JP2017030235A - Heat-shielding material, heat-insulating material and window glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-shielding material, a heat insulating material and a window glass which suppress deterioration in transparency caused by a working liquid used when applying to an adherend.SOLUTION: There are provided a heat-shielding material, a heat-insulating material and a window glass 30 which comprise: a support 3; a metal containing-layer 2 containing a metal element; an organic particle-containing layer 1 containing organic particles having an average particle diameter of 0.1 μm to 15 μm and a glass transition temperature of 100°C or more; an adhesive layer 6; and a glass substrate 7 in this order.SELECTED DRAWING: Figure 4

Description

  The present invention relates to a heat shielding material, a heat insulating material, and a window glass.

In recent years, as one of energy saving measures for reducing carbon dioxide emissions, a heat shielding material used for windows of automobiles and buildings has been developed. The heat shielding material includes a heat ray absorption type material having re-radiation of absorbed heat rays (radiation is about 1/3 of the absorbed heat ray energy) and a heat ray reflection type material having no re-radiation. From the viewpoint of heat shield efficiency, the heat shield material is desirably a heat ray reflective material.
In consideration of application to windows of automobiles and buildings, the heat shielding material is required to have high transparency of the material itself and high heat shielding efficiency.

Various heat shielding materials as described above have been proposed.
For example, a base material, a metal particle-containing layer containing at least one kind of metal particles, and an overcoat layer disposed in close contact with at least one surface of the metal particle-containing layer, There has been proposed a heat ray shielding material having 60% by number or more of hexagonal or circular plate-like metal particles and an overcoat layer containing fine particles (see, for example, Patent Document 1).

  An electromagnetic wave transmissive laminate comprising a substrate and a metal particle-containing layer containing at least one kind of metal particles disposed on the substrate, wherein the metal particles are hexagonal or circular plate-like metal. An electromagnetic wave transmissive laminate having 60% by number or more of particles has been proposed (see, for example, Patent Document 2).

JP 2013-228694 A JP-A-2015-51608

By the way, a heat shielding material used for a window of an automobile or a building may be used by being attached to the window via an adhesive. As a method for affixing the heat shielding material to the window, there is a method for affixing the heat shielding material after applying a construction liquid to the window. In this case, the heat shielding material pasted using the construction liquid may have a problem that transparency may decrease (haze increases) when several days to several weeks have passed since pasting, which may be a problem.
The heat ray shielding material described in Patent Document 1 and the electromagnetic wave transmissive laminate described in Patent Document 2 are not assumed to be attached using a construction liquid, and the transparency of the material derived from the construction liquid is reduced. It has not been studied to suppress this.

  The present invention has been made in view of the above, and it is an object of the present invention to provide a heat shielding material, a heat insulating material, and a window glass in which a decrease in transparency derived from a construction liquid used during construction on an adherend is suppressed. And

Specific means for solving the problems include the following aspects.
<1> A support, a metal-containing layer containing a metal element, and an organic particle-containing layer containing organic particles having an average particle diameter of 0.1 μm to 15 μm and a glass transition temperature of 100 ° C. or higher. Heat shielding material in this order.

<2> The heat-shielding material according to <1>, wherein the metal-containing layer includes flat metal particles.
<3> The heat shielding material according to <2>, wherein the flat metal particles are flat silver particles.
<4> The heat shielding material according to any one of <1> to <3>, wherein the average particle diameter of the organic particles is 0.35 μm to 5.0 μm.
<5> The heat shielding material according to any one of <1> to <4>, wherein the organic particle-containing layer has a thickness of 0.2 μm to 1.5 μm.

<6> The heat shielding material according to any one of <1> to <5>, wherein the ratio of the average particle diameter of the organic particles to the thickness of the organic particle-containing layer is 1.15 to 3.75.
<7> The shielding according to any one of <1> to <6>, wherein the content of the organic particles is 0.5% by mass to 5.5% by mass with respect to the total solid content of the organic particle-containing layer. Thermal material.
<8> The shielding according to any one of <1> to <7>, wherein the content of the organic particles is 1.5% by mass to 3.5% by mass with respect to the total solid content of the organic particle-containing layer. Thermal material.

<9> The heat shielding material according to any one of <1> to <8>, wherein the glass transition temperature of the organic particles is 200 ° C. or higher.
<10> The heat shielding material according to any one of <1> to <9>, wherein the organic particles are particles of a hydrophobic resin.
<11> The heat shielding material according to any one of <1> to <10>, wherein the organic particles are poly (meth) acrylate particles.
<12> The heat shielding material according to any one of <1> to <11>, wherein the organic particles are particles of polymethyl methacrylate.
<13> The heat shielding material according to any one of <1> to <12>, having a protective layer containing inorganic particles on the side opposite to the side having the metal-containing layer of the support.
<14> The heat shielding material according to any one of <1> to <13>, wherein the organic particle-containing layer has an organic wax content of 1% by mass or less based on the total solid content of the organic particle-containing layer.

<15> The heat insulation material including the heat shielding material according to any one of <1> to <14> and fibrous metal particles disposed on the side opposite to the side having the metal-containing layer of the support of the heat shielding material. And a heat insulating material.

<16> A window glass having the heat shielding material according to any one of <1> to <14> or the heat insulating material according to <15>, an adhesive layer, and a glass substrate in this order.
<17> The window glass according to <16>, wherein the heat shielding material or the heat insulating material is disposed with the side having the organic particle-containing layer facing the pressure-sensitive adhesive layer.

  ADVANTAGE OF THE INVENTION According to this invention, the thermal-insulation material, heat insulation material, and window glass in which the fall of the transparency derived from the construction liquid used at the time of construction to a to-be-adhered body was suppressed are provided.

It is the schematic which shows an example of the heat insulation material of this invention. It is the schematic which shows another example of the heat shielding material of this invention. It is the schematic which shows an example of the heat insulation material of this invention. It is the schematic which shows an example of the window glass of this invention. It is the schematic perspective view which showed an example of the shape of the flat metal particle preferably used for the heat-shielding material of this invention, Comprising: A circular flat metal particle is shown. It is the schematic perspective view which showed an example of the shape of the flat metal particle preferably used for the heat-shielding material of this invention, Comprising: A hexagonal flat metal particle is shown.

Hereinafter, the heat shielding material, the heat insulating material, and the window glass of the present invention will be described in detail.
In this specification, the numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
In this specification, (meth) acrylate means at least one of acrylate and methacrylate. Moreover, (meth) acryl means at least one of acrylic and methacryl.

