい。
（ｉ）繊維状金属粒子含有層に含まれる元素（ｂ）の物質量と、繊維状金属粒子含有層に含まれる金属元素（ａ）の物質量との比〔（元素（ｂ）のモル数）／（金属元素（ａ）のモル数）〕が０．１０／１～２２／１の範囲にある。
（ｉｉ）繊維状金属粒子含有層においてゾルゲル硬化物の形成に使用されるアルコキシド化合物の質量と、繊維状金属粒子含有層に含まれる金属ナノワイヤなどの繊維状金属粒子の質量の比〔（アルコキシド化合物の含有量）／（金属ナノワイヤなどの繊維状金属粒子の含有量）〕が０．２５／１～３０／１の範囲にある。 The fibrous metal particle-containing layer preferably satisfies at least one of the following conditions (i) and (ii), more preferably satisfies at least the following condition (ii), and satisfies the following conditions (i) and (ii): It is particularly preferable to satisfy it.
(I) Ratio of the amount of the element (b) contained in the fibrous metal particle-containing layer to the amount of the metal element (a) contained in the fibrous metal particle-containing layer [(number of moles of the element (b) ) / (Number of moles of metal element (a))] is in the range of 0.10 / 1 to 22/1.
(Ii) Ratio of the mass of the alkoxide compound used for forming the sol-gel cured product in the fibrous metal particle-containing layer and the mass of the fibrous metal particles such as metal nanowires contained in the fibrous metal particle-containing layer [(alkoxide compound Content) / (content of fibrous metal particles such as metal nanowires)] is in the range of 0.25 / 1 to 30/1.
　繊維状金属粒子含有層は、前述の金属ナノワイヤなどの繊維状金属粒子の使用量に対する特定アルコキシド化合物の使用量の比率、即ち、〔（特定アルコキシド化合物の質量）／（金属ナノワイヤなどの繊維状金属粒子の質量）〕の比が０．２５／１～３０／１の範囲で形成され得ることが好ましい。上記質量比が０．２５／１以上である場合、断熱性（繊維状金属粒子の導電性が高いことに起因すると考えられる）と透明性が優れると同時に、耐摩耗性、耐熱性、湿熱耐久性および耐屈曲性の全てが優れた繊維状金属粒子含有層となり得る。上記質量比が３０／１以下である場合、導電性および耐屈曲性が優れた繊維状金属粒子含有層となり得る。
　上記質量比は、より好ましくは０．５／１～２５／１の範囲、更に好ましくは１／１～２０／１、最も好ましくは２／１～１５／１の範囲である。質量比を好ましい範囲とすることで、得られた繊維状金属粒子含有層は、高い断熱性と高い透明性（可視光透過率およびヘイズ）と、を有すると共に、耐摩耗性、耐熱性および湿熱耐久性に優れ、かつ耐屈曲性に優れることになり、好適な物性を有する断熱フィルムを安定的に得ることができる。 The fibrous metal particle-containing layer has a ratio of the usage amount of the specific alkoxide compound to the usage amount of the fibrous metal particles such as the above-described metal nanowire, that is, [(mass of the specific alkoxide compound) / (fibrous metal such as the metal nanowire). The ratio of the mass of particles)] is preferably in the range of 0.25 / 1 to 30/1. When the mass ratio is 0.25 / 1 or more, the heat insulation (conceived to be due to the high conductivity of the fibrous metal particles) and the transparency are excellent, and at the same time, the wear resistance, heat resistance, and wet heat durability. It can be a fibrous metal particle-containing layer that is excellent in both properties and bending resistance. When the said mass ratio is 30/1 or less, it can become a fibrous metal 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 most preferably in the range of 2/1 to 15/1. By making the mass ratio within a preferable range, the obtained fibrous metal particle-containing layer has high heat insulating properties and high transparency (visible light transmittance and haze), as well as wear resistance, heat resistance, and wet heat. It will be excellent in durability and bend resistance, and a heat insulating film having suitable physical properties can be obtained stably.
－導電性高分子－
　本発明の断熱フィルムは、前述の繊維状金属粒子含有層のバインダーの主成分が導電性高分子であることが好ましい。導電性高分子も赤外線を効果的に遮断し、断熱性を発揮する。これは導電性高分子の自由電子によるプラズマ吸収波長が、地上気温付近の物体の放射よりも短波長側にあり、そのプラズマ吸収波長より高波長の電磁波を反射するためと考えられる。
　繊維状金属粒子含有層のバインダーの主成分に用いられる導電性高分子としては、特開２０１２－１８９６８３号公報の［００３８］～［００４６］および実施例に記載の導電性高分子を好ましく用いることができる。具体的には、導電性高分子は、一般に共役型の二重結合を基本骨格に有する有機高分子で、具体的にはポリチオフェン、ポリピロール、ポリアニリン、ポリアセチレン、ポリパラフェニレン、ポリフラン、ポリフルオレン、ポリフェニレンビニレン、これらの誘導体、およびこれらを構成する単量体の共重合体から選ばれた導電性高分子のいずれか１種又は２種以上の混合物が好ましく挙げられる。中でも、水又はその他の溶媒に対して可溶性、又は分散性を有し、高い導電性および透明性を示す、ポリチオフェン誘導体が好ましい。特に、下記式（Ｉ）： -Conductive polymer-
In the heat insulating film of the present invention, the main component of the binder in the fibrous metal particle-containing layer is preferably a conductive polymer. Conductive polymers also effectively block infrared rays and exhibit heat insulation. This is thought to be because the plasma absorption wavelength due to free electrons of the conductive polymer is shorter than the radiation of an object near the ground temperature, and reflects electromagnetic waves having a wavelength higher than the plasma absorption wavelength.
As the conductive polymer used as the main component of the binder of the fibrous metal particle-containing layer, the conductive polymers described in JP-A-2012-189683, [0038] to [0046] and Examples are preferably used. Can do. Specifically, the conductive polymer is generally an organic polymer having a conjugated double bond as a basic skeleton, specifically, polythiophene, polypyrrole, polyaniline, polyacetylene, polyparaphenylene, polyfuran, polyfluorene, polyphenylene. Preferable examples include any one kind or a mixture of two or more kinds of conductive polymers selected from vinylene, derivatives thereof, and copolymers of monomers constituting them. Among these, polythiophene derivatives that are soluble or dispersible in water or other solvents and exhibit high conductivity and transparency are preferable. In particular, the following formula (I):
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
（式中、Ｒ１およびＲ２は、それぞれ独立して水素原子若しくは炭素原子数１～４のアルキル基を表し、又はＲ１およびＲ２が相互に結合して任意に置換されていても良い炭素原子数１～４のアルキレン基を形成し、ｎは５０～１０００の整数を表す）で表される繰り返し単位を含むポリチオフェン誘導体が好ましい。 (Wherein R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or R 1 and R 2 may be bonded to each other and optionally substituted) A polythiophene derivative containing a repeating unit represented by (forms an alkylene group having 1 to 4 carbon atoms, and n represents an integer of 50 to 1000) is preferable.
　式（Ｉ）において、Ｒ１およびＲ２が相互に結合して形成される、置換されていても良い炭素原子数１～４のアルキレン基としては、具体的にはアルキル基で置換されたメチレン基、任意に炭素原子数１～１２のアルキル基又はフェニル基で置換されたエチレン－１，２基、プロピレン－１，３基、ブテン－１，４基を形成する基等が挙げられる。 In the formula (I), the optionally substituted alkylene group having 1 to 4 carbon atoms formed by bonding R 1 and R 2 to each other is specifically methylene substituted with an alkyl group. Groups, groups that form ethylene-1,2 groups, propylene-1,3 groups, butene-1,4 groups optionally substituted with alkyl groups having 1 to 12 carbon atoms or phenyl groups.
　式（Ｉ）におけるＲ１およびＲ２として、好ましくはメチル基又はエチル基であるか、Ｒ１およびＲ２が相互に結合して形成するメチレン基、エチレン－１，２基又はプロピレン－１，３基である。特に好ましいポリチオフェン誘導体としては、下記式（ＩＩ）： R 1 and R 2 in the formula (I) are preferably a methyl group or an ethyl group, or a methylene group, an ethylene-1, 2 group, or a propylene-1, formed by combining R 1 and R 2 with each other Three groups. Particularly preferred polythiophene derivatives include the following formula (II):
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
（式中、ｐは５０～１０００の整数を表す）で示される繰り返し単位、即ち、ポリ（３，４－エチレンジオキシチオフェン）単位を有するポリチオフェン誘導体である。 (Wherein p represents an integer of 50 to 1000), that is, a polythiophene derivative having a poly (3,4-ethylenedioxythiophene) unit.
　導電性高分子は、更にドーパント（電子供与剤）を含むことが好ましい。ドーパントとしては、例えば、ポリスチレンスルホン酸、ポリアクリル酸、ポリメタクリル酸、ポリマレイン酸、ポリビニルスルホン酸が好ましく挙げられる。特に、ポリスチレンスルホン酸が好ましい。これらにより導電性高分子の導電性を向上することができ、繊維状金属粒子含有層の断熱性を高めることができる。ドーパントの数平均分子量（ｎｕｍｂｅｒ　ａｖｅｒａｇｅ　ｍｏｌｅｃｕｌａｒ　ｗｅｉｇｈｔ；Ｍｎ）は、好ましくは１，０００～２，０００，０００であり、特に好ましくは２，０００～５００，０００である。 The conductive polymer preferably further contains a dopant (electron donor). Preferred examples of the dopant include polystyrene sulfonic acid, polyacrylic acid, polymethacrylic acid, polymaleic acid, and polyvinyl sulfonic acid. In particular, polystyrene sulfonic acid is preferable. By these, the electroconductivity of a conductive polymer can be improved and the heat insulation of a fibrous metal particle content layer can be improved. The number average molecular weight (Mn) of the dopant is preferably 1,000 to 2,000,000, particularly preferably 2,000 to 500,000.
　ドーパントの含有量は導電性高分子１００質量部に対して、通常２０～２０００質量部であり、好ましくは、４０～２００質量部である。例えば、式（ＩＩ）のポリチオフェン誘導体を導電性高分子とし、ポリスチレンスルホン酸をドーパントとして使用する場合はポリチオフェン１００質量部に対して、ポリスチレンスルホン酸１００～２００質量部が好ましく、特に１２０～１８０質量部が好ましい。 The content of the dopant is usually 20 to 2000 parts by mass, preferably 40 to 200 parts by mass with respect to 100 parts by mass of the conductive polymer. For example, when a polythiophene derivative of the formula (II) is used as a conductive polymer and polystyrene sulfonic acid is used as a dopant, 100 to 200 parts by mass of polystyrene sulfonic acid is preferable with respect to 100 parts by mass of polythiophene, and particularly 120 to 180 parts by mass. Part is preferred.
－有機高分子ポリマー－
　繊維状金属粒子含有層のバインダーの主成分に用いられる有機高分子ポリマーの具体例には、ポリメタクリル酸、ポリメタクリレート（例えば、ポリ（メタクリル酸メチル））、ポリアクリレート、およびポリアクリロニトリルなどのポリアクリル酸、ポリビニルアルコール（ＰＶＡ）、ポリエステル（例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリエステルナフタレート、およびポリカーボネート）、フェノールまたはクレゾール－ホルムアルデヒド（Ｎｏｖｏｌａｃｓ（登録商標））、ポリスチレン、ポリビニルトルエン、ポリビニルキシレン、ポリイミド、ポリアミド、ポリアミドイミド、ポリエーテルイミド、ポリスルフィド、ポリスルホン、ポリフェニレン、およびポリフェニルエーテルなどの高芳香性を有する高分子、ポリウレタン（ＰＵ；例えば三井化学（株）製タケラック（登録商標）ＷＳ－４０００）、エポキシ、ポリオレフィン（例えば、ポリプロピレン、ポリメチルペンテン、およびポリシクロオレフィン）、アクリロニトリル－ブタジエン－スチレン共重合体（ＡＢＳ）、セルロース、シリコーンおよびその他のシリコン含有高分子（例えば、ポリシルセスキオキサンおよびポリシラン、（株）トクシキ製ＳＱ１００など）、ポリ塩化ビニル（ＰＶＣ）、ポリビニルアセテート、ポリノルボルネン、合成ゴム、およびフッ化炭素系重合体（例えば、ポリビニリデンフルオライド、ポリテトラフルオロエチレン（ＴＦＥ）、またはポリヘキサフルオロプロピレン）、フルオロ－オレフィンの共重合体（例えば、旭硝子株式会社製「ＬＵＭＩＦＬＯＮ」（登録商標））、および非晶質フルオロカーボン重合体または共重合体（例えば、旭硝子株式会社製の「ＣＹＴＯＰ」（登録商標）またはデュポン社製の「Ｔｅｆｌｏｎ」（登録商標）ＡＦ）が挙げられるがそれだけに限定されない。
　繊維状金属粒子含有層のバインダーの主成分に用いられるポリシクロオレフィンとしては、特開２０１２－１８９６８３号公報の［００２０］～［００２２］および実施例に記載の透明フィルムの材料を好ましく用いることができる。具体的には、繊維状金属粒子含有層のバインダーの主成分に用いられるポリシクロオレフィンは、好ましくはポリノルボルネンである。ポリノルボルネンは、赤外領域の吸収が少なく、断熱性と耐候性に優れる。ポリノルボルネンとして、市販のもの（例えば、日本ゼオン社製、ＺＥＯＮＥＸ（登録商標）あるいはＺＥＯＮＯＲ（登録商標））を用いてもよい。
　これらの有機高分子ポリマーの中でも、繊維状金属粒子含有層の水接触角が９０°以上となるバインダーを用いて繊維状金属粒子含有層を形成する観点からは、シリコーンが好ましい。ただし、シリコーンを用いて繊維状金属粒子含有層を形成しても繊維状金属粒子含有層の水接触角が９０°以上とは限らないため、水接触角が９０°以上となるような構造を主鎖や側鎖に有する変性シリコーン（例えばアクリル変性シリコーン）を用いることがより好ましい。水接触角が９０°以上となるような構造を主鎖や側鎖に有する変性シリコーンとしては、特開平１０－２８６９００号公報の［００１０］に記載の材料を挙げることができ、この公報の内容は本明細書に組み込まれる。変性シリコーンとしては、アクリル変性シリコーンが好ましい。市販の変性シリコーンとしては、大成ファインケミカル（株）製、商品名アクリット　８ＳＳ－７２３などを好ましく用いることができる。 -Organic polymer-
Specific examples of the organic polymer used as the main component of the binder of the fibrous metal particle-containing layer include polymethacrylic acid, polymethacrylate (for example, poly (methyl methacrylate)), polyacrylate, and polyacrylonitrile. Acrylic acid, polyvinyl alcohol (PVA), polyester (eg, polyethylene terephthalate (PET), polyester naphthalate, and polycarbonate), phenol or cresol-formaldehyde (Novolacs®), polystyrene, polyvinyl toluene, polyvinyl xylene, polyimide, Highly aromatic polymers such as polyamide, polyamideimide, polyetherimide, polysulfide, polysulfone, polyphenylene, and polyphenyl ether, Riurethane (PU; Takelac (registered trademark) WS-4000, manufactured by Mitsui Chemicals, Inc.), epoxy, polyolefin (eg, polypropylene, polymethylpentene, and polycycloolefin), acrylonitrile-butadiene-styrene copolymer (ABS) , Cellulose, silicone and other silicon-containing polymers (eg, polysilsesquioxane and polysilane, SQ100 manufactured by Tokushi Co., Ltd.), polyvinyl chloride (PVC), polyvinyl acetate, polynorbornene, synthetic rubber, and fluoride Carbon-based polymers (for example, polyvinylidene fluoride, polytetrafluoroethylene (TFE), or polyhexafluoropropylene), fluoro-olefin copolymers (for example, “LUMIFLON manufactured by Asahi Glass Co., Ltd.) (Registered trademark)), and amorphous fluorocarbon polymers or copolymers (for example, “CYTOP” (registered trademark) manufactured by Asahi Glass Co., Ltd. or “Teflon” (registered trademark) AF manufactured by DuPont). It is not limited to that.
As the polycycloolefin used as the main component of the binder of the fibrous metal particle-containing layer, the transparent film materials described in JP 2012-189683 A, [0020] to [0022] and Examples are preferably used. it can. Specifically, the polycycloolefin used as the main component of the binder of the fibrous metal particle-containing layer is preferably polynorbornene. Polynorbornene has little absorption in the infrared region and is excellent in heat insulation and weather resistance. As the polynorbornene, a commercially available product (for example, ZEONEX (registered trademark) or ZEONOR (registered trademark) manufactured by Nippon Zeon Co., Ltd.) may be used.
Among these organic polymer polymers, silicone is preferable from the viewpoint of forming the fibrous metal particle-containing layer using a binder having a water contact angle of 90 ° or more of the fibrous metal particle-containing layer. However, even if the fibrous metal particle-containing layer is formed using silicone, the water contact angle of the fibrous metal particle-containing layer is not necessarily 90 ° or more. Therefore, the water contact angle is 90 ° or more. It is more preferable to use a modified silicone (for example, acrylic modified silicone) having a main chain or a side chain. Examples of the modified silicone having a structure in which the water contact angle is 90 ° or more in the main chain or the side chain include materials described in [0010] of JP-A-10-286900. Are incorporated herein. As the modified silicone, acrylic modified silicone is preferable. As a commercially available modified silicone, the product name Acrit 8SS-723 manufactured by Taisei Fine Chemical Co., Ltd. can be preferably used.
（その他マトリックス）
　繊維状金属粒子含有層に含まれるバインダーはマトリックスとしての機能も有するが、繊維状金属粒子含有層はさらにバインダー以外のマトリックス（以下、「その他マトリックス」という。）を含んでもよい。ここで「マトリックス」は、金属ナノワイヤなどの繊維状金属粒子を含んで層を形成する物質の総称である。
　その他マトリックスを含む繊維状金属粒子含有層は、後述の液状組成物中に、その他マトリックスを形成し得る材料を含有させておき、これを支持体上に（例えば、塗布により）付与して形成すればよい。
　その他マトリックスは、非感光性のものであっても、フォトレジスト組成物のような感光性のものであっても良い。
　繊維状金属粒子含有層がその他マトリックスを含む場合、バインダーの含有量に対して、例えば０．１０質量％～２０質量％、好ましくは０．１５質量％～１０質量％、更に好ましくは０．２０質量％～５質量％の範囲から選ばれることが断熱性、透明性、膜強度、耐摩耗性および耐屈曲性の優れる繊維状金属粒子含有層が得られるので有利である。 (Other matrix)
Although the binder contained in the fibrous metal particle-containing layer also has a function as a matrix, the fibrous metal particle-containing layer may further contain a matrix other than the binder (hereinafter referred to as “other matrix”). Here, the “matrix” is a general term for substances that form a layer containing fibrous metal particles such as metal nanowires.
The fibrous metal particle-containing layer containing the other matrix is formed by adding a material capable of forming the other matrix to the liquid composition described later and applying it to the support (for example, by coating). That's fine.