In this specification, “heat insulation” means that heat rays having a wavelength of 700 nm to 1200 nm are reflected by an average reflectance of 5% or more. The average reflectance of the heat ray is more preferably 7% or more, particularly preferably 8% or more, and particularly preferably 10% or more.
The average reflectance of heat rays can be measured by V-670 (manufactured by JASCO Corporation) and determined by the method described in JIS A-5759.
Further, “heat insulation” means that far infrared rays having a wavelength of 5 μm to 50 μm are reflected by an average reflectance of 5% or more. The average reflectance of far-infrared rays is more preferably 7% or more, particularly preferably 8% or more, and particularly preferably 10% or more.
The average reflectance of far-infrared rays can be measured by V-670 (manufactured by JASCO Corporation) and determined by the method described in JIS-5759.
Further, the “window glass” is used to include a window glass installed in a building and a window glass installed in a vehicle.

<Heat shielding material>
The heat shielding material is composed of a support, a metal-containing layer containing a metal element, organic particles having an average particle diameter of 0.1 μm to 15 μm and a glass transition temperature of 100 ° C. or higher (hereinafter also referred to as specific organic particles). And an organic particle-containing layer containing (in this order).

Although the operation of the present invention is not clear, the present inventors presume as follows.
A material such as a heat shielding material may be applied via an adhesive layer after applying a construction liquid to an adherend (for example, a glass window) because of the advantage that the application position can be easily corrected. . When a few days to a few weeks have passed after the application of the heat shielding material pasted with the construction liquid, the heat shielding material may become clouded and the transparency may be lowered (haze increases).
Conventionally, various studies have been made as materials having a heat shielding effect, and the heat ray shielding material described in Patent Document 1 and the electromagnetic wave transmissive laminate described in Patent Document 2 have been proposed as described above. However, it is not assumed that these heat shielding materials are pasted using a construction liquid, and no consideration is given to suppressing a decrease in transparency derived from the construction liquid after construction.
The decrease in transparency derived from the above-mentioned construction liquid is caused by the construction liquid penetrating into the metal-containing layer containing the metal component, or disposed between the heat shielding material, the heat shielding material and the adherend. It is considered that this occurs when the construction liquid stays between the PSA layer and the thermal barrier material between the thermal barrier material when the thermal barrier material has a laminated structure. In particular, in the case of a heat shielding material having a laminated structure including a metal-containing layer containing a metal component, the construction liquid is attracted to the metal-containing layer, and the construction liquid easily penetrates into or between the layers. It is thought that the decrease in transparency is likely to occur.
The heat-shielding material of the present invention contains organic particles having a predetermined average particle diameter in the organic particle-containing layer, so that the penetration of the construction liquid into the material is suppressed, resulting in a decrease in transparency derived from the construction liquid. Is considered to be suppressed.
In addition, by including organic particles with a glass transition temperature of 100 ° C. or higher in the organic particle-containing layer, deformation of the organic particles during production of the heat shielding material is suppressed, and the slipperiness of the organic particle-containing layer surface is adjusted to a desired range. can do. Therefore, it is advantageous in terms of productivity, for example, wrinkles during roll winding and roll collapse are less likely to occur.

[Organic particle-containing layer]
The heat shielding material further has an organic particle-containing layer on the metal-containing layer described later on the support. The organic particle-containing layer contains at least one organic particle having an average particle diameter of 0.1 μm to 15 μm and a glass transition temperature of 100 ° C. or higher.
In the heat shielding material of the present invention, since the organic particle-containing layer contains specific organic particles, a decrease in transparency derived from the construction liquid at the time of construction is suppressed.

(Average particle size of organic particles)
The average particle diameter of the organic particles is 0.1 μm to 15 μm.
When the average particle diameter is 0.1 μm or more, the construction liquid is difficult to permeate the layer, so that a decrease in transparency derived from the construction liquid is suppressed. On the other hand, when the average particle size is 15 μm or less, it becomes difficult to form a gap between the organic particle-containing layer and the adjacent layer (for example, the pressure-sensitive adhesive layer), and the construction liquid enters between the organic particle-containing layer and the adjacent layer. Since it becomes difficult, the fall of the transparency derived from a construction liquid is suppressed.
The average particle size is more preferably 0.35 μm to 5.0 μm, and even more preferably 0.8 μm to 1.8 μm. When the average particle diameter is in such a range, the above effect appears more remarkably.

  The average particle diameter (μm) of the organic particles is obtained by taking a scanning electron micrograph (SEM image) of 100 organic particles with a scanning electron microscope (for example, S-3700N, manufactured by Hitachi High-Technologies Corporation). It can be obtained by measuring the particle diameter using a treatment measuring device (Luzex AP; manufactured by Nireco Co., Ltd.) and calculating the arithmetic average value. That is, the average particle diameter referred to in the present invention is expressed by the diameter when the projected shape of the organic particles is circular, and the diameter when it is an irregular shape other than a sphere when the circle has the same area as the projected area. Represented by

(Glass transition temperature of organic particles)
The glass transition temperature (Tg) of the organic particles is 100 ° C. or higher.
Since the glass transition temperature is 100 ° C. or higher, the deformation of the organic particles during the production of the heat shielding material is suppressed, and the slipperiness of the surface of the organic particle-containing layer can be adjusted to a desired range. Is advantageous.
The glass transition temperature is preferably 130 ° C or higher, more preferably 150 ° C or higher, and further preferably 200 ° C or higher. The higher the glass transition temperature, the more prominent the above effect.

The glass transition temperature (Tg) of the organic particles is a value measured under the following conditions using a differential scanning calorimeter “X-DSC7000” (manufactured by SII Nanotechnology). The measurement is performed twice for the same sample, and the second measurement result is adopted.
<Condition>
・ Atmosphere in measurement chamber: Nitrogen (50 mL / min)
・ Raising rate: 5 ° C / min
Measurement start temperature: -100 ° C
-Measurement end temperature: 200 ° C
・ Sample pan: Aluminum pan ・ Measurement sample mass: 5 mg
-Calculation of Tg: Tg was calculated by rounding off the decimal point of the intermediate temperature between the lowering start point and the lowering end point of the DSC chart.

(Content of organic particles)
The content of the organic particles in the organic particle-containing layer is preferably in the following range from the viewpoint of suppressing the decrease in transparency derived from the construction liquid and the surface friction coefficient of the organic particle-containing layer.
The content of the organic particles is preferably 0.3% by mass to 6.0% by mass, more preferably 0.5% by mass to 5.5% by mass with respect to the total solid content of the organic particle-containing layer. 5 mass%-3.5 mass% are still more preferable.
When the content of the organic particles is 0.3% by mass or more, the construction liquid is less likely to pass through the layer, and therefore, a decrease in transparency derived from the construction liquid is further suppressed. On the other hand, when the content is 6.0% by mass or less, the surface friction coefficient (slidability) of the organic particle-containing layer can be adjusted to an appropriate range, and thus the productivity of the heat shielding material is excellent.

(Thickness of organic particle content layer)
The thickness of the organic particle-containing layer is preferably in the following range from the viewpoint of suppressing a decrease in transparency derived from the construction liquid and the surface friction coefficient of the organic particle-containing layer.
The thickness of the organic particle-containing layer is preferably 0.1 μm or more, more preferably 0.1 μm to 1.8 μm, further preferably 0.2 μm to 1.5 μm, and particularly preferably 0.4 μm to 1.3 μm.
Since it becomes difficult for a construction liquid to permeate | transmit a layer as thickness is 0.1 micrometer or more, the fall of the transparency derived from a construction liquid is suppressed more. On the other hand, when the thickness is 1.8 μm or less, the surface friction coefficient (sliding property) of the organic particle-containing layer can be adjusted to an appropriate range, so that the productivity of the heat shielding material is excellent.

The thickness of the organic particle-containing layer can be measured by observing the cross section of the organic particle-containing layer using a scanning electron microscope (for example, S-3700N, manufactured by Hitachi High-Technologies Corporation).
The thickness of the organic particle-containing layer is determined by measuring the thickness of any 10 locations in the cross section of the layer when the organic particles are buried in the organic particle-containing layer and the surface of the layer is smooth, and adopting the arithmetic average value of 10 locations. To do. On the other hand, when there are irregularities on the surface of the organic particle-containing layer, the thickness of an arbitrary 100 points in the cross section of the layer is measured, and the arithmetic average value of 10 points from the thinner one of the measured 100 points is contained in the organic particles. Adopt as thickness in the layer.

(Ratio of the average particle diameter of the organic particles to the thickness of the organic particle-containing layer)
The ratio of the average particle diameter of the organic particles to the thickness of the organic particle-containing layer is within the following range from the viewpoint of suppressing the decrease in transparency derived from the construction liquid and the surface friction coefficient of the organic particle-containing layer. preferable.
The ratio of the average particle diameter of the organic particles to the thickness of the organic particle-containing layer is preferably 1.00 or more, more preferably 1.10 or more and 8.50 or less, and further preferably 1.15 to 3.75.
When the above ratio is 1.00 or more, the surface friction coefficient (sliding property) of the organic particle-containing layer can be adjusted to an appropriate range, so that the productivity of the heat shielding material is excellent. On the other hand, when the above ratio is 3.75 or less, the unevenness of the surface of the organic particle-containing layer does not become too large, and the construction liquid does not stay between the unevenness. More suppressed.

(Shape and type of organic particles)
The organic particles are not particularly limited as long as they are organic compounds having a particle shape. The shape of the particles may be spherical, flat, or hollow.
Although the kind of organic particle is not specifically limited, It is preferable that it is a particle | grain of hydrophobic resin from a viewpoint of suppressing the transparency fall derived from a construction liquid.
Hydrophobic resin particles include poly (meth) acrylate, polystyrene, polyolefin, poly (meth) acrylonitrile, polycarbonate, polytetrafluoroethylene, polyurethane, polyamide, polyacrylamide, polyvinyl acetate, polyvinyl chloride, and polyvinyl acetal. , Polyvinyl butyral, (meth) acryl-styrene copolymer, (meth) acrylonitrile-styrene copolymer, and styrene-divinylbenzene copolymer.
Among them, particles of poly (meth) acrylate, polystyrene, and polyolefin are preferable, particles of poly (meth) acrylate are more preferable from the viewpoint of refractive index, and particles of poly (meth) acrylate are more preferable. Polymethyl methacrylate (PMMA) particles are particularly preferred.

  Monomers that can form poly (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. , Lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-propyl (meth) acrylate, chloro-2-hydroxyethyl (meth) acrylate, diethylene glycol Mono (meth) acrylate, methoxyethyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate and isobornyl (meth) acrylate And the like.

  Monomers capable of forming polystyrene include alkyl styrenes such as styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene and octyl styrene. Halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene and chloromethylstyrene; and nitrostyrene, acetylstyrene and methoxystyrene.

  Monomers that can form polyolefin include alkenes such as ethylene, butylene, and propylene; monomers other than alkenes such as unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid, maleic acid, and maleic anhydride And so on.

The organic particles can be obtained by polymerizing one or more of the above monomers by a known method.
The organic particles may be used in the form of an aqueous dispersion called a so-called latex.
Regarding the method for producing the aqueous dispersion, there are a method by emulsification and a method by emulsification dispersion, the former being preferred. For a specific method, for example, the method described in Japanese Patent No. 3699935 can be referred to.

  As the organic particles, those already marketed as a dispersion may be used. When using commercially available organic particles as a dispersion, it can be used after powdered by a known method such as freeze-drying.

  Specific examples of commercially available organic particles include MP-300 (manufactured by Soken Chemical Co., Ltd., PMMA particles, average particle size 0.1 μm, Tg 128 ° C.), MP-1451 (manufactured by Soken Chemical Co., Ltd., PMMA particles, Average particle size 0.15 μm, Tg 128 ° C.), MP-2200 (manufactured by Soken Chemical Co., Ltd., PMMA particles, average particle size 0.35 μm, Tg 128 ° C.), MP-1000 (manufactured by Soken Chemical Co., Ltd., PMMA particles, Average particle size 0.4 μm, Tg 128 ° C.), MX-80H3wT (manufactured by Soken Chemical Co., Ltd., PMMA particles, average particle size 0.8 μm, Tg 200 ° C. or more), MX-150 (manufactured by Soken Chemical Co., Ltd., PMMA particles) , Average particle size 1.5 μm, Tg 200 ° C. or higher), MX-180TA (manufactured by Soken Chemical Co., Ltd., PMMA particles, average particle size 1.8 μm, Tg 200 ° C. or higher), MX-300 (綜Chemical, PMMA particles, average particle size 3.0 μm, Tg 200 ° C. or higher), MX-500 (Soken Chemicals, PMMA particles, average particle size 5.0 μm, Tg 200 ° C. or higher), MX-1000 (Manufactured by Soken Chemical Co., Ltd., PMMA particles, average particle size 10 μm, Tg 200 ° C. or higher), MX-1500H (manufactured by Soken Chemical Co., Ltd., PMMA particles, average particle size 15 μm, Tg 200 ° C. or higher), SX-130H (Soken Chemical Co., Ltd., polystyrene particles, average particle size 1.3 μm, Tg 200 ° C. or higher, Chemipearl (registered trademark) W900 (Mitsui Chemicals, polyolefin particles, average particle size 0.8, Tg 132 ° C.), etc. Can be mentioned.