In addition, the matrix may be non-photosensitive or photosensitive such as a photoresist composition.
When the fibrous metal particle-containing layer contains other matrix, for example, 0.10% by mass to 20% by mass, preferably 0.15% by mass to 10% by mass, and more preferably 0.20% with respect to the content of the binder. It is advantageous to select from the range of 5% by mass to 5% by mass because a fibrous metal particle-containing layer having excellent heat insulating properties, transparency, film strength, abrasion resistance and bending resistance can be obtained.
－水接触角を調整するための添加剤－
　繊維状金属粒子含有層が最表面である場合は、繊維状金属粒子含有層に添加剤を添加する方法により、繊維状金属粒子含有層の水接触角が９０°以上にすることができる。
　繊維状金属粒子含有層の水接触角を調整するための添加剤としては、界面活性剤、シランカップリング剤、フッ素樹脂などの撥水性材料からなるフィラーなどを用いることができる。
　繊維状金属粒子含有層に用いる界面活性剤としては、特開２０１４－６９７号公報の［００８７］～［００９０］に記載の材料を挙げることができ、この公報の内容は本明細書に組み込まれる。界面活性剤としては、フッ素系界面活性剤が好ましい。市販のフッ素系界面活性剤としては、ＡＧＣセイミケミカル（株）製、商品名サーフロンなどを好ましく用いることができる。 -Additive for adjusting water contact angle-
When the fibrous metal particle-containing layer is the outermost surface, the water contact angle of the fibrous metal particle-containing layer can be 90 ° or more by a method of adding an additive to the fibrous metal particle-containing layer.
As an additive for adjusting the water contact angle of the fibrous metal particle-containing layer, a filler made of a water repellent material such as a surfactant, a silane coupling agent, or a fluororesin can be used.
Examples of the surfactant used for the fibrous metal particle-containing layer include materials described in JP-A-2014-697, [0087] to [0090], and the contents of this publication are incorporated herein. . As the surfactant, a fluorine-based surfactant is preferable. As a commercially available fluorosurfactant, AGC Seimi Chemical Co., Ltd., a brand name Surflon, etc. can be used preferably.
－分散剤－
　分散剤は、光重合性組成物中における前述の金属ナノワイヤなどの繊維状金属粒子が凝集することを防止しつつ分散させるために用いられる。分散剤としては、金属ナノワイヤを分散させることができれば特に制限はなく、目的に応じて適宜選択することができる。例えば、顔料分散剤として市販されている分散剤を利用でき、特に金属ナノワイヤに吸着する性質を持つ高分子分散剤が好ましい。このような高分子分散剤としては、例えばポリビニルピロリドン、ＢＹＫシリーズ（登録商標、ビックケミー社製）、ソルスパースシリーズ（登録商標、日本ルーブリゾール社製など）、アジスパーシリーズ（登録商標、味の素株式会社製）などが挙げられる。
　繊維状金属粒子含有層中における分散剤の含有量は、特開２０１３－２２５４６１号公報の［００８６］～［００９５］に記載のバインダーを用いる場合、のバインダー１００質量部に対し、０．１質量部～５０質量部が好ましく、０．５質量部～４０質量部がより好ましく、１質量部～３０質量部が特に好ましい。
　バインダーに対する分散剤の含有量を０．１質量部以上とすることで、分散液中での金属ナノワイヤなどの繊維状金属粒子の凝集が効果的に抑制され、５０質量部以下とすることで、塗布工程において安定な液膜が形成され、塗布ムラの発生が抑制されるため好ましい。 -Dispersant-
A dispersing agent is used in order to disperse | distribute, preventing that fibrous metal particles, such as the above-mentioned metal nanowire in the photopolymerizable composition, aggregate. The dispersant is not particularly limited as long as the metal nanowires can be dispersed, and can be appropriately selected according to the purpose. For example, a commercially available dispersant can be used as a pigment dispersant, and a polymer dispersant having a property of adsorbing to metal nanowires is particularly preferable. Examples of such polymer dispersants include polyvinylpyrrolidone, BYK series (registered trademark, manufactured by Big Chemie), Solsperse series (registered trademark, manufactured by Nihon Lubrizol, etc.), Ajisper series (registered trademark, Ajinomoto Co., Inc.). Manufactured).
The content of the dispersant in the fibrous metal particle-containing layer is 0.1 mass relative to 100 mass parts of the binder when the binder described in [0086] to [0095] of JP2013-225461A is used. To 50 parts by mass, preferably 0.5 to 40 parts by mass, more preferably 1 to 30 parts by mass.
By setting the content of the dispersant with respect to the binder to 0.1 parts by mass or more, aggregation of fibrous metal particles such as metal nanowires in the dispersion is effectively suppressed, and by setting the content to 50 parts by mass or less. This is preferable because a stable liquid film is formed in the coating process and the occurrence of coating unevenness is suppressed.
－溶媒－
　溶媒は、前述の金属ナノワイヤなどの繊維状金属粒子並びにバインダーを含む組成物を支持体の表面、または接着層付き支持体の接着層の表面に膜状に形成するための塗布液とするために使用される成分であり、目的に応じて適宜選択することができる。溶媒は、バインダーを０．１質量％以上溶解できるものであれば何でもよく、水、アルコール系溶媒、ケトン系溶媒、エーテル系溶媒、炭化水素系溶媒、芳香族系溶媒、ハロゲン系溶媒などが挙げられる。この溶媒は、前述の金属ナノワイヤの分散液の溶媒の少なくとも一部が兼ねていてもよい。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。
　このような溶媒を含む塗布液の固形分濃度は、０．１質量％～２０質量％の範囲であることが好ましい。 -solvent-
The solvent is a coating solution for forming a composition containing fibrous metal particles such as the above-described metal nanowires and a binder on the surface of the support or the surface of the adhesive layer of the support with an adhesive layer. It is a component used and can be appropriately selected according to the purpose. The solvent may be anything as long as it can dissolve the binder in an amount of 0.1% by mass or more, and includes water, alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents, aromatic solvents, halogen solvents, and the like. It is done. This solvent may also serve as at least a part of the solvent of the metal nanowire dispersion described above. These may be used individually by 1 type and may use 2 or more types together.
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.
－金属腐食防止剤－
　繊維状金属粒子含有層は金属ナノワイヤなどの繊維状金属粒子の金属腐食防止剤を含有することが好ましい。このような金属腐食防止剤としては、特に制限はなく、目的に応じて適宜選択することができるが、例えばチオール類、アゾール類などが好適である。
　金属腐食防止剤を含有させることで、防錆効果を発揮させることができ、繊維状金属粒子含有層の経時による断熱性および透明性の低下を抑制することができる。金属腐食防止剤は繊維状金属粒子含有層形成用組成物中に、適した溶媒で溶解した状態、又は粉末で添加するか、後述する導電層用塗布液による導電膜を作製後に、これを金属腐食防止剤浴に浸すことで付与することができる。
　金属腐食防止剤を添加する場合、繊維状金属粒子含有層中におけるその含有量は、金属ナノワイヤなどの繊維状金属粒子の含有量に対して０．５質量％～１０質量％であることが好ましい。 -Metal corrosion inhibitor-
The fibrous metal particle-containing layer preferably contains a metal corrosion inhibitor for fibrous metal particles such as metal nanowires. There is no restriction | limiting in particular as such a metal corrosion inhibitor, Although it can select suitably according to the objective, For example, thiols, azoles, etc. are suitable.
By containing a metal corrosion inhibitor, it is possible to exert a rust prevention effect, and it is possible to suppress a decrease in heat insulation and transparency of the fibrous metal particle-containing layer over time. The metal corrosion inhibitor is added to the composition for forming a fibrous metal particle-containing layer in a state dissolved in a suitable solvent, or in powder form, or after forming a conductive film with a conductive layer coating solution described later, It can be applied by soaking in a corrosion inhibitor bath.
When the metal corrosion inhibitor is added, the content in the fibrous metal particle-containing layer is preferably 0.5% by mass to 10% by mass with respect to the content of the fibrous metal particles such as metal nanowires. .
　その他マトリックスとしては、前述の金属ナノワイヤなどの繊維状金属粒子の製造の際に使用された分散剤としての高分子化合物を、マトリックスを構成する成分の少なくとも一部として使用することが可能である。 As the other matrix, it is possible to use a polymer compound as a dispersant used in the production of the fibrous metal particles such as the above-described metal nanowires as at least a part of the components constituting the matrix.
－他の導電性材料－
　繊維状金属粒子含有層には、金属ナノワイヤなどの繊維状金属粒子に加え、他の導電性材料、例えば、導電性粒子などを本発明の効果を損なわない限りにおいて併用しうる。導電性粒子としては、例えば金属粒子、スズドープ酸化インジウム（Ｉｎｄｉｕｍ　Ｔｉｎ　Ｏｘｉｄｅ；ＩＴＯ）粒子、アンチモンドープ酸化スズ（Ａｎｔｉｍｏｎｙ　Ｔｉｎ　Ｏｘｉｄｅ；ＡＴＯ）粒子、セシウムドープ酸化タングステン（ｃｅｓｉｕｍ－ｄｏｐｅｄ　ｔｕｎｇｓｔｅｎ　ｏｘｉｄｅ；ＣＷＯ）粒子などの導電性酸化物粒子が挙げられる。特に、ＩＴＯが繊維状金属粒子含有層の赤外線反射を増加させるため好ましい。効果の観点からは、金属ナノワイヤなどの繊維状金属粒子（好ましくは、アスペクト比が１０以上の金属ナノワイヤ）の含有比率は、金属ナノワイヤなどの繊維状金属粒子を含む導電性材料の総量に対して体積基準で、５０％以上が好ましく、６０％以上がより好ましく、７５％以上が特に好ましい。金属ナノワイヤなどの繊維状金属粒子の含有比率を５０％とすることにより、高い断熱性を有する繊維状金属粒子含有層を容易に得ることができる。
　また、金属ナノワイヤなどの繊維状金属粒子以外の形状の導電性粒子は、繊維状金属粒子含有層における導電性に大きく寄与しない上に可視光領域に吸収を持つ場合がある。特に導電性粒子が金属であって、球形などのプラズモン吸収が強い形状ではないことが、繊維状金属粒子含有層の透明度が悪化しないようにする観点から好ましい。 -Other conductive materials-
In the fibrous metal particle-containing layer, in addition to fibrous metal particles such as metal nanowires, other conductive materials such as conductive particles can be used in combination as long as the effects of the present invention are not impaired. Examples of the conductive particles include metal particles, tin-doped indium oxide (ITO) particles, antimony-doped tin oxide (ATO) particles, and cesium-doped tungsten oxide (CWO) particles. The conductive oxide particles are listed. In particular, ITO is preferable because it increases the infrared reflection of the fibrous metal particle-containing layer. From the viewpoint of the effect, the content ratio of fibrous metal particles such as metal nanowires (preferably metal nanowires having an aspect ratio of 10 or more) is based on the total amount of conductive material including fibrous metal particles such as metal nanowires. On a volume basis, it is preferably 50% or more, more preferably 60% or more, and particularly preferably 75% or more. By setting the content ratio of fibrous metal particles such as metal nanowires to 50%, a fibrous metal particle-containing layer having high heat insulating properties can be easily obtained.
In addition, conductive particles having a shape other than the fibrous metal particles such as metal nanowires may not significantly contribute to the conductivity in the fibrous metal particle-containing layer and may have absorption in the visible light region. In particular, it is preferable from the viewpoint of preventing the transparency of the fibrous metal particle-containing layer from deteriorating that the conductive particle is a metal and does not have a strong plasmon absorption shape such as a sphere.
　ここで、金属ナノワイヤなどの繊維状金属粒子の比率は、下記のように求めることができる。例えば、繊維状金属粒子が銀ナノワイヤであり、導電性粒子が銀粒子である場合には、銀ナノワイヤ水分散液をろ過して、銀ナノワイヤと、それ以外の導電性粒子とを分離し、誘導結合プラズマ（Ｉｎｄｕｃｔｉｖｅｌｙ　Ｃｏｕｐｌｅｄ　Ｐｌａｓｍａ；ＩＣＰ）発光分析装置を用いてろ紙に残っている銀の量と、ろ紙を透過した銀の量とを各々測定し、金属ナノワイヤの比率を算出することができる。金属ナノワイヤなどの繊維状金属粒子のアスペクト比は、ろ紙に残っている金属ナノワイヤなどの繊維状金属粒子をＴＥＭで観察し、３００個の金属ナノワイヤなどの繊維状金属粒子の短軸長および長軸長をそれぞれ測定することにより算出される。 Here, the ratio of fibrous metal particles such as metal nanowires can be obtained as follows. For example, when the fibrous metal 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 The ratio of the metal nanowires can be calculated by measuring the amount of silver remaining on the filter paper and the amount of silver transmitted through the filter paper using an coupled plasma (Inductively Coupled Plasma; ICP) emission spectrometer. The aspect ratio of fibrous metal particles such as metal nanowires is determined by observing the fibrous metal particles such as metal nanowires remaining on the filter paper with a TEM, and the short axis length and long axis of the fibrous metal particles such as 300 metal nanowires. Calculated by measuring each length.
（膜厚）
　繊維状金属粒子含有層の平均膜厚は、通常、０．００５μｍ～２μｍの範囲で選択される。例えば、平均膜厚を０．００１μｍ以上０．５μｍ以下とすることで、十分な耐久性、膜強度が得られる。特に、平均膜厚を０．０１μｍ～０．１μｍの範囲とすれば、製造上の許容範囲が確保され得るので好ましい。
　前述の条件（ｉ）および（ｉｉ）の少なくとも一つを満たす繊維状金属粒子含有層とすることで、断熱性と透明性とを高く維持しうるとともに、ゾルゲル硬化物に起因して、金属ナノワイヤなどの繊維状金属粒子が安定に固定化されるとともに、高い強度と耐久性とを実現し得ることが好ましい。例えば、繊維状金属粒子含有層の膜厚を０．００５μｍ～０．５μｍという薄層としても、実用上問題のない耐摩耗性、耐熱性、湿熱耐久性および耐屈曲性を有する繊維状金属粒子含有層を得ることができる。このため、本発明の一実施形態である断熱フィルムは種々の用途に好適に使用される。薄層を必要とする態様では、膜厚は、０．００５μｍ～０．５μｍとしてもよく、０．００７μｍ～０．３μｍがさらに好ましく、０．００８μｍ～０．２μｍがより好ましく、０．０１μｍ～０．１μｍが最も好ましい。このように繊維状金属粒子含有層をより薄層とすることで、繊維状金属粒子含有層の透明性がさらに向上し得る。 (Film thickness)
The average film thickness of the fibrous metal particle-containing layer is usually selected in the range of 0.005 μm to 2 μm. For example, by setting the average film thickness to 0.001 μm or more and 0.5 μm or less, sufficient durability and film strength can be obtained. In particular, if the average film thickness is in the range of 0.01 μm to 0.1 μm, an acceptable range in manufacturing can be secured, which is preferable.
By making the fibrous metal particle-containing layer satisfying at least one of the above-mentioned conditions (i) and (ii), it is possible to maintain high heat insulating properties and transparency, and due to the sol-gel cured product, metal nanowires It is preferable that fibrous metal particles such as can be stably fixed and can achieve high strength and durability. For example, even if the thickness of the fibrous metal particle-containing layer is a thin layer of 0.005 μm to 0.5 μm, the fibrous metal particles have wear resistance, heat resistance, wet heat durability, and bending resistance that do not cause any practical problems. A containing layer can be obtained. For this reason, the heat insulation film which is one Embodiment of this invention is used suitably for various uses. In an embodiment requiring a thin layer, the film thickness may be 0.005 μm to 0.5 μm, more preferably 0.007 μm to 0.3 μm, more preferably 0.008 μm to 0.2 μm, and more preferably 0.01 μm to 0.2 μm. 0.1 μm is most preferable. Thus, by making the fibrous metal particle-containing layer thinner, the transparency of the fibrous metal particle-containing layer can be further improved.
　繊維状金属粒子含有層の平均膜厚は、電子顕微鏡による繊維状金属粒子含有層断面の直接観察により、繊維状金属粒子含有層の膜厚を５点測定し、その算術平均値として算出される。なお、繊維状金属粒子含有層の膜厚は例えば、触針式表面形状測定器（Ｄｅｋｔａｋ（登録商標）１５０、Ｂｒｕｋｅｒ　ＡＸＳ製）を用いて、繊維状金属粒子含有層を形成した部分と繊維状金属粒子含有層を除去した部分の段差として測定することもできる。しかし、繊維状金属粒子含有層を除去する際に支持体の一部まで除去してしまう恐れがあることがあり、また形成される繊維状金属粒子含有層が薄膜なため誤差が生じやすい。そのため、後述の実施例においては電子顕微鏡を用いて測定される平均膜厚を記載している。 The average film thickness of the fibrous metal particle-containing layer is calculated as an arithmetic average value by measuring the thickness of the fibrous metal particle-containing layer at five points by directly observing the cross section of the fibrous metal particle-containing layer with an electron microscope. . The film thickness of the fibrous metal particle-containing layer is, for example, a portion of the fibrous metal particle-containing layer formed using a stylus type surface shape measuring instrument (Dektak (registered trademark) 150, manufactured by Bruker AXS) and a fibrous shape. It can also be measured as a step in the portion from which the metal particle-containing layer has been removed. However, when removing the fibrous metal particle-containing layer, there is a possibility that even a part of the support may be removed, and an error is likely to occur because the formed fibrous metal particle-containing layer is a thin film. Therefore, in the below-mentioned Example, the average film thickness measured using an electron microscope is described.
＜表面層＞
　本発明の断熱フィルムは、繊維状金属粒子含有層の支持体とは反対の面上に、さらに水接触角が９０°以上である表面層を含むことが好ましい。 <Surface layer>
It is preferable that the heat insulation film of this invention contains the surface layer whose water contact angle is 90 degrees or more further on the surface opposite to the support body of a fibrous metal particle content layer.