(Content of organic wax)
Conventionally, an organic wax has been used as a component for improving the slipperiness of the surface of the heat shielding material. In a layer containing such an organic wax, the organic wax tends to be unevenly distributed on the surface of the layer, and the adhesiveness to an adjacent layer (for example, an adhesive layer) tends to depend on the physical properties of the organic wax. For this reason, the desired adhesion may not be obtained depending on the type of the organic wax.
From the above points, the heat shielding material of the present invention preferably has an organic wax content of 1% by mass or less, more preferably 0.5% by mass or less, based on the total solid content of the organic particle-containing layer. The content is more preferably 0.1% by mass or less, and particularly preferably 0% by mass (not included).
When the content of the organic wax is 1% by mass or less, the adhesion with an adjacent layer becomes more excellent.
Specific examples of organic waxes include plant waxes such as carnauba wax, candelilla wax, rice wax, wood wax, jojoba oil, palm wax, rosin-modified wax, aucuric wax, sugar cane wax, esparto wax, and bark wax; Animal waxes such as beeswax, lanolin, whale wax, ibota wax, shellac wax; mineral waxes such as montan wax, ozokerite, ceresin wax; petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam; And synthetic hydrocarbon waxes such as polyethylene wax, oxidized polyethylene wax, polypropylene wax and oxidized polypropylene wax.

(binder)
The organic particle-containing layer preferably contains a binder.
There is no restriction | limiting in particular as a binder, According to the objective, it can select suitably, For example, thermosetting resins, such as urethane resin, (meth) acrylic resin, silicone resin, melamine resin, alkyd resin, a fluororesin, or light Examples thereof include curable resins.
Of these, (meth) acrylic resins and urethane resins are preferred.
Only 1 type may be used for a binder and it may combine 2 or more types.

-(Meth) acrylic resin-
The (meth) acrylic resin is a polymer obtained by homopolymerizing or copolymerizing with other monomers a (meth) acrylic monomer such as a monomer capable of forming the poly (meth) acrylic acid ester described above. It is a coalescence. Examples of the other monomer copolymerized with the (meth) acrylic monomer include a polymer having a carbon-carbon double bond. Examples of the polymer include a block copolymer and a graft copolymer. The (meth) acrylic resin may have at least one group selected from a hydroxy group and an amino group, from the viewpoint of improving the adhesion with an adjacent layer.

-Urethane resin-
Urethane resin is a general term for polymers having a urethane bond in the main chain, and examples thereof include resins obtained by reaction of diisocyanate and polyol. Examples of the diisocyanate include TDI (toluene diisocyanate), MDI (diphenylmethane diisocyanate), NDI (naphthalene diisocyanate), TODI (tolidine diisocyanate), HDI (hexamethylene diisocyanate), IPDI (isophorone diisocyanate), and the like.
Examples of the polyol include ethylene glycol, propylene glycol, glycerin, hexanetriol and the like. Further, as the isocyanate, a resin obtained by subjecting a urethane resin obtained by the reaction of diisocyanate and polyol to chain extension treatment to increase the molecular weight can also be used. The diisocyanate, polyol, and chain extension treatment described above are described in, for example, “Polyurethane Handbook” (edited by Keiji Iwata, Nikkan Kogyo Shimbun, published in 1987).

A commercially available binder may be used.
For example, as the urethane resin, Superflex (registered trademark) 150HS, 110, 420 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Hydran (registered trademark) HW350 (manufactured by DIC Corporation), Takelac (registered trademark) WS400, WS5100 (made by Mitsui Chemicals, Inc.) is mentioned.
As the (meth) acrylic resin, Aquabrid (registered trademark) AS-563A (manufactured by Daicel Finechem Co., Ltd.), Julimer (registered trademark) ET-410 (manufactured by Toagosei Co., Ltd.), Bonlon (registered trademark) PS002 ( Mitsui Chemicals).

(Surfactant)
The organic particle-containing layer may contain a surfactant.
Examples of the surfactant include known anionic surfactants, nonionic surfactants, cationic surfactants, fluorine surfactants, and silicone surfactants. The surfactant is described in, for example, “Surfactant Handbook” (Nishi Ichiro, Imai Shunichiro, Kasai Shozo, Sangyo Tosho Co., Ltd., 1960). As the surfactant, an anionic surfactant or a nonionic surfactant is particularly preferable.
Only one type of surfactant may be used, or two or more types may be combined.

A commercially available product may be used as the surfactant.
Commercially available anionic surfactants include Lapisol (registered trademark) A-90, A-80, BW-30, B-90, C-70 (manufactured by NOF Corporation), NIKKOL (registered trademark). OTP-100 (above, manufactured by Nikko Chemical Co., Ltd.), Kohakuur (registered trademark) ON, L-40, Phosphanol (registered trademark) 702 (above, manufactured by Toho Chemical Industry Co., Ltd.), Viewlite (registered trademark) ) A-5000, SSS (manufactured by Sanyo Chemical Industries, Ltd.) and the like.

  Commercially available nonionic surfactants include Naroacti (registered trademark) CL-95, HN-100 (trade name: manufactured by Sanyo Chemical Industries, Ltd.), Risolex BW400 (trade name: manufactured by Higher Alcohol Industry Co., Ltd.) EMALEX (registered trademark) ET-2020 (manufactured by Nippon Emulsion Co., Ltd.), Unilube (registered trademark) 50MB-26, Nonion (registered trademark) IS-4 (manufactured by NOF Corporation) and the like. It is done.

  Commercially available cationic surfactants include, for example, phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid type (Co) polymer, Polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

  Examples of commercially available fluorosurfactants include MegaFac (registered trademark) F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F781 (above, manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Limited), Surflon (registered trademark) S-382, SC-101, SC-103, SC-104, SC -105, SC1068, SC-381, SC-383, S393, KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA).

  Examples of commercially available silicone surfactants include, for example, Tore Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (above, manufactured by Toray Dow Corning Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF4452 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, BYK330 (above, BYK Chemie) Etc.).

(Other ingredients)
The organic particle-containing layer may contain other components such as a crosslinking agent, a matting agent, and an ultraviolet absorber as necessary.
There is no restriction | limiting in particular as a crosslinking agent, Crosslinking agents, such as an epoxy type crosslinking agent, an isocyanate type crosslinking agent, a melamine type crosslinking agent, a carbodiimide type crosslinking agent, an oxazoline type crosslinking agent, are mentioned. Of these, carbodiimide crosslinking agents and oxazoline crosslinking agents are preferred. Specific examples of the carbodiimide crosslinking agent include Carbodilite (registered trademark) V-02-L2 (manufactured by Nisshinbo Chemical Co., Ltd.).

-Formation of organic particle-containing layer-
The formation method of an organic particle content layer is not specifically limited. From the viewpoint of cost reduction, it is preferable to form by coating. The coating method at this time is not particularly limited, and a known method can be used. For example, a coating solution of a composition for forming an organic particle-containing layer is prepared, and a dip coater, a die coater, a slit coater, Examples thereof include a coating method using a bar coater, a gravure coater, or the like.

[Metal-containing layer]
The heat shielding material has a metal-containing layer containing a metal element on a support.
When the heat shielding material has the metal-containing layer, the material can reflect the heat rays, and the heat shielding effect can be obtained. The metal-containing layer is a layer containing at least one metal element.
The metal element is preferably at least one metal element selected from the group consisting of the fourth period, the fifth period, and the sixth period of the periodic table (IUPAC 1991), and at least one kind selected from Groups 2-14 More preferably, at least one metal element selected from Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, Group 13, and Group 14 is further included. It is particularly preferable that these metal elements are contained as a main component.

  Specific examples of metal elements include silver, gold, aluminum, copper, rhodium, nickel, platinum, tin, cobalt, palladium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, titanium, and bismuth. , Antimony, cadmium, chromium, zinc, lead and the like. Among these, silver, gold, aluminum, copper, rhodium, nickel, platinum, tin, cobalt, palladium, and iridium are preferable, silver, gold, aluminum, copper, rhodium, nickel, and platinum are more preferable, and silver is particularly preferable.

The metal element in the metal-containing layer may be contained in any form, for example, an aspect in which the metal-containing layer is contained as metal particles, and an aspect in which the metal-containing layer itself is a metal film and a metal oxide film Is mentioned.
Especially, it is preferable to contain as a metal particle from a viewpoint of coexistence with heat insulation and transparency.

(Metal particles)
The metal particles are preferably flat metal particles (flat metal particles), and more preferably segregate the flat metal particles on one surface of the metal-containing 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. Of these, silver is more preferable.
That is, the metal-containing layer preferably contains silver particles, and more preferably contains tabular silver particles.

-Flat metal particles-
The tabular metal particles are not particularly limited as long as they are tabular particles having two main planes, and can be appropriately selected according to the purpose, for example, a triangular shape, a quadrangular shape, a hexagonal shape, an octagonal shape, Examples include a circular shape. Among these, a hexagonal or more polygonal shape or a circular shape is more preferable in terms of high visible light transmittance.
The circular flat metal particles are not particularly limited as long as the flat metal particles have no corners and are round when viewed from above the main plane with a transmission electron microscope (TEM). Can be selected as appropriate.
The hexagonal flat metal particles are not particularly limited as long as the flat metal particles are hexagonal when observed from above the main plane with a transmission electron microscope (TEM), and are appropriately selected according to the purpose. For example, the hexagonal corners may be acute or dull, but the corners are preferably dull in that the absorption in the visible light region can be reduced. There is no restriction | limiting in particular as a grade of the dullness of an angle | corner, According to the objective, it can select suitably.

  Of the metal particles that may be present in the metal-containing layer, the content ratio of hexagonal or circular tabular metal particles is preferably as large as possible, and more preferably 60% by number or more based on the total number of metal particles. Preferably, 65% by number or more is more preferable, and 70% by number or more is particularly preferable. When the proportion of the flat metal particles is 60% by number or more, the visible light transmittance is increased.

-Planar orientation and existence state of tabular metal particles-
The main plane of the hexagonal or circular tabular metal particles is oriented in the range of 0 ° to ± 30 ° on the average with respect to one surface of the metal-containing layer (the surface of the support for the heat shielding material). It is preferable that the plane orientation is more preferable in the range of 0 ° to ± 20 ° on average, and it is particularly preferable that the plane orientation is in the range of 0 ° to ± 10 ° on average. Further, the plate-like metal particles whose plane orientation is in the range of 0 ° to ± 30 ° on average is preferably 50% by number or more of all plate-like metal particles, more preferably 70% by number or more, More preferably, it is 90% by number or more.
The presence state of the flat metal particles is not particularly limited and may be appropriately selected depending on the purpose. For example, the embodiments described in paragraphs [0050] to [0059] of JP-A No. 2014-184688 are preferable.

-Average particle diameter (average equivalent circle diameter) and coefficient of variation of flat metal particles-
The average particle diameter can be obtained by a known method of measuring the projected area of a flat metal particle on a transmission electron micrograph and correcting the photographing magnification. The equivalent circle diameter is obtained by taking a transmission electron micrograph of particles obtained by the above method into image processing software ImageJ, performing image processing, and calculating the diameter of a circle having an area equal to the projected area of each particle. Can be obtained at A particle size distribution (particle size distribution) is obtained by the statistics of the equivalent circle diameter D of 200 flat metal particles, and the average particle diameter (average equivalent circle diameter) can be obtained by calculating the arithmetic average. The coefficient of variation in the particle size distribution of the flat metal particles can be obtained by a value (%) obtained by dividing the standard deviation of the particle size distribution by the above-mentioned average particle diameter (average circle equivalent diameter).
In the heat shielding material, the coefficient of variation in the particle size distribution of the flat metal particles is preferably 35% or less, more preferably 30% or less, and particularly preferably 20% or less. The variation coefficient is preferably 35% or less because the reflection wavelength region of the heat ray in the heat shielding material becomes sharp.
There is no restriction | limiting in particular as a magnitude | size of a metal particle, According to the objective, it can select suitably, An average particle diameter has preferable 10 nm-500 nm, 20 nm-300 nm are more preferable, 50 nm-200 nm are further more preferable.