（表面層の組成）
　表面層としては特に制限は無いが、優れた耐擦性を有することが好ましい。表面層の組成としては、フッ素を含有する材料またはケイ素を含有する材料などが好ましく、フッ素を含有する材料がより好ましい。
　本発明の断熱フィルムは、表面層の主成分がフッ素を含有する材料またはケイ素を含有する材料であることが耐擦性を高める観点から好ましい。
　水接触角が９０°以上である表面層を形成するためのフッ素を含有する材料としては、フッ素樹脂、フッ素原子含有の単分子膜などを挙げることができる。
　表面層に用いるフッ素樹脂としては、特開２００２－１２７３１０号公報の［００２１］～［００２２］に記載のフッ素樹脂を挙げることができ、この公報の内容は本明細書に組み込まれる。他のフッ素樹脂としては、フッ化炭素系重合体（例えば、ポリビニリデンフルオライド、ポリテトラフルオロエチレン（ＴＦＥ）、またはポリヘキサフルオロプロピレン）、フルオロ－オレフィンの共重合体（例えば、旭硝子株式会社製「ＬＵＭＩＦＬＯＮ」（登録商標））、および非晶質フルオロカーボン重合体または共重合体（例えば、旭硝子株式会社製の「ＣＹＴＯＰ」（登録商標）またはデュポン社製の「Ｔｅｆｌｏｎ」（登録商標）ＡＦ）が挙げられる。市販のフッ素樹脂としては、旭硝子（株）製、商品名サイトップＣＴＸ－１０９ＭＰなどを好ましく用いることができる。
　表面層に用いるフッ素原子含有の単分子膜を形成するための材料としては、特開２０１３－２４５８４９号公報の［００８６］～［００９３］に記載の材料を挙げることができ、この公報の内容は本明細書に組み込まれる。市販の単分子膜を形成するための材料としては、ダイキン工業（株）製、商品名オプツールＤＳＸなどを好ましく用いることができる。本発明の断熱フィルムは、表面層が単分子膜であることが断熱性（初期Ｕ値）を改善する観点から好ましい。
　水接触角が９０°以上である表面層を形成するためのケイ素を含有する材料としては、疎水化シリカ、変性シリコーンなどを挙げることができ、疎水化シリカが断熱性（初期Ｕ値）を改善する観点からより好ましい。
　表面層に用いる疎水化シリカとしては、特開２０１３－１２３６６０号公報の［００４０］～［００４３］に記載の材料を挙げることができ、この公報の内容は本明細書に組み込まれる。疎水化シリカとしては、疎水性ヒュームドシリカが好ましい。市販の疎水化シリカとしては、日本アエロジル（株）製、商品名ＡＥＲＯＳＩＬ　Ｒ　２０２などを好ましく用いることができる。
　表面層に用いる変性シリコーンとしては、特開平１０－２８６９００号公報の［００１０］に記載の材料を挙げることができ、この公報の内容は本明細書に組み込まれる。変性シリコーンとしては、アクリル変性シリコーンが好ましい。市販の変性シリコーンとしては、大成ファインケミカル（株）製、商品名アクリット　８ＳＳ－７２３などを好ましく用いることができる。
　表面層は、透湿度が低いことが、断熱性の湿熱耐久性を改善する観点から好ましい。表面層の透湿度としては、水蒸気透過率と膜厚の積を指標とすることができる。本発明において表面層に好ましく用いることができる水蒸気透過率の低い材料としては、ケイ素を含有する材料などを挙げることができる。表面層の水蒸気透過率としては例えば１０ｇ／ｍ２・ｄａｙ以下が好ましく、５ｇ／ｍ２・ｄａｙ以下がより好ましく、１ｇ／ｍ２・ｄａｙ以下が特に好ましい。 (Surface layer composition)
Although there is no restriction | limiting in particular as a surface layer, It is preferable to have the outstanding abrasion resistance. As the composition of the surface layer, a fluorine-containing material or a silicon-containing material is preferable, and a fluorine-containing material is more preferable.
In the heat insulating film of the present invention, the main component of the surface layer is preferably a material containing fluorine or a material containing silicon from the viewpoint of improving the abrasion resistance.
Examples of the fluorine-containing material for forming the surface layer having a water contact angle of 90 ° or more include a fluororesin and a fluorine-containing monomolecular film.
Examples of the fluororesin used for the surface layer include the fluororesins described in JP-A-2002-127310, [0021] to [0022], and the contents of this gazette are incorporated herein. Other fluororesins include fluorocarbon polymers (eg, polyvinylidene fluoride, polytetrafluoroethylene (TFE), or polyhexafluoropropylene), fluoro-olefin copolymers (eg, manufactured by Asahi Glass Co., Ltd.). "LUMIFLON" (registered trademark)) and amorphous fluorocarbon polymer or copolymer (for example, "CYTOP" (registered trademark) manufactured by Asahi Glass Co., Ltd. or "Teflon" (registered trademark) AF manufactured by Asahi Glass Co., Ltd.) Can be mentioned. As a commercially available fluororesin, the product name Cytop CTX-109MP manufactured by Asahi Glass Co., Ltd. can be preferably used.
Examples of the material for forming a fluorine atom-containing monomolecular film used for the surface layer include the materials described in JP-A-2013-245849, [0086] to [0093]. Incorporated herein. As a material for forming a commercially available monomolecular film, trade name OPTOOL DSX manufactured by Daikin Industries, Ltd. can be preferably used. In the heat insulating film of the present invention, the surface layer is preferably a monomolecular film from the viewpoint of improving heat insulating properties (initial U value).
Examples of the silicon-containing material for forming a surface layer having a water contact angle of 90 ° or more include hydrophobized silica and modified silicone. Hydrophobized silica improves heat insulation (initial U value). It is more preferable from the viewpoint of.
Examples of the hydrophobized silica used for the surface layer include materials described in JP-A-2013-123660, [0040] to [0043], and the contents of this publication are incorporated herein. As the hydrophobized silica, hydrophobic fumed silica is preferable. As a commercially available hydrophobized silica, Nippon Aerosil Co., Ltd. product name AEROSIL R 202 etc. can be used preferably.
Examples of the modified silicone used for the surface layer include materials described in JP-A-10-286900, [0010], and the contents of this publication are incorporated herein. As the modified silicone, acrylic modified silicone is preferable. As a commercially available modified silicone, the product name Acrit 8SS-723 manufactured by Taisei Fine Chemical Co., Ltd. can be preferably used.
The surface layer preferably has a low moisture permeability from the viewpoint of improving heat-insulating wet heat durability. As the moisture permeability of the surface layer, the product of the water vapor transmission rate and the film thickness can be used as an index. Examples of the material having a low water vapor transmission rate that can be preferably used for the surface layer in the present invention include silicon-containing materials. Preferably, for example 10g / m 2 · day or less as the water vapor transmission rate of the surface layer, 5 g / m or less, more preferably 2 · day, 1g / m 2 · day or less are particularly preferred.
（表面層の膜厚）
　本発明の断熱フィルムは、前述の表面層の膜厚が１μｍ以下であることが断熱性の初期値を改善する観点から好ましく、０．５μｍ以下であることがより好ましく、０．３μｍ以下であることが特に好ましい。 (Film thickness of the surface layer)
In the heat insulating film of the present invention, the film thickness of the surface layer is preferably 1 μm or less from the viewpoint of improving the initial value of heat insulating properties, more preferably 0.5 μm or less, and 0.3 μm or less. It is particularly preferred.
　表面層には、屈折率を調整したり、表面硬度を増加させる目的で、酸化物粒子を含有させてもよい。酸化物粒子としては、例えば、酸化ケイ素、酸化チタン、酸化ジルコニウムなどが挙げられる。表面層が、断熱フィルムの最表層となるため、屈折率の低い酸化ケイ素を用いることが反射防止の点から好ましく、中空粒子の酸化ケイ素を用いることが特に好ましい。
　酸化物粒子の粒径は、１～５００ｎｍの範囲が好ましく、１０～２００ｎｍの範囲がより好ましい。酸化物粒子の添加量は、１～５０質量％の範囲が好ましく、１０～４０質量％の範囲がより好ましい。 The surface layer may contain oxide particles for the purpose of adjusting the refractive index or increasing the surface hardness. Examples of the oxide particles include silicon oxide, titanium oxide, and zirconium oxide. Since the surface layer is the outermost layer of the heat insulating film, it is preferable to use silicon oxide having a low refractive index from the viewpoint of antireflection, and it is particularly preferable to use silicon oxide of hollow particles.
The particle size of the oxide particles is preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 200 nm. The amount of oxide particles added is preferably in the range of 1 to 50% by mass, and more preferably in the range of 10 to 40% by mass.
＜中間層＞
　断熱フィルムは、支持体と繊維状金属粒子含有層との間に少なくとも一層の中間層を有することが好ましい。支持体と繊維状金属粒子含有層との間に中間層を設けることにより、支持体と繊維状金属粒子含有層との密着性、繊維状金属粒子含有層の全光透過率、繊維状金属粒子含有層のヘイズ、および繊維状金属粒子含有層の膜強度のうちの少なくとも一つの向上を図り得る。
　中間層としては、支持体と繊維状金属粒子含有層との接着力を向上させるための接着剤層、繊維状金属粒子含有層に含まれる成分との相互作用により機能性を向上させる機能性層などが挙げられ、目的に応じて適宜設けられる。 <Intermediate layer>
The heat insulating film preferably has at least one intermediate layer between the support and the fibrous metal particle-containing layer. By providing an intermediate layer between the support and the fibrous metal particle-containing layer, the adhesion between the support and the fibrous metal particle-containing layer, the total light transmittance of the fibrous metal particle-containing layer, and the fibrous metal particles It is possible to improve at least one of the haze of the containing layer and the film strength of the fibrous metal particle-containing layer.
As the intermediate layer, an adhesive layer for improving the adhesive force between the support and the fibrous metal particle-containing layer, and a functional layer that improves functionality by interaction with the components contained in the fibrous metal particle-containing layer Etc., and are appropriately provided depending on the purpose.
　中間層を更に有する断熱フィルムの構成について、図面を参照しながら説明する。
　図５においては、支持体上に中間層（第１の接着層３１と第２の接着層）を有してなる接着層付きの支持体１０１上に繊維状金属粒子含有層２０が設けられている。支持体１０と繊維状金属粒子含有層２０との間に、支持体１０との親和性に優れた第１の接着層３１と、繊維状金属粒子含有層２０との親和性に優れた第２の接着層３２とを含む中間層を備える。
　図５以外の構成の中間層を有していてもよく、例えば、支持体１０と繊維状金属粒子含有層２０との間に、図５の実施形態と同様の第１の接着層３１および第２の接着層３２に加え、繊維状金属粒子含有層２０に隣接して機能性層を備えて構成される中間層を有することも好ましい（不図示）。 The structure of the heat insulation film which further has an intermediate | middle layer is demonstrated referring drawings.
In FIG. 5, the fibrous metal particle-containing layer 20 is provided on a support 101 with an adhesive layer having an intermediate layer (first adhesive layer 31 and second adhesive layer) on the support. Yes. Between the support 10 and the fibrous metal particle-containing layer 20, the first adhesive layer 31 excellent in affinity with the support 10 and the second excellent in affinity between the fibrous metal particle-containing layer 20. The intermediate layer including the adhesive layer 32 is provided.
An intermediate layer having a configuration other than that in FIG. 5 may be included. For example, the first adhesive layer 31 and the first adhesive layer 31 similar to those in the embodiment in FIG. 5 are provided between the support 10 and the fibrous metal particle-containing layer 20. In addition to the two adhesive layers 32, it is also preferable to have an intermediate layer configured to include a functional layer adjacent to the fibrous metal particle-containing layer 20 (not shown).
＜近赤外線遮蔽層＞
　さらに、近赤外遮蔽材料を用いることで、近赤外光の遮蔽性を高めることができる。
　近赤外遮蔽材料としては、平板状金属粒子（例えば、銀ナノディスク）、有機多層膜、球状の金属酸化物粒子（例えば、スズドープ酸化インジウム（ＩＴＯ）粒子、アンチモンドープ酸化スズ（ＡＴＯ）粒子、セシウムドープ酸化タングステン（ＣＷＯ）粒子）などを挙げることができる。
　また、近赤外遮蔽材料は、近赤外線遮蔽層に含まれることが好ましく、近赤外線遮蔽層を単独で形成する材料であることがより好ましい。
　近赤外線遮蔽層は、含まれる材料によって熱線反射型の近赤外線反射層と熱線吸収型の近赤外線吸収層に分けられる。 <Near-infrared shielding layer>
Furthermore, by using a near-infrared shielding material, the shielding property of near-infrared light can be improved.
As the near-infrared shielding material, flat metal particles (for example, silver nanodisks), organic multilayer films, spherical metal oxide particles (for example, tin-doped indium oxide (ITO) particles, antimony-doped tin oxide (ATO) particles, Cesium-doped tungsten oxide (CWO) particles).
Moreover, it is preferable that a near-infrared shielding material is contained in a near-infrared shielding layer, and it is more preferable that it is a material which forms a near-infrared shielding layer independently.
The near-infrared shielding layer is divided into a heat ray reflection type near infrared reflection layer and a heat ray absorption type near infrared absorption layer depending on the material contained therein.
（平板状金属粒子を用いた近赤外線反射層）
　熱線遮蔽性（日射熱取得率）の観点からは、吸収した光の屋内への再放射（吸収した日射エネルギーの約１／３量）がある熱線吸収型より再放射がない熱線反射型が望ましい。近赤外光の反射をする観点からは、近赤外遮蔽材料として平板状金属粒子を用いることが好ましい。このような平板状金属粒子を用いた近赤外線反射層は、特開２０１３－２２８６９４号公報の［００１９］～［００４６］、特開２０１３－０８３９７４号公報、特開２０１３－０８０２２２号公報、特開２０１３－０８０２２１号公報、特開２０１３－０７７００７号公報、特開２０１３－０６８９４５号公報などに記載の近赤外遮蔽材料を用いることができ、これらの公報の記載は本明細書に組み込まれる。
　具体的には、近赤外線反射層は、少なくとも１種の金属粒子を含有する層であり、金属粒子が、六角形状乃至円形状の平板状金属粒子を６０個数％以上有し、六角形状乃至円形状の平板状金属粒子の主平面が、近赤外線反射層の一方の表面に対して平均０°～±３０°の範囲で面配向していることが好ましい。
　金属粒子の材料としては、特に制限はなく、目的に応じて適宜選択することができるが、熱線（近赤外線）の反射率が高い点から、銀、金、アルミニウム、銅、ロジウム、ニッケル、白金などが好ましい。 (Near-infrared reflective layer using flat metal particles)
From the viewpoint of heat ray shielding (acquisition rate of solar heat), a heat ray reflection type with no re-radiation is desirable rather than a heat ray absorption type with re-radiation of absorbed light into the room (about 1/3 of the absorbed solar energy). . From the viewpoint of reflecting near-infrared light, it is preferable to use flat metal particles as the near-infrared shielding material. A near-infrared reflective layer using such flat metal particles is disclosed in JP 2013-228694 A [0019] to [0046], JP 2013-083974 A, JP 2013-080222 A, JP The near-infrared shielding materials described in JP2013-080221A, JP2013-077007A, JP2013-068945A, and the like can be used, and the descriptions of these publications are incorporated in this specification.
Specifically, the near-infrared reflective layer is a layer containing at least one kind of metal particles, and the metal particles have 60% by number or more of hexagonal or circular plate-like metal particles, and the hexagonal or circular shape. It is preferable that the main plane of the shaped flat metal particles is plane-oriented in an average range of 0 ° to ± 30 ° with respect to one surface of the near-infrared reflective layer.
The material of the metal particles is not particularly limited and can be appropriately selected according to the purpose. However, silver, gold, aluminum, copper, rhodium, nickel, platinum are preferred because of the high heat ray (near infrared) reflectance. Etc. are preferable.
（有機多層膜、球状の金属酸化物粒子を用いた近赤外線反射層）
　有機多層膜を用いた近赤外線反射層としては、特開２０１２－２５６０４１号公報の［００３９］～［００４４］に記載のものを好ましく用いることができ、この公報の記載は本明細書に組み込まれる。
　球状の金属酸化物粒子を用いた近赤外線反射層としては、特開２０１３－３７０１３号公報の［００３８］～［００３９］に記載のものを好ましく用いることができ、この公報の記載は本明細書に組み込まれる。 (Organic multilayer film, near-infrared reflective layer using spherical metal oxide particles)
As the near-infrared reflective layer using an organic multilayer film, those described in JP-A-2012-256041 [0039] to [0044] can be preferably used, and the description of this publication is incorporated herein. .
As the near-infrared reflective layer using spherical metal oxide particles, those described in [0038] to [0039] of JP 2013-37013 A can be preferably used. Incorporated into.
（近赤外線吸収層）
　繊維状金属粒子含有層の表面に結露した水滴を早く水蒸気化する観点からは、近赤外線遮蔽層の中でも断熱フィルム上に熱を発生させやすい熱線吸収型の近赤外線吸収層が好ましい。
　近赤外線吸収層としては、特開２０１４－２４０９０７号公報の［００３３］、特開２０１４－２１４２９９号公報の［００１１］～［００２２］、特開２０１４－１４８５６７号公報の［００１３］～［００１７］、特開２０１４－１３９６１７号公報の［００１０］～［００３４］、特開２０１４－８０４６６号公報の［００２２］～［００３５］に記載のものを好ましく用いることができ、これらの公報の記載は本明細書に組み込まれる。 (Near-infrared absorbing layer)
From the viewpoint of quickly steaming water droplets condensed on the surface of the fibrous metal particle-containing layer, a near-infrared absorbing layer of a heat ray absorption type that easily generates heat on the heat insulating film is preferable among the near-infrared shielding layers.
As the near-infrared absorption layer, [0033] of Japanese Patent Application Laid-Open No. 2014-240907, [0011] to [0022] of Japanese Patent Application Laid-Open No. 2014-214299, and [0013] to [0017] of Japanese Patent Application Laid-Open No. 2014-148567. JP-A-2014-139617, [0010] to [0034], JP-A-2014-80466, [0022] to [0035] can be preferably used. Incorporated in the description.
＜粘着層＞
　本発明の断熱フィルムは、粘着層を有することが好ましい。粘着層は、紫外線吸収剤を含むことができる。
　粘着層の形成に利用可能な材料としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ポリビニルブチラール（ＰＶＢ）樹脂、アクリル樹脂、スチレン／アクリル樹脂、ウレタン樹脂、ポリエステル樹脂、シリコーン樹脂などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。これらの材料からなる粘着層は、塗布により形成することができる。
　さらに、粘着層には帯電防止剤、滑剤、ブロッキング防止剤などを添加してもよい。
　粘着層の厚みとしては、０．１μｍ～１０μｍが好ましい。 <Adhesive layer>
The heat insulating film of the present invention preferably has an adhesive layer. The adhesive layer can contain an ultraviolet absorber.
The material that can be used for forming the adhesive layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyvinyl butyral (PVB) resin, acrylic resin, styrene / acrylic resin, urethane resin, polyester resin And silicone resin. These may be used individually by 1 type and may use 2 or more types together. An adhesive layer made of these materials can be formed by coating.
Furthermore, you may add an antistatic agent, a lubricant, an antiblocking agent, etc. to the adhesion layer.
The thickness of the adhesive layer is preferably 0.1 μm to 10 μm.
＜断熱フィルムの製造方法＞
　本発明の断熱フィルムを製造するための方法としては特に制限はないが、以下の製造方法が好ましい。
　断熱フィルムの製造方法は、銀を主成分とする繊維状金属粒子およびバインダーを含む繊維状金属粒子含有層形成用の塗布液を支持体上に塗布して繊維状金属粒子含有層を形成する工程を含むことが好ましい。
　水接触角が９０°以上である表面層形成用の塗布液を前述の繊維状金属粒子含有層の上に塗布して表面層を形成する工程と、を含むことも好ましい。 <Method for producing heat insulating film>
Although there is no restriction | limiting in particular as a method for manufacturing the heat insulation film of this invention, The following manufacturing methods are preferable.