-Thickness and aspect ratio of flat metal particles-
The thickness of the flat metal particles is preferably 14 nm or less, more preferably 5 nm to 14 nm, and particularly preferably 5 nm to 12 nm.
There is no restriction | limiting in particular as an aspect-ratio of a flat metal particle, Although it can select suitably according to the objective, From the point from which the reflectance in the infrared region of wavelength 800nm-1800nm becomes high, it is 6 ~ 40 is preferable and 10-35 is more preferable. When the aspect ratio is 6 or more, the reflection wavelength is larger than 800 nm, and when it is 40 or less, the reflection wavelength is smaller than 1,800 nm, and the heat ray reflectivity is further improved.
The aspect ratio means a value obtained by dividing the average particle diameter (average circle equivalent diameter) of the flat metal particles by the average particle thickness of the flat metal particles.
For example, when the flat metal particles are circular, the aspect ratio is a value obtained by dividing the diameter D shown in FIG. 5 by the thickness a.
When the flat metal particles are hexagonal, the aspect ratio is a value obtained by dividing the equivalent circle diameter D shown in FIG. 6 by the thickness a.
The particle thickness corresponds to the distance between main planes of the flat metal particles, and can be measured by an atomic force microscope (AFM) or a transmission electron microscope (TEM).
The method for measuring the average particle thickness by AFM is not particularly limited and can be appropriately selected according to the purpose. For example, a flat metal particle dispersion containing flat metal particles is dropped onto a plate glass and dried. And a method of measuring the thickness of one flat metal particle.
There is no restriction | limiting in particular as a measuring method of the average particle thickness by TEM, According to the objective, it can select suitably, For example, the particle dispersion containing a flat metal particle was dripped on the silicon substrate, and it was made to dry. Thereafter, a coating process by carbon vapor deposition or metal vapor deposition is performed, a cross section is created by focused ion beam (FIB) processing, and the cross section is observed by TEM to measure the thickness of the particles.

-Area ratio of tabular metal particles-
The total value B of the area of the flat metal particles with respect to the area A of the base material when viewed from above (the total projected area A of the metal-containing layer when viewed from the direction perpendicular to the metal-containing layer) The area ratio [(B / A) × 100] as a ratio is preferably 15% or more, and more preferably 20% or more. When the area ratio is 15% or more, the maximum reflectance of the heat ray increases, and a higher heat shielding effect can be obtained.
Here, the area ratio can be measured, for example, by performing image processing on an image obtained by SEM observation of the heat shield material from above or an image obtained by AFM (atomic force microscope) observation.

-Arrangement of tabular metal particles-
The arrangement of the flat metal particles in the metal-containing layer is preferably uniform. Uniform arrangement here means the coefficient of variation of the distance between the nearest particles of each particle when the distance to the nearest particle (distance between the nearest particles) for each particle is expressed as the distance between the centers of the particles. = Standard deviation ÷ average value) is small. The variation coefficient of the closest interparticle distance is preferably as small as possible, preferably 30% or less, more preferably 20% or less, more preferably 10% or less, and ideally 0%. When the coefficient of variation of the distance between the nearest particles is large, it is not preferable because the flat metal particles and the aggregation between the particles occur in the metal-containing layer and the haze tends to deteriorate. The distance between the closest particles can be measured by observing the coated surface of the metal-containing layer with an SEM or the like.

-Method for synthesizing tabular metal particles-
The method for synthesizing the flat metal particles is not particularly limited and may be appropriately selected depending on the intended purpose. For example, liquid phase methods such as a chemical reduction method, a photochemical reduction method, an electrochemical reduction method, etc. It is mentioned as what can synthesize circular flat metal particles. Among these, a liquid phase method such as a chemical reduction method or a photochemical reduction method is particularly preferable in terms of shape and size controllability. After synthesizing hexagonal to triangular tabular metal particles, hexagonal to triangular tabular metal is obtained by, for example, etching with a dissolved species that dissolves silver nitric acid and sodium sulfite, and aging by heating. Hexagonal or circular flat metal particles may be obtained by blunting the corners of the particles.

  As a method for synthesizing the flat metal particles, in addition to the above, after seed crystals are fixed in advance on the surface of a transparent substrate such as a material or glass, the metal particles (for example, Ag) may be grown in a flat plate shape.

  In the heat shielding material, the flat metal particles may be subjected to further treatment in order to impart desired characteristics. The further treatment is not particularly limited and may be appropriately selected depending on the purpose. For example, formation of a high refractive index shell layer described in paragraphs [0068] to [0070] of JP-A No. 2014-184688 And adding various additives described in paragraphs [0072] to [0073] of JP-A No. 2014-184688.

(binder)
The metal-containing layer may contain a binder.
There is no restriction | limiting in particular as a binder, According to the objective, it can select suitably. The heat shielding material preferably contains a polymer as a binder for the metal-containing layer, and more preferably contains a transparent polymer. Examples of the polymer include polyvinyl acetal resin, polyvinyl alcohol resin, polyvinyl butyral resin, (meth) acrylic resin, polycarbonate resin, polyvinyl chloride resin, (saturated) polyester resin, urethane resin, natural polymers such as gelatin and cellulose, etc. And other polymers.
Among them, the main component of the polymer is preferably at least one of polyvinyl alcohol resin, polyvinyl butyral resin, polyvinyl chloride resin, (saturated) polyester resin, and urethane resin, and the polyester resin and urethane resin are preferably hexagonal or 80% by number or more of the circular plate-like metal particles is more preferable from the viewpoint of easily existing in the range of d / 2 from the surface of the metal-containing layer, and a urethane resin is a viewpoint of further improving the rubbing resistance of the heat shielding material. Is particularly preferred.
Among polyester resins, a saturated polyester resin is more particularly preferable from the viewpoint of imparting excellent weather resistance since it does not contain a double bond. Moreover, it is more preferable to have a hydroxyl group or a carboxy group at the molecular end from the viewpoint of obtaining high hardness, durability and heat resistance by curing with a water-soluble or water-dispersible curing agent or the like.
As the polymer, commercially available polymers can be preferably used. For example, Plus Coat Z-867, which is a water-soluble polyester resin manufactured by Kyoyo Chemical Industry Co., Ltd., and Hydran HW350 manufactured by DIC Co., Ltd. Can do.
In the present specification, the main component of the polymer refers to a polymer component occupying 50% by mass or more of the polymer contained in the binder.
The content of the polyester resin and the urethane resin with respect to the metal particles that can be contained in the metal-containing layer is preferably 1% by mass to 10000% by mass, more preferably 10% by mass to 1000% by mass, and more preferably 20% by mass to It is especially preferable that it is 500 mass%. By setting the binder contained in the metal-containing layer to be in the above range or more, physical properties such as rubbing resistance can be further improved.
The refractive index n of the binder is preferably 1.4 to 1.7.
When the thickness of the hexagonal or circular plate-like metal particles is a, the heat shielding material is composed of 80% by number or more of hexagonal or circular plate-like metal particles with a / 10 or more in the thickness direction as a polymer. It is preferably covered, more preferably a / 10 to 10a in the thickness direction is covered with the polymer, and particularly preferably a / 8 to 4a is covered with the polymer. As described above, the hexagonal or circular plate-like metal particles are embedded in the metal-containing layer at a certain ratio or more, whereby the rubbing resistance can be further increased.