The method for producing a heat insulating film is a step of forming a fibrous metal particle-containing layer by applying a coating solution for forming a fibrous metal particle-containing layer containing fibrous metal particles mainly composed of silver and a binder onto a support. It is preferable to contain.
It is also preferable to include a step of forming a surface layer by applying a coating solution for forming a surface layer having a water contact angle of 90 ° or more on the fibrous metal particle-containing layer.
　繊維状金属粒子含有層を支持体上に形成する方法としては、バインダーを繊維状金属粒子含有層形成用の塗布液に用いる場合は、一般的な塗布方法で行うことができる。
　ある実施態様では、繊維状金属粒子含有層形成用の塗布液は、金属ナノワイヤなどの繊維状金属粒子の水分散液を調製し、これと前述の特定アルコキシド化合物由来の金属酸化物以外の材料（例えば前述の導電性高分子）を主成分とするバインダーとを混合して調製されてもよい。 As a method for forming the fibrous metal particle-containing layer on the support, when a binder is used for the coating liquid for forming the fibrous metal particle-containing layer, a general coating method can be used.
In one embodiment, the coating liquid for forming the fibrous metal particle-containing layer is prepared by preparing an aqueous dispersion of fibrous metal particles such as metal nanowires, and a material other than the metal oxide derived from the specific alkoxide compound described above ( For example, it may be prepared by mixing a binder mainly composed of the aforementioned conductive polymer).
　一方、繊維状金属粒子含有層を支持体上に形成する方法としては、例えば前述の特定アルコキシド化合物由来の金属酸化物を主成分とするバインダーを用いる場合、繊維状金属粒子含有層形成用の塗布液（以下、「ゾルゲル塗布液」ともいう）を、支持体上に塗布して液膜を形成すること、および、この液膜中で特定アルコキシド化合物の加水分解と重縮合の反応（以下、この加水分解と重縮合の反応を「ゾルゲル反応」ともいう。）を起こさせることにより繊維状金属粒子含有層を形成すること、を少なくとも含む方法により製造することができる。この方法は、更に必要に応じて、繊維状金属粒子含有層形成用の塗布液中に溶媒として含まれ得る水を加熱により蒸発させること（乾燥）を含んでもよく含まなくてもよい。
　ある実施態様では、ゾルゲル塗布液は、金属ナノワイヤなどの繊維状金属粒子の水分散液を調製し、これと特定アルコキシド化合物とを混合して調製されてもよい。ある実施態様では、特定アルコキシド化合物を含む水溶液を調製し、この水溶液を加熱して特定アルコキシド化合物の少なくとも一部を加水分解および重縮合させてゾル状態とし、このゾル状態にある水溶液と金属ナノワイヤなどの繊維状金属粒子の水分散液とを混合してゾルゲル塗布液を調製してもよい。
　ゾルゲル反応を促進させるために、酸性触媒または塩基性触媒を併用することが反応効率を高められるので、実用上好ましい。 On the other hand, as a method of forming the fibrous metal particle-containing layer on the support, for example, when a binder mainly composed of the metal oxide derived from the specific alkoxide compound is used, the coating for forming the fibrous metal particle-containing layer is used. A liquid (hereinafter also referred to as “sol-gel coating liquid”) is applied onto a support to form a liquid film, and a hydrolysis and polycondensation reaction of a specific alkoxide compound in the liquid film (hereinafter referred to as this The reaction of hydrolysis and polycondensation is also referred to as “sol-gel reaction.”) To form a fibrous metal particle-containing layer by causing a reaction. This method may or may not include the evaporation (drying) of water that can be contained as a solvent in the coating liquid for forming the fibrous metal particle-containing layer as necessary.
In one embodiment, the sol-gel coating solution may be prepared by preparing an aqueous dispersion of fibrous metal particles such as metal nanowires and mixing this with a specific alkoxide compound. In one embodiment, an aqueous solution containing a specific alkoxide compound is prepared, and the aqueous solution is heated to hydrolyze and polycondensate at least a part of the specific alkoxide compound to form a sol state. A sol-gel coating solution may be prepared by mixing with an aqueous dispersion of fibrous metal particles.
In order to promote the sol-gel reaction, it is practically preferable to use an acidic catalyst or a basic catalyst in combination because the reaction efficiency can be increased.
　塗布後は任意の方法で乾燥することができ、加熱して乾燥することが好ましい。
　前述の特定アルコキシド化合物由来の金属酸化物を主成分とするバインダーを用いる場合、支持体上に形成されたゾルゲル塗布液の塗布膜中においては、特定アルコキシド化合物の加水分解および縮合の反応が起こるが、その反応を促進させるために、上記塗布膜を加熱、乾燥することが好ましい。ゾルゲル反応を促進させるための加熱温度は、３０℃～２００℃の範囲が適しており、５０℃～１８０℃の範囲がより好ましい。
　加熱、乾燥時間は１０秒間～３００分間が好ましく、１分間～１２０分間がより好ましい。 After coating, it can be dried by any method, and is preferably dried by heating.
In the case of using the binder mainly composed of the metal oxide derived from the specific alkoxide compound, hydrolysis and condensation reaction of the specific alkoxide compound occurs in the coating film of the sol-gel coating liquid formed on the support. In order to promote the reaction, the coating film is preferably heated and dried. The heating temperature for promoting the sol-gel reaction is suitably in the range of 30 ° C. to 200 ° C., more preferably in the range of 50 ° C. to 180 ° C.
The heating and drying time is preferably 10 seconds to 300 minutes, more preferably 1 minute to 120 minutes.
（塗布方法）
　繊維状金属粒子含有層の形成方法において、前述の各工程における塗布方法には特に制限はなく、一般的な塗布方法で行うことができ、目的に応じて適宜選択することができる。例えばロールコート法、バーコート法、ディップコーティング法、スピンコーティング法、キャスティング法、ダイコート法、ブレードコート法、グラビアコート法、カーテンコート法、スプレーコート法、ドクターコート法、などが挙げられる。 (Application method)
In the method for forming the fibrous metal particle-containing layer, there is no particular limitation on the coating method in each step described above, and it can be performed by a general coating method and can be appropriately selected according to the purpose. 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.
（表面層の形成）
　表面層形成用の塗布液は、繊維状金属粒子含有層と同様の溶媒を用いることで、繊維状金属粒子含有層上に、均一な液膜を形成することができる。
　繊維状金属粒子含有層の上に塗布して表面層を形成する方法としては、特に制限はなく、繊維状金属粒子含有層と同様の塗布方法で行うことができる。 (Formation of surface layer)
The coating liquid for forming the surface layer can form a uniform liquid film on the fibrous metal particle-containing layer by using the same solvent as the fibrous metal particle-containing layer.
There is no restriction | limiting in particular as a method of apply | coating on a fibrous metal particle content layer, and forming a surface layer, It can carry out with the application | coating method similar to a fibrous metal particle content layer.
［断熱ガラス、窓］
　本発明の断熱ガラスは、本発明の断熱フィルムと、ガラスとを積層した断熱ガラスである。
　本発明の窓は、窓用透明支持体と、窓用透明支持体に貼り合わせた本発明の断熱フィルムを含む窓である。
　窓用透明支持体は、厚み０．５ｍｍ以上の窓用透明支持体であることが好ましく、厚み１ｍｍ以上の窓用透明支持体であることがより好ましく、窓用透明支持体の厚みに起因する熱伝導を抑制して温暖性を高める観点からは厚み２ｍｍ以上の窓用透明支持体であることが特に好ましい。
　窓用透明支持体は一般的には、板状またはシート状のものが使用される。
　窓用透明支持体としては、白板ガラス、青板ガラス、シリカコート青板ガラス等の透明ガラス；ポリカーボネート、ポリエーテルスルホン、ポリエステル、アクリル樹脂、塩化ビニル樹脂、芳香族ポリアミド樹脂、ポリアミドイミド、ポリイミド等の合成樹脂の樹脂板などを挙げることができる。これらの中でも、窓用透明支持体が、透明ガラスまたは樹脂板であることが好ましく、透明ガラスであることがより好ましい。
　ガラスや窓ガラスを構成する成分としては特に制限は無く、ガラスや窓ガラスとして、例えば、白板ガラス、青板ガラス、シリカコート青板ガラス等の透明ガラスを用いることができる。
　なお、本発明に用いられるガラスは、表面が平滑であることが好ましく、フロートガラスであることが好ましい。
　本発明の断熱ガラスの可視光透過率を求める際に、本発明の断熱フィルムを３ｍｍの青板ガラスに貼り合わせて測定することが好ましい。３ｍｍの青板ガラスについてはＪＩＳＡ５７５９に記載されているガラスを使用することが好ましい。
　本発明の断熱フィルムは、窓の内側、すなわち窓ガラスの屋内側に貼り付ける。
　本発明の断熱ガラスまたは本発明の窓は、本発明の断熱フィルムの繊維状金属粒子含有層が、支持体の窓（ガラス）側の面とは反対側の面上に配置される。本発明では、繊維状金属粒子含有層は、その層の厚みにもよるが繊維状金属粒子含有層と屋内側の最外面の距離が５μｍ以内にあることが断熱性を高める観点から好ましく、０．１～５μｍ以内にあることが特に好ましく、２～４μｍ以内であることが更に特に好ましい。
　また、本発明の断熱フィルムの繊維状金属粒子含有層は屋内側の最外層の次の層にあることが断熱性を高める観点から好ましい。 [Insulated glass, windows]
The heat insulation glass of this invention is the heat insulation glass which laminated | stacked the heat insulation film of this invention, and glass.
The window of this invention is a window containing the heat insulating film of this invention bonded together to the transparent support body for windows, and the transparent support body for windows.
The transparent support for windows is preferably a transparent support for windows having a thickness of 0.5 mm or more, more preferably a transparent support for windows having a thickness of 1 mm or more, and is caused by the thickness of the transparent support for windows. From the viewpoint of suppressing heat conduction and increasing warmth, a transparent support for windows having a thickness of 2 mm or more is particularly preferable.
The transparent support for windows is generally a plate or sheet.
As transparent support for windows, 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. Examples thereof include a resin plate of resin. Among these, it is preferable that the transparent support body for windows is a transparent glass or a resin board, and it is more preferable that it is transparent glass.
There is no restriction | limiting in particular as a component which comprises glass and window glass, Transparent glass, such as white plate glass, blue plate glass, silica coat blue plate glass, can be used as glass and window glass, for example.
The glass used in the present invention preferably has a smooth surface, and is preferably float glass.
When calculating | requiring the visible light transmittance | permeability of the heat insulation glass of this invention, it is preferable to bond and measure the heat insulation film of this invention on a 3 mm blue plate glass. About 3 mm blue plate glass, it is preferable to use the glass described in JISA5759.
The heat insulation film of this invention is affixed on the inner side of a window, ie, the indoor side of a window glass.
In the heat insulating glass of the present invention or the window of the present invention, the fibrous metal particle-containing layer of the heat insulating film of the present invention is disposed on the surface of the support opposite to the surface on the window (glass) side. In the present invention, although the fibrous metal particle-containing layer depends on the thickness of the layer, the distance between the fibrous metal particle-containing layer and the outermost surface on the indoor side is preferably within 5 μm from the viewpoint of enhancing the heat insulating property. It is particularly preferably 1 to 5 μm or less, and particularly preferably 2 to 4 μm or less.
In addition, the fibrous metal particle-containing layer of the heat insulating film of the present invention is preferably in the layer next to the outermost layer on the indoor side from the viewpoint of improving heat insulating properties.
　本発明の断熱ガラスまたは本発明の窓は、近赤外線遮蔽層をなるべく太陽光側に設置している方が、屋内へ入射しようとする赤外線をあらかじめ反射できるため好ましく、この観点において近赤外線遮蔽層を太陽光入射側に設置されるように粘着層を積層することが好ましい。具体的には近赤外線遮蔽層の上、または、近赤外線遮蔽層上に設けられたオーバーコート層等の機能性層の上に粘着層を設け、その粘着層を介して窓ガラスへ貼合することが好ましい。
　窓ガラスに本発明の断熱フィルムを貼り付ける際、粘着層を塗工、あるいは、ラミネートにより設けた本発明の断熱フィルムを準備し、あらかじめ窓ガラス表面と本発明の断熱フィルムの粘着層表面に界面活性剤（主にアニオン系）を含んだ水溶液を噴霧してから、粘着層を介して窓ガラスに本発明の断熱フィルムを設置すると良い。水分が蒸発するまでの間、粘着層の粘着力は落ちるため、ガラス表面では本発明の断熱フィルムの位置の調整が可能である。窓ガラスに対する本発明の断熱フィルムの貼り付け位置が定まった後、スキージー等を用いて窓ガラスと本発明の断熱フィルムの間に残る水分をガラス中央から端部に向けて掃き出すことにより、窓ガラス表面に本発明の断熱フィルムを固定できる。このようにして、窓ガラスに本発明の断熱フィルムを設置することが可能である。 In the heat insulating glass of the present invention or the window of the present invention, it is preferable that the near infrared shielding layer is installed on the sunlight side as much as possible because it can reflect the infrared rays entering the indoor in advance. From this viewpoint, the near infrared shielding layer It is preferable to laminate the adhesive layer so that is placed on the sunlight incident side. Specifically, an adhesive layer is provided on the near-infrared shielding layer or a functional layer such as an overcoat layer provided on the near-infrared shielding layer, and is bonded to the window glass through the adhesive layer. It is preferable.
When the heat insulating film of the present invention is applied to the window glass, the heat insulating film of the present invention prepared by coating or laminating the adhesive layer is prepared, and the interface between the window glass surface and the adhesive layer surface of the heat insulating film of the present invention is prepared in advance. After spraying an aqueous solution containing an activator (mainly anionic), the heat insulating film of the present invention may be installed on the window glass through an adhesive layer. Until the moisture evaporates, the adhesive force of the adhesive layer decreases, and therefore the position of the heat insulating film of the present invention can be adjusted on the glass surface. After the attachment position of the heat insulating film of the present invention to the window glass is determined, the window glass is swept away from the glass center toward the edge by using a squeegee or the like to leave moisture remaining between the window glass and the heat insulating film of the present invention. The heat insulation film of this invention can be fixed to the surface. Thus, it is possible to install the heat insulation film of this invention in a window glass.
＜建築材料、建築物、乗物＞
　本発明の断熱フィルム、断熱ガラスおよび窓は、使用される態様に特に制限はなく、目的に応じて適宜選択することができる。例えば、乗物用、建築材料や建築物用、農業用などが挙げられる。これらの中でも、省エネルギー効果の点で、建築材料、建築物、乗物に用いられることが好ましい。
　建築材料は、本発明の断熱フィルムまたは本発明の断熱ガラスを含む建築材料である。
　建築物は、本発明の断熱フィルム、本発明の断熱ガラス、本発明の建築材料または本発明の窓を含む建築物である。建築物としては、家、ビル、倉庫などを挙げることができる。
　乗物は、本発明の断熱フィルム、本発明の断熱ガラスまたは本発明の窓を含む乗物である。乗物としては、自動車、鉄道車両、船舶などを挙げることができる。 <Building materials, buildings, vehicles>
There is no restriction | limiting in particular in the aspect used for the heat insulation film of this invention, heat insulation glass, and a window, According to the objective, it can select suitably. For example, for vehicles, building materials, buildings, agriculture and the like. Among these, it is preferable to be used for building materials, buildings, and vehicles in terms of energy saving effect.
A building material is a building material containing the heat insulation film of this invention or the heat insulation glass of this invention.
The building is a building including the heat insulating film of the present invention, the heat insulating glass of the present invention, the building material of the present invention, or the window of the present invention. Examples of buildings include houses, buildings, and warehouses.
The vehicle is a vehicle including the heat insulating film of the present invention, the heat insulating glass of the present invention or the window of the present invention. Examples of the vehicle include an automobile, a railway vehicle, and a ship.
　以下に実施例と比較例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.
［繊維状金属粒子のサイズの測定法］
＜繊維状金属粒子の平均短径（平均直径）と平均長径（平均長軸長）＞
　透過型電子顕微鏡（ＴＥＭ；日本電子株式会社製、ＪＥＭ－２０００ＦＸ）を用いて拡大観察される繊維状金属粒子から、ランダムに選択した３００個の繊維状金属粒子の短径（短軸長、直径）と長径（長軸長）を測定し、その平均値から繊維状金属粒子の平均短径（平均短軸長、平均直径）と平均長径（平均長軸長）を求めた。 [Measurement method of size of fibrous metal particles]
<Average short diameter (average diameter) and average long diameter (average long axis length) of fibrous metal particles>
The short diameter (short axis length, diameter) of 300 fibrous metal particles randomly selected from the fibrous metal particles magnified using a transmission electron microscope (TEM; JEM-2000FX, manufactured by JEOL Ltd.) ) And the major axis (major axis length) were measured, and the average minor axis (average minor axis length, average diameter) and average major axis (average major axis length) of the fibrous metal particles were determined from the average value.
［調製例１］
＜銀ナノワイヤ水分散液（１）の調製＞
　予め、下記の添加液Ａ、ＧおよびＨを調製した。 [Preparation Example 1]
<Preparation of silver nanowire aqueous dispersion (1)>
The following additive solutions A, G and H were prepared in advance.
（添加液Ａ）
　硝酸銀粉末５．１ｇを純水５００ｍＬに溶解した。その後、１ｍｏｌ／Ｌのアンモニア水を透明になるまで添加した。そして、全量が１０００ｍＬになるように純水を添加した。 (Additive liquid A)
5.1 g of silver nitrate powder was dissolved in 500 mL of pure water. Then, 1 mol / L ammonia water was added until it became transparent. And the pure water was added so that the whole quantity might be set to 1000 mL.
（添加液Ｇ）
　グルコース粉末１ｇを２８０ｍＬの純水で溶解して、添加液Ｇを調製した。 (Additive liquid G)
1 g of glucose powder was dissolved in 280 mL of pure water to prepare additive solution G.
（添加液Ｈ）
　ＨＴＡＢ（ヘキサデシル－トリメチルアンモニウムブロミド）粉末４ｇを２２０ｍＬの純水で溶解して、添加液Ｈを調製した。 (Additive liquid H)
An additive solution H was prepared by dissolving 4 g of HTAB (hexadecyl-trimethylammonium bromide) powder in 220 mL of pure water.