(Other additives)
The metal-containing layer may contain a crosslinking agent, a surfactant, an antioxidant, and a dispersant as other additives.
The crosslinking agent is not particularly limited, and examples thereof include an epoxy crosslinking agent, an isocyanate crosslinking agent, a melamine crosslinking agent, a carbodiimide crosslinking agent, and an oxazoline crosslinking agent. Of these, carbodiimide crosslinking agents and oxazoline crosslinking agents are preferred. Specific examples of the carbodiimide-based crosslinking agent include, for example, Carbodilite (registered trademark) V-02-L2 (manufactured by Nisshinbo Chemical Co., Ltd.). It is preferable to contain a component derived from 1% by mass to 20% by mass of the crosslinking agent with respect to the total binder in the metal-containing layer, and more preferably 2% by mass to 20% by mass.
As surfactants, known surfactants such as anionic surfactants and nonionic surfactants can be used. Specific examples of surfactants include, for example, Lapisol (registered trademark) A-90 (Japan). Oil Co., Ltd.), NAROACTY (registered trademark) CL-95 (Sanyo Chemical Industries Co., Ltd.), and Ripar 870P (Lion Co., Ltd.). It is preferable that a metal content layer contains 0.05 mass%-10 mass% surfactant with respect to content of all the binders in a metal content layer, and 0.1 mass%-5 mass% are more preferable. .

The metal-containing layer may contain an antioxidant such as mercaptotetrazole or ascorbic acid in order to prevent oxidation of metals such as silver constituting the flat metal particles. Further, for the purpose of preventing oxidation, an oxidation sacrificial layer such as Ni may be formed on the surface of the flat metal particles. Further, it may be covered with a metal oxide film such as SiO ₂ for the purpose of blocking oxygen.
Examples of the dispersant include dispersants such as a low molecular weight dispersant and a high molecular weight dispersant containing at least one of nitrogen element such as quaternary ammonium salts and amines, sulfur element, and phosphorus element.

(Metal film, metal oxide film)
The metal-containing layer in the heat shielding material may contain a metal element in a form other than the metal particles. For example, the metal-containing layer itself may be a metal film or a metal oxide film.
Examples of the metal film include films made of a metal or an alloy such as silver, gold, aluminum, copper, palladium, platinum, tin, indium, zinc, titanium, cadmium, iron, cobalt, chromium, and nickel.
Examples of the metal oxide film include antimony-doped tin oxide and tin-doped indium oxide films.

(Metal-containing layer thickness)
The thickness of the metal-containing layer is preferably 5 nm to 120 nm, more preferably 7 nm to 80 nm, and particularly preferably 10 nm to 40 nm.

~ Formation of metal-containing layer ~
The method for forming the metal-containing layer is not particularly limited and can be appropriately selected depending on the purpose. For example, a dispersion liquid for forming a metal-containing layer is formed on the surface of the support by using a dip coater, a die coater, or a slit. Examples thereof include a method of coating with a coater, bar coater, gravure coater, etc., a surface orientation method such as an LB film (Langmuir-Blodgett film) method, a self-organization method, and a spray coating method.
In addition, in order to accelerate | stimulate plane orientation, after apply | coating the dispersion liquid for metal-containing layer formation, you may accelerate | stimulate by passing through pressure-bonding rollers, such as a calender roller and a laminating roller.
When the metal-containing layer is a metal film or a metal oxide film, a wet method such as a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, a chemical method such as CVD or a plasma CVD method, etc. The film can be formed according to a method appropriately selected in consideration of suitability with the material to be used.

The metal-containing layer forming dispersion may contain an antifoaming agent or a preservative.
In the preparation and redispersion of metal particles, the reaction solution and the coarse dispersion may be vigorously stirred. Although depending on the properties of the target liquid, the foam is stabilized by the presence of a substance that lowers the surface tension. Therefore, foaming is promoted when the metal particle dispersion contains a surfactant or a dispersant. . Therefore, it is preferable to contain an antifoamer.

Antifoaming agent is selected from general ones such as surfactants, polyether antifoaming agents, ester antifoaming agents, higher alcohol antifoaming agents, mineral oil antifoaming agents, silicone antifoaming agents, etc. Can be used. Among these, surfactants are preferably used because they can exhibit a high defoaming effect when added in a small amount and are excellent in stability over time.
When used in an aqueous system, those having high lipophilicity and easily spreading on the liquid surface, that is, those having a low HLB (Hydrophile-Lipophile Balance) value are preferably used. When used in an aqueous system, the HLB value is preferably 7 or less, more preferably 5 or less, and most preferably 3 or less.
As the antifoaming agent, a commercially available product can be used. For example, Pluronic 31R1 (manufactured by BASF) can be preferably used.
As the preservative, for example, the preservatives described in paragraphs [0073] to [0090] of JP-A No. 2014-184688 can be used.

[Support]
The heat shielding material has a support.
There is no restriction | limiting in particular as a support body, A well-known support body can be used.
The support is preferably an optically transparent support. For example, a support having a visible light transmittance of 70% or more, preferably 80% or more, or a material having a high transmittance in the near infrared region. Can be mentioned.
The visible light transmittance can be measured using an ultraviolet-visible near-infrared spectrometer (manufactured by JASCO Corporation, using V-670, integrating sphere unit ISN-723).