　次に、以下のようにして、銀ナノワイヤ水分散液（１）を調製した。
　純水４１０ｍＬを三口フラスコ内に入れ、２０℃にて攪拌しながら、添加液Ｈ　８２．５ｍＬ、および添加液Ｇ　２０６ｍＬをロートにて添加した（一段目）。この液に、添加液Ａ　２０６ｍＬを流量２．０ｍＬ／分、攪拌回転数８００ｒｐｍ（ｒｏｕｎｄ　ｐｅｒ　ｍｉｎｕｔｅｓ）で添加した（二段目）。その１０分間後、添加液Ｈを８２．５ｍＬ添加した（三段目）。その後、３℃／分で内温７３℃まで昇温した。その後、攪拌回転数を２００ｒｐｍに落とし、５．５時間加熱した。得られた水分散液を冷却した。
　限外濾過モジュールＳＩＰ１０１３（商品名、旭化成株式会社製、分画分子量：６，０００）、マグネットポンプ、およびステンレスカップをシリコーン製チューブで接続し、限外濾過装置とした。
　上述の冷却後の水分散液を限外濾過装置のステンレスカップに入れ、ポンプを稼動させて限外濾過を行った。限外濾過モジュールからの濾液が５０ｍＬになった時点で、ステンレスカップに９５０ｍＬの蒸留水を加え、洗浄を行った。前述の洗浄を電気伝導度（東亜ディーケーケー（株）製ＣＭ－２５Ｒで測定）が５０μＳ／ｃｍ以下になるまで繰り返した後、濃縮を行い、０．８４％銀ナノワイヤ水分散液（１）を得た。得られた銀ナノワイヤ水分散液（１）を、調製例１の銀ナノワイヤ水分散液とした。得られた調製例１の銀ナノワイヤ水分散液に含まれる繊維状金属粒子である銀ナノワイヤについて、前述のようにして平均短軸長、平均長軸長、および繊維状金属粒子の短軸長の変動係数を測定した。その結果、平均短軸長１７．２ｎｍ、平均長軸長３４．２μｍ、変動係数が１７．８％の銀ナノワイヤを得たことがわかった。以後、「銀ナノワイヤ水分散液（１）」と表記する場合は、上記方法で得られた銀ナノワイヤ水分散液を示す。 Next, a silver nanowire aqueous dispersion (1) 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 through a funnel while stirring at 20 ° C. (first stage). To this solution, 206 mL of additive solution A was added at a flow rate of 2.0 mL / min and at a stirring rotation speed of 800 rpm (round per minutes) (second stage). Ten minutes later, 82.5 mL of additive liquid H was added (third stage). Thereafter, the internal temperature was raised to 73 ° C. at 3 ° C./min. Then, the stirring rotation speed was reduced to 200 rpm and heated for 5.5 hours. 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 obtain an ultrafiltration device.
The aqueous dispersion after cooling was put into a stainless cup of an ultrafiltration device, and the ultrafiltration was performed by operating a pump. When the filtrate from the ultrafiltration module reached 50 mL, 950 mL of distilled water was added to the stainless steel cup for washing. The above washing was repeated until the electric conductivity (measured with CM-25R manufactured by Toa DKK Co., Ltd.) was 50 μS / cm or less, followed by concentration to obtain a 0.84% silver nanowire aqueous dispersion (1). It was. The obtained silver nanowire aqueous dispersion (1) was used as the silver nanowire aqueous dispersion of Preparation Example 1. For the silver nanowires that are the fibrous metal particles contained in the aqueous silver nanowire dispersion of Preparation Example 1 obtained, the average minor axis length, the average major axis length, and the minor axis length of the fibrous metal particles were as described above. The coefficient of variation was measured. As a result, it was found that a silver nanowire having an average minor axis length of 17.2 nm, an average major axis length of 34.2 μm, and a coefficient of variation of 17.8% was obtained. Hereinafter, the expression “silver nanowire aqueous dispersion (1)” indicates the silver nanowire aqueous dispersion obtained by the above method.
［調製例２］
＜接着層付き支持体（ＰＥＴ基板；図５中の符号１０１）の作製＞
　下記の配合で接着用溶液１を調製した。
（接着用溶液１）
・タケラック（登録商標）ＷＳ－４０００　　　　　　　　　５．０質量部
（コーティング用ポリウレタン、固形分濃度３０％、三井化学（株）製）
・界面活性剤　　　　　　　　　　　　　　　　　　　　　　０．３質量部
（商品名：ナロアクティーＨＮ－１００、三洋化成工業（株）製）
・界面活性剤　　　　　　　　　　　　　　　　　　　　　　０．３質量部
（サンデット（登録商標）ＢＬ、固形分濃度４３％、三洋化成工業（株）製）
・水　　　　　　　　　　　　　　　　　　　　　　　　　９４．４質量部 [Preparation Example 2]
<Preparation of support with adhesive layer (PET substrate; reference numeral 101 in FIG. 5)>
A bonding solution 1 was prepared with the following composition.
(Adhesive solution 1)
-Takelac (registered trademark) WS-4000 5.0 parts by mass (polyurethane for coating, solid content concentration 30%, manufactured by Mitsui Chemicals, Inc.)
・ Surfactant 0.3 part by mass (Brand name: NAROACTY HN-100, manufactured by Sanyo Chemical Industries, Ltd.)
・ Surfactant 0.3 part by mass (Sandet (registered trademark) BL, solid content concentration 43%, manufactured by Sanyo Chemical Industries, Ltd.)
・ 94.4 parts by mass of water
　支持体として用いる厚さ７５μｍのＰＥＴフィルム（図５中の符号１０）の一方の表面にコロナ放電処理を施し、このコロナ放電処理を施した表面に、上記の接着用溶液１を塗布し１２０℃で２分間乾燥させて、厚さが０．１１μｍの第１の接着層（図５中の符号３１）を形成した。 One surface of a 75 μm-thick PET film (reference numeral 10 in FIG. 5) used as a support is subjected to corona discharge treatment, and the adhesive solution 1 is applied to the surface subjected to the corona discharge treatment, and the temperature is 120 ° C. And dried for 2 minutes to form a first adhesive layer (reference numeral 31 in FIG. 5) having a thickness of 0.11 μm.
　以下の配合で、接着用溶液２を調製した。
（接着用溶液２）
・テトラエトキシシラン　　　　　　　　　　　　　　　　　５．０質量部
（商品名：ＫＢＥ－０４、信越化学工業（株）製）
・３－グリシドキシプロピルトリメトキシシラン　　　　　　３．２質量部
（商品名：ＫＢＭ－４０３、信越化学工業（株）製）
・２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン
　　　　　　　　　　　　　　　　　　　　　　　　　　　　１．８質量部
（商品名：ＫＢＭ－３０３、信越化学工業（株）製）
・酢酸水溶液（酢酸濃度＝０．０５％、ｐＨ＝５．２）　　１０．０質量部
・硬化剤　　　　　　　　　　　　　　　　　　　　　　　　０．８質量部
（ホウ酸、和光純薬工業（株）製）
・コロイダルシリカ　　　　　　　　　　　　　　　　　　６０．０質量部
（スノーテックス（登録商標）Ｏ、平均粒子径１０ｎｍ～２０ｎｍ、固形分濃度２０％、ｐＨ（ｐｏｗｅｒ　ｏｆ　Ｈｙｄｒｏｇｅｎ　ｉｏｎ　ｃｏｎｃｅｎｔｒａｔｉｏｎ）＝２．６、日産化学工業（株）製）
・界面活性剤　　　　　　　　　　　　　　　　　　　　　　０．２質量部
（商品名：ナロアクティーＨＮ－１００、三洋化成工業（株）製）
・界面活性剤　　　　　　　　　　　　　　　　　　　　　　０．２質量部
（サンデット（登録商標）ＢＬ、固形分濃度４３％、三洋化成工業（株）製） An adhesive solution 2 was prepared with the following composition.
(Adhesive solution 2)
-5.0 parts by mass of tetraethoxysilane (trade name: KBE-04, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ 3.2 parts by mass of 3-glycidoxypropyltrimethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ 1.8 parts by mass of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (trade name: KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.)
Acetic acid aqueous solution (acetic acid concentration = 0.05%, pH = 5.2) 10.0 parts by mass Curing agent 0.8 parts by mass (Boric acid, manufactured by Wako Pure Chemical Industries, Ltd.)
Colloidal silica 60.0 parts by mass (Snowtex (registered trademark) O, average particle size 10 nm to 20 nm, solid content concentration 20%, pH (power of hydrogen ion concentration) = 2.6, manufactured by Nissan Chemical Industries, Ltd. )
・ Surfactant 0.2 parts by mass (trade name: NAROACTY HN-100, manufactured by Sanyo Chemical Industries, Ltd.)
-Surfactant 0.2 parts by mass (Sandet (registered trademark) BL, solid content concentration 43%, manufactured by Sanyo Chemical Industries, Ltd.)
　接着用溶液２は、以下の方法で調製した。酢酸水溶液を激しく攪拌しながら、３－グリシドキシプロピルトリメトキシシランを、この酢酸水溶液中に３分間かけて滴下した。次に、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシランを酢酸水溶液中に強く攪拌しながら３分間かけて添加した。次に、テトラエトキシシランを、酢酸水溶液中に強く攪拌しながら５分かけて添加し、その後２時間攪拌を続けた。次に、コロイダルシリカと、硬化剤と、界面活性剤とを順次添加し、接着用溶液２を調製した。 接着 Adhesive solution 2 was prepared by the following method. While the aqueous acetic acid solution was vigorously stirred, 3-glycidoxypropyltrimethoxysilane was dropped into the aqueous acetic acid solution over 3 minutes. Next, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was added to the aqueous acetic acid solution over 3 minutes with vigorous stirring. Next, tetraethoxysilane was added to the acetic acid aqueous solution over 5 minutes with vigorous stirring, and then stirring was continued for 2 hours. Next, colloidal silica, a curing agent, and a surfactant were sequentially added to prepare an adhesive solution 2.
　前述の第１の接着層（図５中の符号３１）の表面をコロナ放電処理したのち、その表面に、上記の接着用溶液２をバーコート法により塗布し、１７０℃で１分間加熱して乾燥し、厚さ０．５μｍの第２の接着層（図５中の符号３２）を形成して、接着層付きの支持体（ＰＥＴ基板；図５中の符号１０１）を得た。 After the surface of the first adhesive layer (reference numeral 31 in FIG. 5) is subjected to corona discharge treatment, the adhesive solution 2 is applied to the surface by a bar coating method and heated at 170 ° C. for 1 minute. It dried and formed the 2nd contact bonding layer (code | symbol 32 in FIG. 5) of thickness 0.5 micrometer, and obtained the support body (PET board | substrate; code | symbol 101 in FIG. 5) with the contact bonding layer.
［実施例１］
＜繊維状金属粒子含有層の塗布による形成＞
　下記組成のアルコキシド化合物の溶液を６０℃で１時間撹拌して均一になったことを確認した。調製した溶液をゾルゲル溶液とした。
（アルコキシド化合物の溶液）
・テトラエトキシシラン　　　　　　　　　　　　　　　　　５．０質量部
（商品名：ＫＢＥ－０４、信越化学工業（株）製）
・１％酢酸水溶液　　　　　　　　　　　　　　　　　　　１０．０質量部
・蒸留水　　　　　　　　　　　　　　　　　　　　　　　　４．０質量部
　なお、ゾルゲル溶液中のテトラエトキシシランはゾルゲル反応後にはゾルゲル硬化物のＳｉＯ２として膜中に存在するため、下記表１の繊維状金属粒子含有層のバインダー材料には「ゾルゲルＳｉＯ２」として記載した。
　得られたゾルゲル溶液２．０９質量部と、調製例１で得られた銀ナノワイヤ水分散液（１）３２．７０質量部を混合し、さらに蒸留水で希釈して繊維状金属粒子含有層形成用の塗布液であるゾルゲル塗布液を得た。
　上記の接着層付き支持体の第２の接着層の表面にコロナ放電処理を施し、その表面にバーコート法で銀量が０．０４０ｇ／ｍ２、全固形分塗布量が０．１２０ｇ／ｍ２となるように上記ゾルゲル塗布液を塗布した。そののち、１７５℃で１分間乾燥してゾルゲル反応を起こさせて、繊維状金属粒子含有層を形成した。繊維状金属粒子含有層におけるテトラエトキシシラン（アルコキシド化合物）／銀ナノワイヤの質量比は２／１となった。 [Example 1]
<Formation by application of fibrous metal particle-containing layer>
The solution of the alkoxide compound having the following composition was stirred at 60 ° C. for 1 hour to confirm that the solution became uniform. The prepared solution was used as a sol-gel solution.
(Alkoxide compound solution)
-5.0 parts by mass of tetraethoxysilane (trade name: KBE-04, manufactured by Shin-Etsu Chemical Co., Ltd.)
1% acetic acid aqueous solution 10.0 parts by mass Distilled water 4.0 parts by mass In addition, since tetraethoxysilane in the sol-gel solution exists in the film as SiO 2 of the sol-gel cured product after the sol-gel reaction, The binder material of the fibrous metal particle-containing layer is described as “sol-gel SiO 2 ”.
2.09 parts by mass of the obtained sol-gel solution and 32.70 parts by mass of the aqueous silver nanowire dispersion (1) obtained in Preparation Example 1 are mixed and further diluted with distilled water to form a fibrous metal particle-containing layer. A sol-gel coating liquid, which is a coating liquid for use, was obtained.
The surface of the second adhesive layer of the above support with an adhesive layer is subjected to a corona discharge treatment, and the surface is coated with a silver amount of 0.040 g / m 2 and the total solid content applied amount is 0.120 g / m. The sol-gel coating solution was applied so as to be 2 . After that, it was dried at 175 ° C. for 1 minute to cause a sol-gel reaction to form a fibrous metal particle-containing layer. The mass ratio of tetraethoxysilane (alkoxide compound) / silver nanowire in the fibrous metal particle-containing layer was 2/1.
＜表面層の塗布による形成＞
（表面層組成物）
　表面層組成物として、フッ素樹脂の９質量％溶液（商品名サイトップＣＴＸ－１０９ＭＰ、旭硝子（株）製）を準備した。 <Formation by application of surface layer>
(Surface layer composition)
As the surface layer composition, a 9% by mass solution of fluororesin (trade name Cytop CTX-109MP, manufactured by Asahi Glass Co., Ltd.) was prepared.
（塗布方法）
　繊維状金属粒子含有層の表面上に、上記の表面層組成物を、アプリケーターを用いて乾燥後の膜厚が０．２μｍとなるように塗布し、１７０℃で１分間加熱して乾燥して表面層を形成し、実施例１の断熱フィルムを得た。 (Application method)
On the surface of the fibrous metal particle-containing layer, the above surface layer composition is applied using an applicator so that the film thickness after drying is 0.2 μm, and dried by heating at 170 ° C. for 1 minute. A surface layer was formed to obtain a heat insulating film of Example 1.
［実施例２］
　実施例１において、上記の表面層組成物を乾燥後の膜厚が０．８μｍとなるように塗布した以外は実施例１と同様にして、実施例２の断熱フィルムを得た。 [Example 2]
In Example 1, the heat insulation film of Example 2 was obtained like Example 1 except having apply | coated said surface layer composition so that the film thickness after drying might be set to 0.8 micrometer.
［実施例３］
　実施例１において、上記の表面層組成物を乾燥後の膜厚が１．５μｍとなるように塗布した以外は実施例１と同様にして、実施例３の断熱フィルムを得た。 [Example 3]
In Example 1, the heat insulation film of Example 3 was obtained like Example 1 except having apply | coated said surface layer composition so that the film thickness after drying might be set to 1.5 micrometers.
［実施例４］
＜表面層組成物＞
　表面層材料として用いるフッ素樹脂（商品名オプツール　ＤＳＸ、ダイキン工業（株）製）を、パーフルオロヘキサンで０．１質量％に希釈した溶液を表面層組成物として準備した。 [Example 4]
<Surface layer composition>
A solution obtained by diluting a fluororesin (trade name: OPTOOL DSX, manufactured by Daikin Industries, Ltd.) used as a surface layer material to 0.1% by mass with perfluorohexane was prepared as a surface layer composition.
＜塗布方法＞
　実施例１と同様にして調製した繊維状金属粒子含有層の表面上に、上記の表面層組成物を引き上げ速度１ｃｍ／ｍｉｎでディップ塗布し、６０℃、相対湿度９０％の環境にて１時間放置した後、パーフルオロヘキサンを染み込ませた不織布で表面のムラがなくなるまで拭き取りを行って表面層を形成し、実施例４の断熱フィルムを得た。得られた表面層は、Ｘ線反射率測定により単分子膜であることを確認した。 <Application method>
On the surface of the fibrous metal particle-containing layer prepared in the same manner as in Example 1, the above surface layer composition was dip-coated at a lifting speed of 1 cm / min, and the environment was 60 ° C. and relative humidity 90% for 1 hour. After leaving, the surface layer was formed by wiping with a non-woven fabric soaked with perfluorohexane until the surface unevenness was eliminated, and the heat insulating film of Example 4 was obtained. The obtained surface layer was confirmed to be a monomolecular film by X-ray reflectivity measurement.
［実施例５］
＜疎水性シリカ分散液＞
　エタノール２００質量部に、表面層材料である疎水性ヒュームドシリカ粒子（商品名ＡＥＲＯＳＩＬ　Ｒ　２０２、日本アエロジル（株）製）を添加し、疎水性シリカ分散液を調製した。 [Example 5]
<Hydrophobic silica dispersion>
Hydrophobic fumed silica particles (trade name AEROSIL R 202, manufactured by Nippon Aerosil Co., Ltd.) as a surface layer material were added to 200 parts by mass of ethanol to prepare a hydrophobic silica dispersion.
＜塗布方法＞
　実施例１と同様にして調製した繊維状金属粒子含有層の表面上に、上記の疎水性シリカ分散液を、アプリケーターを用いて乾燥後の膜厚が０．２μｍとなるように塗布し、１７０℃で１分間加熱して乾燥して表面層を形成し、実施例５の断熱フィルムを得た。 <Application method>
On the surface of the fibrous metal particle-containing layer prepared in the same manner as in Example 1, the hydrophobic silica dispersion was applied using an applicator so that the film thickness after drying was 0.2 μm. A surface layer was formed by heating at 0 ° C. for 1 minute and drying to obtain a heat insulating film of Example 5.
［実施例６］
＜アクリルシリコーン系疎水性組成物＞
　表面層材料として、ＵＶ（Ｕｌｔｒａｖｉｏｌｅｔ）反応性基を有するアクリルシリコーンポリマーのメトキシプロパノールであるアクリルシリコーン系疎水性組成物（商品名アクリット　８ＳＳ－７２３、大成ファインケミカル（株）製）を準備した。 [Example 6]
<Acrylic silicone-based hydrophobic composition>
As a surface layer material, an acrylic silicone-based hydrophobic composition (trade name Acryt 8SS-723, manufactured by Taisei Fine Chemical Co., Ltd.), which is an acrylic silicone polymer methoxypropanol having UV (Ultraviolet) reactive groups, was prepared.
＜塗布方法＞
　実施例１と同様にして調製した繊維状金属粒子含有層の表面上に、上記のアクリルシリコーン系疎水性組成物を、アプリケーターを用いて乾燥後の膜厚が０．２μｍとなるように塗布し、６０℃で１０分間加熱して乾燥した。その後、ＵＶ照射によりアクリルシリコーンポリマーのＵＶ反応性基を硬化させて表面層を形成し、実施例６の断熱フィルムを得た。 <Application method>
On the surface of the fibrous metal particle-containing layer prepared in the same manner as in Example 1, the above acrylic silicone-based hydrophobic composition was applied using an applicator so that the film thickness after drying was 0.2 μm. And dried at 60 ° C. for 10 minutes. Thereafter, the UV reactive group of the acrylic silicone polymer was cured by UV irradiation to form a surface layer, and the heat insulating film of Example 6 was obtained.
［実施例７］
＜繊維状金属粒子含有層の塗布による形成＞
　実施例１で得られたゾルゲル溶液２．０９質量部と、調製例１で得られた銀ナノワイヤ水分散液（１）３２．７０質量部と、フッ素系界面活性剤（商品名サーフロン、ＡＧＣセイミケミカル（株）製）０．１質量部とを混合し、さらに蒸留水で希釈して繊維状金属粒子含有層形成用の塗布液であるゾルゲル塗布液を得た。
　上記の接着層付き支持体の第２の接着層の表面にコロナ放電処理を施し、その表面にバーコート法で銀量が０．０４０ｇ／ｍ２、全固形分塗布量が０．１２０ｇ／ｍ２となるように上記ゾルゲル塗布液を塗布した。そののち、１７５℃で１分間乾燥してゾルゲル反応を起こさせて、繊維状金属粒子含有層を形成した。繊維状金属粒子含有層におけるテトラエトキシシラン（アルコキシド化合物）／銀ナノワイヤの質量比は２／１となった。
　得られた積層体を実施例７の断熱フィルムとした。 [Example 7]
<Formation by application of fibrous metal particle-containing layer>
2.09 parts by mass of the sol-gel solution obtained in Example 1, 32.70 parts by mass of the silver nanowire aqueous dispersion (1) obtained in Preparation Example 1, and a fluorosurfactant (trade name Surflon, AGC Seimi Chemical Co., Ltd.) 0.1 parts by mass was mixed and further diluted with distilled water to obtain a sol-gel coating solution which is a coating solution for forming a fibrous metal particle-containing layer.
The surface of the second adhesive layer of the above support with an adhesive layer is subjected to a corona discharge treatment, and the surface is coated with a silver amount of 0.040 g / m 2 and the total solid content applied amount is 0.120 g / m. The sol-gel coating solution was applied so as to be 2 . After that, it was dried at 175 ° C. for 1 minute to cause a sol-gel reaction to form a fibrous metal particle-containing layer. The mass ratio of tetraethoxysilane (alkoxide compound) / silver nanowire in the fibrous metal particle-containing layer was 2/1.
The obtained laminated body was used as the heat insulating film of Example 7.
［実施例８］
＜ＰＥＤＯＴ／ＰＳＳバインダーを用いた繊維状金属粒子含有層の形成＞
　下記組成のポリスチレンスルホン酸（ＰＳＳ）をドープしたポリ（３，４－エチレンジオキシチオフェン）（ＰＥＤＯＴ）溶液を調製した。
・ポリ（３，４－エチレンジオキシチオフェン）水分散体　５０．０質量部
（ＣｌｅｖｉｏｓＰ　ＡＩ　４０８３、ヘレウス（株）製）
・蒸留水　　　　　　　　　　　　　　　　　　　　　　　　２．０質量部
・エタノール　　　　　　　　　　　　　　　　　　　　　　８．０質量部
　得られたＰＥＤＯＴ溶液１８．０質量部と、調製例１で得られた銀ナノワイヤ水分散液（１）３２．７０質量部を混合し、さらに蒸留水で希釈して、繊維状金属粒子含有層形成用の塗布液である銀ナノワイヤ分散ＰＥＤＯＴ塗布液を得た。
　上記の接着層付き支持体の第２の接着層の表面にコロナ放電処理を施し、その表面にバーコート法で銀量が０．０４０ｇ／ｍ２、全固形分塗布量が０．１２０ｇ／ｍ２となるように上記銀ナノワイヤ分散ＰＥＤＯＴ塗布液を塗布した。そののち、１００℃で２分間乾燥して、ＰＥＤＯＴ／ＰＳＳバインダーを用いた繊維状金属粒子含有層を形成した。ＰＥＤＯＴ／ＰＳＳバインダーを用いた繊維状金属粒子含有層におけるバインダー／銀ナノワイヤの質量比は２／１となった。
　上記のＰＥＤＯＴ／ＰＳＳバインダーを用いた繊維状金属粒子含有層の表面上に、実施例２と同様にして表面層を形成して、実施例８の断熱フィルムを得た。 [Example 8]
<Formation of fibrous metal particle-containing layer using PEDOT / PSS binder>
A poly (3,4-ethylenedioxythiophene) (PEDOT) solution doped with polystyrene sulfonic acid (PSS) having the following composition was prepared.
-Poly (3,4-ethylenedioxythiophene) aqueous dispersion 50.0 parts by mass (CleviosP AI 4083, manufactured by Heraeus Co., Ltd.)
-2.0 parts by mass of distilled water-8.0 parts by mass of ethanol 18.0 parts by mass of the obtained PEDOT solution and 32.70 parts by mass of the silver nanowire aqueous dispersion (1) obtained in Preparation Example 1 were mixed. Furthermore, it diluted with distilled water, and obtained the silver nanowire dispersion | distribution PEDOT coating liquid which is a coating liquid for fibrous metal particle content layer formation.
The surface of the second adhesive layer of the above support with an adhesive layer is subjected to a corona discharge treatment, and the surface is coated with a silver amount of 0.040 g / m 2 and the total solid content applied amount is 0.120 g / m. The silver nanowire-dispersed PEDOT coating solution was applied so as to be 2 . After that, it was dried at 100 ° C. for 2 minutes to form a fibrous metal particle-containing layer using a PEDOT / PSS binder. The mass ratio of binder / silver nanowire in the fibrous metal particle-containing layer using the PEDOT / PSS binder was 2/1.
On the surface of the fibrous metal particle-containing layer using the PEDOT / PSS binder, a surface layer was formed in the same manner as in Example 2 to obtain a heat insulating film of Example 8.
［実施例９］
＜ＣＯＰバインダーを用いた繊維状金属粒子含有層の形成＞
　調製例１で得られた銀ナノワイヤ水分散液を、分散液の銀ナノワイヤ濃度を変更せずに、ｎ－プロパノールへ溶媒置換したのち、さらに１－イソプロピル－４－メチルシクロヘキサンへ溶媒置換を行った。
　下記組成のシクロオレフィンポリマー（ＣＯＰ）溶液を調製した。
・シクロオレフィンポリマー　　　　　　　　　　　　　　　１．０質量部
（商品名、ゼオネックス４８０Ｒ、日本ゼオン（株）製）
・１－イソプロピル－４－メチルシクロヘキサン　　　　　１５．０質量部
　上記のＣＯＰ溶液３．５０質量部と、上記溶媒置換を行った銀ナノワイヤ水分散液３２．７０質量部を混合し、銀ナノワイヤ分散ＣＯＰ塗布液を得た。
　上記の接着層付き支持体の第２の接着層の表面にコロナ放電処理を施し、その表面にバーコート法で銀量が０．０４０ｇ／ｍ２、全固形分塗布量が０．１２０ｇ／ｍ２となるように上記銀ナノワイヤ分散ＣＯＰ塗布液を塗布した。そののち、１００℃で２分間乾燥して、ＣＯＰバインダーを用いた繊維状金属粒子含有層を形成した。ＣＯＰバインダーを用いた繊維状金属粒子含有層におけるＣＯＰ／銀ナノワイヤの質量比は２／１となった。
　上記のＣＯＰバインダーを用いた繊維状金属粒子含有層の表面上に、実施例２と同様にして表面層を形成して、実施例９の断熱フィルムを得た。 [Example 9]
<Formation of fibrous metal particle-containing layer using COP binder>
The silver nanowire aqueous dispersion obtained in Preparation Example 1 was subjected to solvent substitution with n-propanol without changing the silver nanowire concentration of the dispersion, and then further with 1-isopropyl-4-methylcyclohexane. .
A cycloolefin polymer (COP) solution having the following composition was prepared.
・ 1.0 parts by mass of cycloolefin polymer (trade name, Zeonex 480R, manufactured by Nippon Zeon Co., Ltd.)
1-Isopropyl-4-methylcyclohexane 15.0 parts by mass The above COP solution 3.50 parts by mass and the above-mentioned solvent-substituted silver nanowire aqueous dispersion 32.70 parts by mass are mixed and silver nanowire-dispersed COP coating is performed. A liquid was obtained.
The surface of the second adhesive layer of the above support with an adhesive layer is subjected to a corona discharge treatment, and the surface is coated with a silver amount of 0.040 g / m 2 and the total solid content applied amount is 0.120 g / m. The silver nanowire-dispersed COP coating solution was applied so as to be 2 . After that, it was dried at 100 ° C. for 2 minutes to form a fibrous metal particle-containing layer using a COP binder. The mass ratio of COP / silver nanowire in the fibrous metal particle-containing layer using the COP binder was 2/1.
On the surface of the fibrous metal particle-containing layer using the COP binder, a surface layer was formed in the same manner as in Example 2 to obtain a heat insulating film of Example 9.
［実施例１０］
＜ＰＵバインダーを用いた繊維状金属粒子含有層の形成＞
　下記組成のポリウレタン（ＰＵ）溶液を調製した。
・ポリウレタン水分散液　　　　　　　　　　　　　　　　　５．０質量部
（商品名、タケラック（登録商標）ＷＳ－４０００、三井化学（株）製）
・蒸留水　　　　　　　　　　　　　　　　　　　　　　　９５．０質量部
　得られたＰＵ溶液１５．０質量部と、調製例１で得られた銀ナノワイヤ水分散液（１）３２．７０質量部を混合し、さらに蒸留水で希釈して銀ナノワイヤ分散ＰＵ塗布液を得た。
　上記の接着層付き支持体の第２の接着層の表面にコロナ放電処理を施し、その表面にバーコート法で銀量が０．０４０ｇ／ｍ２、全固形分塗布量が０．１２０ｇ／ｍ２となるように上記銀ナノワイヤ分散ＰＵ塗布液を塗布した。そののち、１２０℃で２分間乾燥して、ＰＵバインダーを用いた繊維状金属粒子含有層を形成した。ＰＵバインダーを用いた繊維状金属粒子含有層におけるＰＵ／銀ナノワイヤの質量比は２／１となった。
　上記のＰＵバインダーを用いた繊維状金属粒子含有層の表面上に、実施例２と同様にして表面層を形成して、実施例１０の断熱フィルムを得た。 [Example 10]
<Formation of fibrous metal particle-containing layer using PU binder>
A polyurethane (PU) solution having the following composition was prepared.
-Polyurethane aqueous dispersion 5.0 parts by mass (trade name, Takerak (registered trademark) WS-4000, manufactured by Mitsui Chemicals, Inc.)
-95.0 parts by mass of distilled water 15.0 parts by mass of the obtained PU solution and 32.70 parts by mass of the silver nanowire aqueous dispersion (1) obtained in Preparation Example 1 were mixed and further diluted with distilled water. Thus, a silver nanowire-dispersed PU coating solution was obtained.
The surface of the second adhesive layer of the above support with an adhesive layer is subjected to a corona discharge treatment, and the surface is coated with a silver amount of 0.040 g / m 2 and the total solid content applied amount is 0.120 g / m. The silver nanowire-dispersed PU coating solution was applied so as to be 2 . Thereafter, it was dried at 120 ° C. for 2 minutes to form a fibrous metal particle-containing layer using a PU binder. The mass ratio of PU / silver nanowires in the fibrous metal particle-containing layer using the PU binder was 2/1.
On the surface of the fibrous metal particle-containing layer using the above PU binder, a surface layer was formed in the same manner as in Example 2 to obtain a heat insulating film of Example 10.
［実施例１１］
＜シリコーンバインダーを用いた繊維状金属粒子含有層の形成＞
　下記組成のシリコーン溶液を調製した。
・シリコーン変性アクリル樹脂（商品名ＳＱ１００、固形分５０％、（株）
トクシキ製）　　　　　　　　　　　　　　　　　　　　　　５．０質量部
・イソシアネート系硬化剤（商品名ＵＡＸ－６１５、（株）トクシキ製）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　１．０質量部
・錫系触媒（商品名ＵＡ－３８、（株）トクシキ製）　　　　０．２質量部
・メチルエチルケトン　　　　　　　　　　　　　　　　　９３．８質量部
　調製例１で得られた銀ナノワイヤ水分散液を、分散液の銀ナノワイヤ濃度を変更せずに、ｎ－プロパノールへ溶媒置換したのち、さらにメチルエチルケトンへ溶媒置換を行った。
　得られたシリコーン溶液４．４質量部と、上記溶媒置換を行った銀ナノワイヤ水分散液３２．７０質量部を混合し、銀ナノワイヤ分散シリコーン塗布液を得た。
　上記の接着層付き支持体の第２の接着層の表面にコロナ放電処理を施し、その表面にバーコート法で銀量が０．０４０ｇ／ｍ２、全固形分塗布量が０．１２０ｇ／ｍ２となるように上記銀ナノワイヤ分散シリコーン塗布液を塗布した。そののち、１００℃で２分間乾燥して、シリコーンバインダーを用いた繊維状金属粒子含有層を形成した。シリコーンバインダーを用いた繊維状金属粒子含有層におけるシリコーン／銀ナノワイヤの質量比は２／１となった。
　上記のシリコーンバインダーを用いた繊維状金属粒子含有層の表面上に、実施例２と同様にして表面層を形成して、実施例１１の断熱フィルムを得た。 [Example 11]
<Formation of fibrous metal particle-containing layer using silicone binder>
A silicone solution having the following composition was prepared.
・ Silicone-modified acrylic resin (trade name SQ100, solid content 50%, Co., Ltd.
5.0 parts by mass / isocyanate curing agent (trade name UAX-615, manufactured by Tokushi Co., Ltd.)
1.0 part by mass / tin-based catalyst (trade name UA-38, manufactured by Tokiki Co., Ltd.) 0.2 part by mass / 93.8 parts by mass of methyl ethyl ketone The silver nanowire aqueous dispersion obtained in Preparation Example 1 was used as a dispersion. Without changing the silver nanowire concentration, the solvent was replaced with n-propanol, and the solvent was further replaced with methyl ethyl ketone.
4.4 parts by mass of the obtained silicone solution and 32.70 parts by mass of the silver nanowire aqueous dispersion subjected to the solvent replacement were mixed to obtain a silver nanowire-dispersed silicone coating liquid.
The surface of the second adhesive layer of the above support with an adhesive layer is subjected to a corona discharge treatment, and the surface is coated with a silver amount of 0.040 g / m 2 and the total solid content applied amount is 0.120 g / m. The silver nanowire-dispersed silicone coating solution was applied so as to be 2 . After that, it was dried at 100 ° C. for 2 minutes to form a fibrous metal particle-containing layer using a silicone binder. The mass ratio of silicone / silver nanowires in the fibrous metal particle-containing layer using the silicone binder was 2/1.
A surface layer was formed in the same manner as in Example 2 on the surface of the fibrous metal particle-containing layer using the above silicone binder to obtain a heat insulating film of Example 11.
［実施例１２］
　断熱フィルムに対し、近赤外線反射層を以下の方法で設けた。 [Example 12]
A near-infrared reflective layer was provided on the heat insulating film by the following method.
＜銀平板粒子分散液Ｂ１の調製＞
（銀平板粒子分散液Ａ１の調製）
　ＮＴＫＲ－４（日本金属工業（株）製）の反応容器にイオン交換水１３Ｌを計量し、ＳＵＳ３１６Ｌ製のシャフトにＮＴＫＲ－４製のプロペラ４枚およびＮＴＫＲ－４製のパドル４枚を取り付けたアジターを備えるチャンバーを用いて撹拌しながら、１０ｇ／Ｌのクエン酸三ナトリウム（無水物）水溶液１．０Ｌを添加して３５℃に保温した。反応容器にさらに８．０ｇ／Ｌのポリスチレンスルホン酸水溶液０．６８Ｌを添加し、更に０．０４ｍｏｌ／Ｌの水酸化ナトリウム水溶液を用いて２３ｇ／Ｌに調製した水素化ホウ素ナトリウム水溶液０．０４１Ｌを添加した。反応容器にさらに０．１０ｇ／Ｌの硝酸銀水溶液１３Ｌを５．０Ｌ／ｍｉｎで添加した。
　反応容器にさらに１０ｇ／Ｌのクエン酸三ナトリウム（無水物）水溶液１．０Ｌとイオン交換水１１Ｌを添加して、更に８０ｇ／Ｌのヒドロキノンスルホン酸カリウム水溶液０．６８Ｌを添加した。撹拌を８００ｒｐｍに上げて、反応容器にさらに０．１０ｇ／Ｌの硝酸銀水溶液８．１Ｌを０．９５Ｌ／ｍｉｎで添加した後、３０℃に降温した。
　反応容器にさらに４４ｇ／Ｌのメチルヒドロキノン水溶液８．０Ｌを添加し、次いで、後述する方法で調製した４０℃のゼラチン水溶液を全量添加した。撹拌を１２００ｒｐｍに上げて、反応容器にさらに後述する方法で調製した亜硫酸銀白色沈殿物混合液を全量添加した。
　調製液のｐＨ変化が止まった段階で、反応容器にさらに１ｍｏｌ／ＬのＮａＯＨ水溶液５．０Ｌを０．３３Ｌ／ｍｉｎで添加した。その後、反応容器にさらに２．０ｇ／Ｌの１－（メタ－スルホフェニル）－５－メルカプトテトラゾールナトリウム水溶液（ＮａＯＨとクエン酸（無水物）とを用いてｐＨ＝７．０±１．０に調節して溶解した）０．１８Ｌを添加し、更に７０ｇ／Ｌの１，２－ベンズイソチアゾリン－３－オン（ＮａＯＨで水溶液をアルカリ性に調節して溶解した）０．０７８Ｌを添加した。このようにして銀平板粒子分散液Ａ１を調製した。 <Preparation of silver tabular grain dispersion B1>
(Preparation of silver tabular grain dispersion A1)
Agitator with 13L of ion-exchanged water measured in a reaction vessel of NTKR-4 (manufactured by Nippon Metal Industry Co., Ltd.) and four NTKR-4 propellers and four NTKR-4 paddles attached to a SUS316L shaft While stirring using a chamber equipped with 1.0 g of 10 g / L trisodium citrate (anhydrous) aqueous solution, 1.0 L was added and kept at 35 ° C. Further, 0.68 L of 8.0 g / L polystyrene sulfonic acid aqueous solution was added to the reaction vessel, and 0.041 mol of sodium borohydride aqueous solution prepared to 23 g / L using 0.04 mol / L sodium hydroxide aqueous solution was added. Added. Further, 13 L of a 0.10 g / L silver nitrate aqueous solution was added to the reaction vessel at 5.0 L / min.
Further, 1.0 L of 10 g / L trisodium citrate (anhydride) aqueous solution and 11 L of ion exchange water were added to the reaction vessel, and further 0.68 L of 80 g / L potassium hydroquinonesulfonate aqueous solution was added. The stirring was increased to 800 rpm, and 8.1 L of a 0.10 g / L silver nitrate aqueous solution was further added to the reaction vessel at 0.95 L / min, and then the temperature was lowered to 30 ° C.
Further, 8.0 L of 44 g / L methylhydroquinone aqueous solution was added to the reaction vessel, and then the whole amount of 40 ° C. gelatin aqueous solution prepared by the method described later was added. The stirring was increased to 1200 rpm, and the silver sulfite white precipitate mixture prepared by the method described later was further added to the reaction vessel.
When the pH change of the preparation liquid stopped, 5.0 L of 1 mol / L NaOH aqueous solution was further added to the reaction vessel at 0.33 L / min. Thereafter, an additional 2.0 g / L of 1- (meta-sulfophenyl) -5-mercaptotetrazole sodium aqueous solution (NaOH and citric acid (anhydride) was added to the reaction vessel to a pH of 7.0 ± 1.0. 0.18 L (adjusted and dissolved) was added, and 0.078 L of 70 g / L 1,2-benzisothiazolin-3-one (the aqueous solution was adjusted to be alkaline with NaOH) was added. In this way, silver tabular grain dispersion liquid A1 was prepared.
－ゼラチン水溶液の調製－
　ＳＵＳ３１６Ｌ製の溶解タンクにイオン交換水１６．７Ｌを計量した。ＳＵＳ３１６Ｌ製のアジターで低速撹拌を行いながら、脱イオン処理を施したアルカリ処理牛骨ゼラチン（ＧＰＣ重量平均分子量２０万）１．４ｋｇを添加した。更に、脱イオン処理、蛋白質分解酵素処理、および過酸化水素による酸化処理を施したアルカリ処理牛骨ゼラチン（ＧＰＣ重量平均分子量２．１万）０．９１ｋｇを添加した。その後４０℃に昇温し、ゼラチンの膨潤と溶解を同時に行って完全に溶解させた。得られた溶液をゼラチン水溶液として、上述の銀平板粒子分散液Ａ１の調製に用いた。 -Preparation of aqueous gelatin solution-
16.7 L of ion-exchanged water was weighed in a dissolution tank made of SUS316L. 1.4 kg of alkali-treated beef bone gelatin (GPC weight average molecular weight 200,000) subjected to deionization treatment was added while stirring at low speed with an agitator made of SUS316L. Furthermore, 0.91 kg of alkali-treated beef bone gelatin (GPC weight average molecular weight 21,000) subjected to deionization treatment, proteolytic enzyme treatment, and oxidation treatment with hydrogen peroxide was added. Thereafter, the temperature was raised to 40 ° C., and gelatin was swollen and dissolved simultaneously to completely dissolve it. The obtained solution was used as an aqueous gelatin solution for the preparation of the above-mentioned silver tabular grain dispersion A1.
－亜硫酸銀白色沈殿物混合液の調製－
　ＳＵＳ３１６Ｌ製の溶解タンクにイオン交換水８．２Ｌを計量し、１００ｇ／Ｌの硝酸銀水溶液８．２Ｌを添加した。ＳＵＳ３１６Ｌ製のアジターで高速撹拌を行いながら、１４０ｇ／Ｌの亜硫酸ナトリウム水溶液２．７Ｌを短時間で添加して、亜硫酸銀の白色沈澱物を含む混合液を調製した。得られた混合液を亜硫酸銀白色沈殿物混合液として、上述の銀平板粒子分散液Ａ１の調製に用いた。この混合液は、使用する直前に調製した。 -Preparation of silver sulfite white precipitate mixture-
In a dissolution tank made of SUS316L, 8.2 L of ion-exchanged water was weighed, and 8.2 L of a 100 g / L silver nitrate aqueous solution was added. While stirring at a high speed with an agitator made of SUS316L, 2.7 L of a 140 g / L sodium sulfite aqueous solution was added in a short time to prepare a mixed solution containing a silver sulfite white precipitate. The obtained mixed liquid was used as a silver sulfite white precipitate mixed liquid for the preparation of the above-mentioned silver tabular grain dispersion liquid A1. This mixture was prepared immediately before use.
（銀平板粒子分散液Ａ１の特性）
　銀平板粒子分散液Ａ１をイオン交換水で希釈し、分光光度計（（株）日立製作所製Ｕ－３５００）を用いて分光吸収を測定したところ、吸収ピーク波長は９００ｎｍであり、半値全幅は２７０ｎｍであった。
　銀平板粒子分散液Ａ１の物理特性は、２５℃においてｐＨ＝９．４（アズワン（株）製ＫＲ５Ｅで測定）、電気伝導度８．１ｍＳ／ｃｍ（東亜ディーケーケー（株）製ＣＭ－２５Ｒで測定）、粘度２．１ｍＰａ・ｓ（（株）エー・アンド・デイ製ＳＶ－１０で測定）であった。得られた銀平板粒子分散液Ａ１は、ユニオンコンテナーＩＩ型（低密度ポリエチレン製、販売元：アズワン（株））の２０Ｌの容器に収納し、３０℃で貯蔵した。 (Characteristics of the tabular silver particle dispersion A1)
When the silver tabular grain dispersion A1 was diluted with ion-exchanged water and spectral absorption was measured using a spectrophotometer (U-3500 manufactured by Hitachi, Ltd.), the absorption peak wavelength was 900 nm, and the full width at half maximum was 270 nm. Met.
The physical properties of the tabular silver particle dispersion A1 are as follows: pH = 9.4 at 25 ° C. (measured with KR5E manufactured by ASONE Co., Ltd.), electrical conductivity of 8.1 mS / cm (measured with CM-25R manufactured by Toa DKK Co., Ltd.) ) And a viscosity of 2.1 mPa · s (measured with SV-10 manufactured by A & D Co., Ltd.). The obtained silver tabular grain dispersion liquid A1 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.
（平板状金属粒子分散液の脱塩および再分散）
　前述の銀平板粒子分散液Ａ１を遠沈管に８００ｇ採取して、１ｍｏｌ／ＬのＮａＯＨおよび０．５ｍｏｌ／Ｌの硫酸のうち少なくとも一方を用いて２５℃でｐＨ＝９．２±０．２に調整した。遠心分離機（日立工機（株）製ｈｉｍａｃＣＲ２２ＧＩＩＩ、アングルローターＲ９Ａ）を用いて、３５℃に設定して、遠沈管中の銀平板粒子分散液Ａ１に９０００ｒｐｍで６０分間の遠心分離操作を行った後、上澄み液を７８４ｇ捨てた。沈殿した銀平板粒子に０．２ｍｍｏｌ／ＬのＮａＯＨ水溶液を加えて合計４００ｇとし、撹拌棒を用いて手撹拌して粗分散液にした（脱塩処理）。
　これと同様の操作で２４本分の粗分散液を調製して合計９６００ｇとし、ＳＵＳ３１６Ｌ製のタンクに添加して混合した。更に、タンクにＰｌｕｒｏｎｉｃ３１Ｒ１（ＢＡＳＦ社製）の１０ｇ／Ｌ溶液（メタノール：イオン交換水＝１：１（体積比）の混合液で希釈）を１０ｃｍ３添加した。プライミクス（株）製オートミクサー２０型（撹拌部はホモミクサーＭＡＲＫＩＩ）を用いて、タンク中の粗分散液に９０００ｒｐｍで１２０分間のバッチ式分散処理（再分散処理）を施した。再分散処理中の液温は５０℃に保った。再分散処理の後、タンク中の再分散液を２５℃に降温してから、プロファイルＩＩフィルター（日本ポール（株）製、製品型式ＭＣＹ１００１Ｙ０３０Ｈ１３）を用いてシングルパスの濾過を行った。 (Desalting and redispersion of flat metal particle dispersion)
800 g of the above-mentioned silver tabular grain dispersion A1 was collected in a centrifuge tube, and the pH was adjusted to 9.2 ± 0.2 at 25 ° C. using at least one of 1 mol / L NaOH and 0.5 mol / L sulfuric acid. It was adjusted. Using a centrifuge (HimacCR22GIII, angle rotor R9A, manufactured by Hitachi Koki Co., Ltd.), the temperature was set to 35 ° C., and the centrifugal separation operation was performed at 9000 rpm for 60 minutes on the silver tabular particle dispersion A1 in the centrifuge tube. Thereafter, 784 g of the supernatant was discarded. A 0.2 mmol / L 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 (desalting treatment).
In the same manner as this, 24 coarse dispersions were prepared to a total of 9600 g, added to a SUS316L tank and mixed. Further, 10 cm 3 of a 10 g / L solution of Pluronic 31R1 (manufactured by BASF) (diluted with a mixed solution of methanol: ion exchange water = 1: 1 (volume ratio)) was added to the tank. Using an automixer type 20 manufactured by Primix Co., Ltd. (stirring section is a homomixer MARKII), the crude dispersion in the tank was subjected to batch dispersion treatment (redispersion treatment) at 9000 rpm for 120 minutes. The liquid temperature during the redispersion treatment was kept at 50 ° C. After the redispersion treatment, the temperature of the redispersed liquid in the tank was lowered to 25 ° C., and single-pass filtration was performed using a profile II filter (manufactured by Nippon Pole Co., Ltd., product type MCY1001Y030H13).
　このようにして、銀平板粒子分散液Ａ１に脱塩処理および再分散処理を施して、銀平板粒子分散液Ｂ１を調製した。 Thus, the silver tabular grain dispersion liquid A1 was subjected to a desalting treatment and a redispersion treatment to prepare a silver tabular grain dispersion liquid B1.
（銀平板粒子分散液Ｂ１の特性）
　銀平板粒子分散液Ｂ１の分光透過率を、銀平板粒子分散液Ａ１と同様の方法で測定したところ、吸収ピーク波長および半値全幅は銀平板粒子分散液Ａ１とほぼ同じ結果であった。
　銀平板粒子分散液Ｂ１の物理特性は、２５℃においてｐＨ＝７．６、電気伝導度０．３７ｍＳ／ｃｍ、粘度１．１ｍＰａ・ｓであった。得られた銀平板粒子分散液Ｂ１は、ユニオンコンテナーＩＩ型の２０Ｌの容器に収納し、３０℃で貯蔵した。 (Characteristics of the tabular silver particle dispersion B1)
When the spectral transmittance of the tabular silver particle dispersion B1 was measured by the same method as that of the tabular silver particle dispersion A1, the absorption peak wavelength and full width at half maximum were almost the same as those of the tabular silver particle dispersion A1.
The physical properties of the tabular silver particle dispersion B1 were pH = 7.6, electrical conductivity of 0.37 mS / cm, and a viscosity of 1.1 mPa · s at 25 ° C. The obtained silver tabular grain dispersion liquid B1 was stored in a 20 L container of Union Container II type and stored at 30 ° C.
＜近赤外線反射層用の塗布液Ｍ１の作製＞
　以下、近赤外線反射層用の塗布液Ｍ１の作製について記載する。塗布液の調製に用いた原材料は、購入した素原料を希釈したり、あるいは分散物にしたりするなど、適宜加工して使用した。 <Preparation of coating liquid M1 for near-infrared reflective layer>
Hereinafter, preparation of the coating liquid M1 for the near-infrared reflective layer will be described. The raw materials used for the preparation of the coating liquid were used after appropriately processing, for example, by diluting purchased raw materials or making them into dispersions.
（近赤外線反射層用の塗布液Ｍ１の調製）
　以下の配合で、近赤外線反射層用の塗布液Ｍ１を調製した。
－塗布液Ｍ１－
水性ウレタン樹脂：ハイドランＨＷ３５０
　（ＤＩＣ（株）製、固形分３０質量％）　　　　　　　　０．２７質量部
上記銀平板粒子分散液Ｂ１　　　　　　　　　　　　　　１０．２４質量部
１－（メチルウレイドフェニル）－５－メルカプトテトラゾール
　（和光純薬工業（株）製、固形分２質量％のアルカリ性水溶液を調製）
　　　　　　　　　　　　　　　　　　　　　　　　　　　０．６１質量部
界面活性剤Ａ：リパール８７０Ｐ
（ライオン（株）製、固形分１質量％イオン交換水希釈）　０．９６質量部
界面活性剤Ｂ：ナロアクティーＣＬ－９５
　（三洋化成工業（株）製、固形分１質量％イオン交換水希釈）
　　　　　　　　　　　　　　　　　　　　　　　　　　　１．１９質量部
メタノール　　　　　　　　　　　　　　　　　　　　　３０．００質量部
蒸留水　　　　　　　　　　　　　　　　　　　　　　　５０．７３質量部 (Preparation of coating solution M1 for the near-infrared reflective layer)
A coating liquid M1 for a near-infrared reflective layer was prepared with the following composition.
-Coating liquid M1-
Aqueous urethane resin: Hydran HW350
(Dic Co., Ltd., solid content: 30% by mass) 0.27 parts by mass Silver tabular grain dispersion B1 10.24 parts by mass 1- (methylureidophenyl) -5-mercaptotetrazole (Wako Pure Chemical Industries, Ltd.) Manufactured, prepared 2% by mass of alkaline aqueous solution)
0.61 part by mass Surfactant A: Lipal 870P
(Manufactured by Lion Co., Ltd., diluted with ion exchange water at a solid content of 1% by mass) 0.96 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 Methanol 30.00 parts by mass Distilled water 50.73 parts by mass
＜近赤外線反射層の塗布による形成＞
　実施例１の断熱フィルムに対し、接着層付き支持体（ＰＥＴ基板；図５中の符号１０１）の繊維状金属粒子含有層が配置された面の裏面に、上記の近赤外線反射層用の塗布液Ｍ１を、ワイヤーバーを用いて１０．６ｃｍ３／ｍ２となるように塗布し、１４０℃で乾燥処理を施して、近赤外線反射層（図５には不図示）を設けた。塗布乾燥後の近赤外線反射層の膜厚は１０ｎｍであった。
　得られた断熱フィルムを、実施例１２の断熱フィルムとした。 <Formation by application of near-infrared reflective layer>
On the back surface of the surface on which the fibrous metal particle-containing layer of the support with an adhesive layer (PET substrate; reference numeral 101 in FIG. 5) is disposed on the heat insulating film of Example 1, the application for the near-infrared reflective layer described above The liquid M1 was applied to be 10.6 cm 3 / m 2 using a wire bar, dried at 140 ° C., and a near-infrared reflective layer (not shown in FIG. 5) was provided. The film thickness of the near-infrared reflective layer after coating and drying was 10 nm.
The obtained heat insulating film was used as the heat insulating film of Example 12.
［比較例１］
　実施例１の断熱フィルムの作製において、表面層無しとした以外は実施例１と同様にして、比較例１の断熱フィルムを得た。 [Comparative Example 1]
In the production of the heat insulating film of Example 1, a heat insulating film of Comparative Example 1 was obtained in the same manner as in Example 1 except that no surface layer was used.
［比較例２］
　実施例９の断熱フィルムの作製において、表面層無しとした以外は実施例９と同様にして、比較例２の断熱フィルムを得た。 [Comparative Example 2]
In the production of the heat insulating film of Example 9, a heat insulating film of Comparative Example 2 was obtained in the same manner as in Example 9 except that no surface layer was used.
［比較例３］
　実施例１０の断熱フィルムの作製において、表面層無しとした以外は実施例１０と同様にして、比較例３の断熱フィルムを得た。 [Comparative Example 3]
In the production of the heat insulating film of Example 10, a heat insulating film of Comparative Example 3 was obtained in the same manner as in Example 10 except that no surface layer was used.
［比較例４］
　実施例１１の断熱フィルムの作製において、表面層無しとした以外は実施例１１と同様にして、比較例４の断熱フィルムを得た。 [Comparative Example 4]
In the production of the heat insulating film of Example 11, a heat insulating film of Comparative Example 4 was obtained in the same manner as in Example 11 except that the surface layer was not used.
［参考例１］
＜ＩＴＯ／Ａｇ／ＩＴＯ系の積層体である赤外線反射層＞
　特開平１０－１３９４８９号公報の実施例１参照に記載の方法にしたがって、支持体上に、ＩＴＯ／Ａｇ／ＩＴＯの積層体である赤外線反射層を設けた。
　上記のＩＴＯ／Ａｇ／ＩＴＯの積層体である赤外線反射層の表面上に、実施例１と同様にして表面層を形成して、参考例１の断熱フィルムを得た。 [Reference Example 1]
<Infrared reflective layer that is a laminate of ITO / Ag / ITO>
According to the method described in Example 1 of JP-A-10-139489, an infrared reflecting layer which is an ITO / Ag / ITO laminate was provided on a support.
A surface layer was formed in the same manner as in Example 1 on the surface of the infrared reflective layer, which was a laminate of the above ITO / Ag / ITO, to obtain a heat insulating film of Reference Example 1.
［参考例２］
　参考例１の断熱フィルムの作製において、表面層無しとした以外は参考例１と同様にして、参考例２の断熱フィルムを得た。 [Reference Example 2]
In the production of the heat insulating film of Reference Example 1, a heat insulating film of Reference Example 2 was obtained in the same manner as Reference Example 1 except that the surface layer was not used.
［断熱ガラスの作製］
＜粘着層の形成＞
　各実施例および比較例で作製した断熱フィルムの繊維状金属粒子含有層と対向する支持体の表面上に、粘着材を以下の方法で貼り合わせ、粘着層を形成した。粘着材としてパナック（株）製パナクリーンＰＤ－Ｓ１（粘着層２５μｍ）を使用して、粘着材の軽剥離セパレータ（シリコーンコートＰＥＴ）を剥がしてから、支持体の表面に貼り合わせた。 [Production of heat insulating glass]
<Formation of adhesive layer>
On the surface of the support opposite to the fibrous metal particle-containing layer of the heat insulating film produced in each Example and Comparative Example, an adhesive material was bonded by the following method to form an adhesive layer. Using Panaclean PD-S1 (adhesive layer 25 μm) manufactured by Panac Co., Ltd. as the adhesive, the light release separator (silicone-coated PET) as an adhesive was peeled off, and then bonded to the surface of the support.
＜断熱ガラスの製造＞
　上記の方法で形成した粘着層から粘着材ＰＤ－Ｓ１の他方の重剥離セパレータ（シリコーンコートＰＥＴ）を剥がし、フィルム施工液であるリアルパーフェクト（リンテック（株）製）の０．５質量％希釈液を使用してソーダ石灰珪酸塩である板ガラス（板ガラス厚み：３ｍｍの青板ガラス）と貼り合わせて、各実施例および比較例の断熱ガラスを作製した。 <Manufacture of heat insulating glass>
The other heavy release separator (silicone-coated PET) of the adhesive material PD-S1 is peeled off from the adhesive layer formed by the above method, and a 0.5% by weight diluted solution of Real Perfect (manufactured by Lintec Corporation), which is a film construction solution Was used to laminate soda lime silicate plate glass (plate glass thickness: 3 mm blue plate glass) to produce heat insulating glass of each of Examples and Comparative Examples.
［評価］
　上記で得られた各実施例および比較例の断熱フィルムまたは断熱ガラスを用いて、後述する各種の評価を実施した。 [Evaluation]
Various evaluations to be described later were performed using the heat insulating films or the heat insulating glasses of the examples and comparative examples obtained above.
＜断熱フィルムの評価＞
（最表面の水接触角）
　各断熱フィルムにおいて、支持体よりも繊維状金属粒子含有層に近い側の最表面について、水接触角を以下の方法で測定した。
　環境条件：２５℃、相対湿度６０％において、接触角計　Ｄｒｏｐ　Ｍａｓｔｅｒ　３００（協和界面化学（株）製）を用い、作製した各断熱フィルムの表面に純水を２μｌ滴下して、θ／２法により接触角［°］を測定し、５回測定して得た値の平均値を最表面の水接触角とした。
　得られた結果を下記表１に記載した。 <Evaluation of heat insulation film>
(Surface water contact angle)
In each heat insulating film, the water contact angle was measured by the following method for the outermost surface closer to the fibrous metal particle-containing layer than the support.
Environmental conditions: At 25 ° C. and a relative humidity of 60%, a contact angle meter Drop Master 300 (manufactured by Kyowa Interface Chemical Co., Ltd.) was used. Then, the contact angle [°] was measured, and the average value of the values obtained by measuring 5 times was defined as the water contact angle of the outermost surface.
The obtained results are shown in Table 1 below.
（耐傷性）
　環境条件：２５℃、相対湿度６０％においてラビングテスタ（ＡＢ３０１、テスター産業（株）製）を用い、作製した各断熱フィルムの表面を、スチールウール（＃００００、日本スチールウール（株）製）に、２００ｇの荷重をかけて、ストローク幅２５ｍｍ、速度３０ｍｍ／ｓｅｃで１０回往復摩擦した。その後の各断熱フィルムの摩擦した表面を目視観察し、以下の評価基準に従ってランク付けした。
評価基準：
ＡＡ；真上から確認できる傷が、０～５本
　Ａ；真上から確認できる傷が、６～１０本
　Ｂ；真上から確認できる傷が、１１～２０本
　Ｃ；真上から確認できる傷が、２１本以上
　得られた結果を下記表１に記載した。 (Scratch resistance)
Environmental conditions: Using a rubbing tester (AB301, manufactured by Tester Sangyo Co., Ltd.) at 25 ° C. and a relative humidity of 60%, the surface of each manufactured heat insulating film is made into steel wool (# 0000, manufactured by Nippon Steel Wool Co., Ltd.). A 200 g load was applied, and reciprocating friction was performed 10 times at a stroke width of 25 mm and a speed of 30 mm / sec. The rubbed surface of each subsequent heat insulating film was visually observed and ranked according to the following evaluation criteria.
Evaluation criteria:
AA: 0 to 5 scratches that can be confirmed from directly above A: 6 to 10 scratches that can be confirmed from directly above B; 11 to 20 scratches that can be confirmed from directly above C; However, 21 or more results are shown in Table 1 below.
（汚れ拭き取り試験）
　環境条件：２５℃、相対湿度６０％において、各断熱フィルム表面に黒マジック（マッキー極細（商品名：ＺＥＢＲＡ製））のペン先（細）にて直径５ｍｍの円形を３周書き込み、書き込み部分を覆うのに十分な量の水をかけた。１０秒後に１０枚重ねに折り束ねたベンコット（商品名、旭化成（株））でベンコットの束がへこむ程度の荷重でかけた水がなくなるまで拭き取った。５名の観察者でマジック跡を目視で以下の５段階で評価し、その平均値を採用した。
評価基準：
ＡＡ；マジック跡が全く見えない
　Ａ；マジック跡がかすかに見える
　Ｂ；マジック跡がうっすらと見える
　Ｃ；マジック跡が見える
　得られた結果を下記表１に記載した。 (Dirt wiping test)
Environmental conditions: At 25 ° C. and 60% relative humidity, write a circle with a diameter of 5 mm three times on the surface of each insulation film with a black magic (Mackey extra fine (trade name: made by ZEBRA)) nib. A sufficient amount of water was applied to cover. After 10 seconds, a becot (trade name, Asahi Kasei Co., Ltd.) that was folded into 10 sheets was wiped off until there was no water applied with a load enough to dent the bundle. Five observers visually evaluated the magic marks in the following five levels, and adopted the average value.
Evaluation criteria:
AA: No magic mark is visible A: Magic mark is faint B: Magic mark is slightly visible C: Magic mark is visible The results obtained are shown in Table 1 below.
＜断熱ガラスの評価＞
（断熱性（Ｕ値）の初期値）
　環境条件：８５℃、相対湿度８５％の恒温高湿槽で１００時間保持する前の断熱性（Ｕ値）の初期値を以下の方法で評価した。
　各断熱ガラスの反射スペクトルを、赤外分光機（ＩＦＳ６６ｖ／Ｓ、ブルカー・オプティクス社製）を用いて波長５μｍ～２５μｍの範囲で測定した。ＪＩＳ　Ａ　５７５９に準拠して熱貫流率（Ｕ値）を算出した。尚、波長２５μｍ～５０μｍの反射率はＪＩＳ　Ａ　５７５９に従って２５μｍの反射率から外挿した。熱貫流率（Ｕ値）が小さいほど、断熱性が高く、好ましい。
　得られた結果を、断熱性（Ｕ値）の「初期値」として下記表１に記載した。 <Evaluation of heat insulating glass>
(Initial value of thermal insulation (U value))
Environmental conditions: The initial value of the heat insulating property (U value) before being held for 100 hours in a constant temperature and high humidity bath at 85 ° C. and 85% relative humidity was evaluated by the following method.
The reflection spectrum of each heat insulating glass was measured in the wavelength range of 5 μm to 25 μm using an infrared spectrometer (IFS66v / S, manufactured by Bruker Optics). The heat transmissibility (U value) was calculated according to JIS A 5759. Incidentally, the reflectance at a wavelength of 25 μm to 50 μm was extrapolated from the reflectance of 25 μm according to JIS A 5759. The smaller the heat transmissibility (U value), the higher the heat insulation, which is preferable.
The obtained results are shown in Table 1 below as “initial value” of heat insulation (U value).
（断熱性の湿熱経時後変化率）
　環境条件：８５℃、相対湿度８５％の恒温高湿槽で１００時間保持した後の断熱性を評価した。
　各断熱ガラスを、環境条件：８５℃、相対湿度８５％の恒温高湿槽で１００時間保持したのち、上記の初期の断熱性の評価と同様の方法で熱貫流率（Ｕ値）を測定し、湿熱経時後の熱貫流率を求めた。
　湿熱処理前の初期の断熱性（湿熱前Ｕ値）に対する湿熱処理後の断熱性（湿熱後Ｕ値）の変化量（絶対値）を百分率で評価した。
　計算式：湿熱経時後変化率＝１００×｜（湿熱前Ｕ値－湿熱後Ｕ値）｜／湿熱前Ｕ値
　得られた結果を、断熱性（Ｕ値）の「湿熱経時後変化率」として下記表１に記載した。 (The rate of change in heat-insulating wet heat over time)
Environmental conditions: The heat insulation after being held for 100 hours in a constant temperature and high humidity bath at 85 ° C. and 85% relative humidity was evaluated.
Each heat insulating glass is held for 100 hours in a constant temperature and high humidity bath at 85 ° C. and 85% relative humidity, and then the heat transmissivity (U value) is measured in the same manner as in the initial evaluation of heat insulation. The heat transmissivity after wet heat aging was determined.
The amount of change (absolute value) of the heat insulating property after wet heat treatment (U value after wet heat) relative to the initial heat insulating property before wet heat treatment (U value before wet heat) was evaluated as a percentage.
Calculation formula: Rate of change after wet heat aging = 100 × | (U value before wet heat−U value after wet heat) | / U value before wet heat The obtained result is used as the “rate of change after wet heat aging” of heat insulation (U value) It described in Table 1 below.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　以上より、本発明の断熱フィルムは、銀を主成分とする繊維状金属粒子およびバインダーを含む繊維状金属粒子含有層を用いた場合に、湿熱経時後の断熱性変化を抑制できることがわかった。
　一方、比較例１～４より、断熱フィルムの最表面の水接触角が９０°未満である場合、湿熱経時後の断熱性変化が大きいことがわかった。特に比較例４より、特開２０１２－２５２１７２号公報の［００４８］に記載されているシリコン樹脂バインダー（シリコーンバインダー）を用いた層が最表面となっている場合であっても、接触角が９０°未満となるシリコーンバインダーを用いた繊維状金属粒子含有層を用いたときは、湿熱経時後の断熱性変化が大きいことがわかった。 From the above, it was found that the heat insulating film of the present invention can suppress a change in heat insulating property after aging with wet heat when using a fibrous metal particle-containing layer containing fibrous metal particles mainly composed of silver and a binder.
On the other hand, from Comparative Examples 1 to 4, it was found that when the water contact angle on the outermost surface of the heat insulating film was less than 90 °, the change in heat insulating property after wet heat aging was large. In particular, from Comparative Example 4, even when the layer using a silicon resin binder (silicone binder) described in [0048] of JP2012-252172A is the outermost surface, the contact angle is 90. It was found that when the fibrous metal particle-containing layer using a silicone binder having a temperature of less than 0 ° was used, the heat insulating property change after wet heat aging was large.
　さらに本発明の断熱フィルムの好ましい態様によれば、耐擦性や、汚れ拭き取り試験結果や、断熱性の初期値も改善できることがわかった。
　各実施例の断熱フィルムを建材の窓に貼ったところ、使用しなかった場合に比べて冬場の平均で１０％エアコンの消費量を抑えられた。
　また、各実施例の断熱フィルムを自動車の窓に貼ったところ、冬場の平均で１５％エアコンの消費量を抑えられた。
　近赤外線反射層との積層の実施例１２では、さらに夏場のエアコン消費量を抑えられた。 Furthermore, according to the preferable aspect of the heat insulation film of this invention, it turned out that abrasion resistance, a dirt wiping test result, and the initial value of heat insulation can also be improved.
When the heat insulation film of each Example was stuck on the window of the building material, the consumption of the air conditioner was reduced by 10% on average in the winter compared with the case where it was not used.
Moreover, when the heat insulation film of each Example was stuck on the window of the car, the consumption of the air conditioner was reduced by 15% on average in winter.
In Example 12 of the lamination with the near-infrared reflective layer, the consumption of the air conditioner in summer was further suppressed.
　本発明の断熱フィルムの好ましい態様によれば、水の接触角１１０°以上であると、相対湿度９０％以上の高湿度環境に断熱フィルムを配置しても、水滴による表面の曇りが目視で明らかに観察しにくくなったことから、湿熱経時後の断熱性変化が抑制できたと考えられる。また、水の接触角が１１０°以上の材料（サイトップ　ＣＴＸ－１０９Ｍ）は、吸水率および水蒸気透過率のうち少なくとも一方が他のバインダーと表面層に使用した材料に比べて低いことが確認できたため、水分の浸透を抑制できたと考えられる。 According to a preferred embodiment of the heat insulating film of the present invention, when the water contact angle is 110 ° or more, even if the heat insulating film is disposed in a high humidity environment having a relative humidity of 90% or more, the cloudiness of the surface due to water droplets is clearly visible Therefore, it is considered that the heat insulation change after wet heat aging could be suppressed. In addition, it can be confirmed that the material having a water contact angle of 110 ° or more (Cytop CTX-109M) has a lower water absorption rate or water vapor transmission rate than the other binder and the material used for the surface layer. Therefore, it is considered that the penetration of moisture could be suppressed.
　本発明の断熱フィルムを用いた本発明の断熱ガラスは、湿熱経時後の断熱性変化を抑制できるため、本発明の断熱フィルムが窓の内側に配置されると湿熱経時後の断熱性変化を抑制できる窓を提供できる。このような本発明の断熱フィルムは、ヘイズの低さと断熱性の高さを両立できる窓を含む建築物や乗物を提供することができる。さらに、既存の近赤外線遮蔽層と組合わせることで、窓の屋外側の光を屋内側に取り入れつつ、窓の屋外側からの光照射による屋内側の温度上昇を抑制でき、窓の屋外側の光が長期にわたって屋内側に取り入れる場合も屋内側から屋外側への熱交換の抑制をすることができるため、このような窓が設けられた建築物や乗物の屋内側（室内側、車内側）を望ましい環境に保つことができる。
　また、本発明の断熱フィルムは、既存の窓（例えば建築物や乗物の窓）に対して、窓の内側に貼ること（内貼り）によっても、湿熱経時後の断熱性変化を抑制できる窓を提供できる。 Since the heat insulating glass of the present invention using the heat insulating film of the present invention can suppress the heat insulating change after the aging of wet heat, the heat insulating property after the aging of the wet heat is suppressed when the heat insulating film of the present invention is arranged inside the window. Can provide a window that can. Such a heat insulating film of the present invention can provide a building or vehicle including a window that can achieve both low haze and high heat insulating properties. Furthermore, by combining with the existing near-infrared shielding layer, it is possible to suppress the temperature rise on the indoor side due to light irradiation from the outdoor side of the window while taking in the light on the outdoor side of the window. Even when light is introduced indoors over a long period of time, heat exchange from the indoor side to the outdoor side can be suppressed, so the indoor side of buildings and vehicles with such windows (indoors, inside the car) Can be kept in the desired environment.
Moreover, the heat insulation film of this invention is a window which can suppress the heat insulation change after time-lapse | temporality of moist heat also by pasting inside a window (internal sticking) with respect to the existing window (for example, window of a building or a vehicle). Can be provided.
１０　　　支持体
２０　　　繊維状金属粒子含有層
２１　　　表面層
３１　　　第１の接着層
３２　　　第２の接着層
４１　　　近赤外線遮蔽層
５１　　　粘着層
６１　　　ガラス
１０１　　接着層付きの支持体
１０２　　断熱部材
１０３　　断熱フィルム
１１１　　断熱ガラス
ＩＮ　　　屋内側
ＯＵＴ　　屋外側 DESCRIPTION OF SYMBOLS 10 Support body 20 Fibrous metal particle content layer 21 Surface layer 31 1st adhesive layer 32 2nd adhesive layer 41 Near-infrared shielding layer 51 Adhesion layer 61 Glass 101 Support body 102 with an adhesive layer Thermal insulation member 103 Thermal insulation film 111 Thermal insulation Glass IN Indoor side OUT Outdoor side

Claims (14)

  1. 　支持体と、
    　前記支持体の一方の面上に配置され、銀を主成分とする繊維状金属粒子およびバインダーを含む繊維状金属粒子含有層とを有する断熱フィルムであって、
    　前記断熱フィルムの最表面の水接触角が９０°以上である、断熱フィルム。     A support;
    A heat insulating film that is disposed on one surface of the support and has a fibrous metal particle-containing layer containing fibrous metal particles mainly containing silver and a binder,
    The heat insulation film whose water contact angle of the outermost surface of the said heat insulation film is 90 degrees or more.
  2. 　前記断熱フィルムの水接触角が９０°以上である前記最表面が、前記支持体よりも前記繊維状金属粒子含有層に近い側の最表面である、請求項１に記載の断熱フィルム。 The heat insulating film according to claim 1, wherein the outermost surface having a water contact angle of 90 ° or more of the heat insulating film is an outermost surface closer to the fibrous metal particle-containing layer than the support.
  3. 　前記繊維状金属粒子含有層の前記支持体とは反対の面上に、さらに水接触角が９０°以上である表面層を含む、請求項１または２に記載の断熱フィルム。 The heat insulating film according to claim 1 or 2, further comprising a surface layer having a water contact angle of 90 ° or more on a surface opposite to the support of the fibrous metal particle-containing layer.
  4. 　前記表面層の主成分が、フッ素を含有する材料またはケイ素を含有する材料である、請求項３に記載の断熱フィルム。 The heat insulating film according to claim 3, wherein the main component of the surface layer is a material containing fluorine or a material containing silicon.
  5. 　前記表面層の膜厚が、１μｍ以下である、請求項３または４に記載の断熱フィルム。 The heat insulating film according to claim 3 or 4, wherein the surface layer has a thickness of 1 µm or less.
  6. 　前記表面層が、単分子膜である、請求項３～５のいずれか一項に記載の断熱フィルム。 The heat insulating film according to any one of claims 3 to 5, wherein the surface layer is a monomolecular film.
  7. 　前記繊維状金属粒子含有層の前記バインダーの主成分が、ケイ素を含有する材料である、請求項１～６のいずれか一項に記載の断熱フィルム。 The heat insulating film according to any one of claims 1 to 6, wherein a main component of the binder of the fibrous metal particle-containing layer is a material containing silicon.
  8. 　前記支持体の前記繊維状金属粒子含有層が配置された面とは反対の面に、さらに近赤外線遮蔽層を含む、請求項１～７のいずれか一項に記載の断熱フィルム。 The heat insulating film according to any one of claims 1 to 7, further comprising a near-infrared shielding layer on a surface opposite to the surface on which the fibrous metal particle-containing layer of the support is disposed.
  9. 　前記断熱フィルムの最表面の水接触角が１１０°以上である、請求項１～８のいずれか一項に記載の断熱フィルム。 The heat insulating film according to any one of claims 1 to 8, wherein a water contact angle on the outermost surface of the heat insulating film is 110 ° or more.
  10. 　前記支持体が、透明フィルムである、請求項１～９のいずれか一項に記載の断熱フィルム。 The heat insulating film according to any one of claims 1 to 9, wherein the support is a transparent film.
  11. 　前記繊維状金属粒子の平均長軸長が５～５０μｍである、請求項１～１０のいずれか一項に記載の断熱フィルム。 The heat insulating film according to any one of claims 1 to 10, wherein an average major axis length of the fibrous metal particles is 5 to 50 袖 m.
  12. 　窓の内側に配置され、
    　前記繊維状金属粒子含有層が、前記支持体の前記窓側の面とは反対側の面上に配置される、請求項１～１１のいずれか一項に記載の断熱フィルム。     Placed inside the window,
    The heat insulating film according to any one of claims 1 to 11, wherein the fibrous metal particle-containing layer is disposed on a surface of the support opposite to the window-side surface.
  13. 　請求項１～１２のいずれか一項に記載の断熱フィルムと、ガラスとを積層した、断熱ガラス。 A heat insulating glass obtained by laminating the heat insulating film according to any one of claims 1 to 12 and glass.
  14. 　窓用透明支持体と、前記窓用透明支持体に貼り合わせた請求項１～１２のいずれか一項に記載の断熱フィルムを含む、窓。 A window comprising the transparent support for windows and the heat insulating film according to any one of claims 1 to 12 bonded to the transparent support for windows.
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