  There is no restriction | limiting in particular about a shape, a structure, a magnitude | size, material, etc. as a support body, According to the objective, it can select suitably. Examples of the shape include a flat plate shape, and the structure may be a single layer structure or a laminated structure, and the size may depend on the size of the heat shielding material. It can be selected appropriately.

  There is no restriction | limiting in particular as a material of a support body, According to the objective, it can select suitably, For example, polyolefin, such as polyethylene, a polypropylene, poly 4-methylpentene-1, polybutene-1, polyethylene terephthalate, polyethylene naphthalate Polyester such as: Polycarbonate, polyvinyl chloride, polyphenylene sulfide, polyether sulfone, polyethylene sulfide, polyphenylene ether, polystyrene, (meth) acrylic resin, polyamide resin, polyimide resin, cellulose resin such as cellulose acetate, or these materials A laminated material is mentioned. Among these, a polyethylene terephthalate material is particularly preferable.

  There is no restriction | limiting in particular as thickness of a support body, It can select suitably according to the intended purpose of heat-shielding material, Although it is about 10 micrometers-about 500 micrometers normally, the thinner one is preferable from a viewpoint of thin film formation. The thickness of the support is preferably 10 μm to 100 μm, more preferably 20 μm to 75 μm, and particularly preferably 35 μm to 75 μm. If the thickness of the support is sufficiently thick, adhesion failure tends to be difficult to occur. Further, if the support is sufficiently thin, when it is bonded to a building material or a window glass of an automobile as a heat shielding material, the rigidity as the material is not too high and the construction tends to be easy. Furthermore, when the support is sufficiently thin, the visible light transmittance is increased, and the raw material cost tends to be suppressed.

[Protective layer]
The heat shielding material may have a protective layer containing inorganic particles (hereinafter also referred to as a hard coat layer) on the side opposite to the side having the metal-containing layer of the support.
When heat shielding material is produced in rolls, the heat shielding material has a protective layer, making it easy to adjust the slipperiness with the organic particle-containing layer to an appropriate range, so that wrinkles and roll collapse during roll winding are possible. Less likely to occur.
Moreover, when the heat-shielding material has a protective layer, the scratch resistance of the material is improved, and it is possible to suppress a decrease in transparency due to the material being damaged.

(Inorganic particles)
The protective layer contains at least one kind of inorganic particles.
Examples of the inorganic particles include metal oxide particles. As specific examples of the metal oxide particles, particles such as silica, alumina, zirconia, and titania are preferably used, and silica particles are particularly preferably used from the viewpoint of crosslinking with a binder described later.

As silica particles, dry powdery silica produced by combustion of silicon tetrachloride or colloidal silica in which silicon dioxide or a hydrate thereof is dispersed in water can be used. When using dry powdery silica, it can be used by dispersing in water using an ultrasonic disperser or the like.
Silica particles are not particularly limited, and specifically, Seahoster series such as Seahoster KE-P10 (manufactured by Nippon Shokubai Co., Ltd.) and Snowtex (registered trademark) series such as Snowtex (registered trademark) OZL-35 ( Nissan Chemical Industries, Ltd.).

The average particle size of the inorganic particles is preferably 60 nm to 350 nm, more preferably 65 nm to 300 nm, and even more preferably 70 nm to 250 nm.
When the average particle size of the inorganic particles is 60 nm or more, the anti-blocking property of the protective layer is easily obtained. On the other hand, when the average particle size of the inorganic particles is 350 nm or less, light is scattered in the film or on the film surface. Therefore, the transparency of the layer becomes higher.
The average particle diameter of the inorganic particles can be measured by the same method as the average particle diameter of the organic particles described above.

The content of inorganic particles in the protective layer is preferably 30% by volume or more, more preferably 35% by volume or more, and more preferably 40% by volume or more based on the total solid content of the protective layer. . The content of the inorganic particles is preferably 60% by volume or less, more preferably 55% by volume or less, and further preferably 50% by volume or less.
In addition, 2 or more types of inorganic particles may be used in combination, in which case the total amount of all types used is within the above range.

(binder)
The protective layer preferably contains a binder.
The binder may be an inorganic binder or an organic binder. The binder is preferably an inorganic binder from the viewpoint of scratch resistance of the protective layer.
As an inorganic binder, the binder hardened | cured including the epoxy group containing alkoxysilane, the epoxy group non-containing alkoxysilane, and the metal complex is mentioned, for example.

As the alkoxysilane (hereinafter, epoxy group-containing alkoxysilane and epoxy group-free alkoxysilane are also collectively referred to as “alkoxysilane”), it is preferable to use a water-soluble or water-dispersible material. Use of a water-soluble or water-dispersible material is preferable from the viewpoint of reducing environmental pollution caused by volatile organic compounds (VOC).
Each of the epoxy group-containing alkoxysilane and the epoxy group-free alkoxysilane preferably has a hydrolyzable group. Silanol is produced | generated when a hydrolysable group is hydrolyzed in acidic aqueous solution, and an oligomer is produced | generated when silanols condense.

  The content ratio of the epoxy group-containing alkoxysilane to the total amount of alkoxysilane is preferably 20% by mass to 100% by mass. About the minimum of the content rate of an epoxy-group-containing alkoxysilane, 25 mass% or more is preferable and 30 mass% or more is more preferable. Moreover, about an upper limit, 90 mass% or less is more preferable, 85 mass% or less is further more preferable, and 80 mass% or less is further more preferable. When the content ratio of the epoxy group-containing alkoxysilane with respect to the total amount of alkoxysilane is within the above range, it is advantageous for improving the stability of the composition when an aqueous composition for forming a protective layer is prepared, It becomes easy to form a strong protective layer.

  The epoxy group-containing alkoxysilane is an alkoxysilane having an epoxy group. Any epoxy group-containing alkoxysilane may be used as long as it has one or more epoxy groups in one molecule, and the number of epoxy groups is not particularly limited. In addition to the epoxy group, the epoxy group-containing alkoxysilane may further have a group such as an alkyl group, an amide group, a urethane group, a urea group, an ester group, a hydroxy group, or a carboxy group.

  As the epoxy group-containing alkoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Ethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl A triethoxysilane etc. can be mentioned. Examples of commercially available products include KBE-403 (manufactured by Shin-Etsu Chemical Co., Ltd.).

  The epoxy group-free alkoxysilane is an alkoxysilane having no epoxy group. The epoxy group-free alkoxysilane may be an alkoxysilane having no epoxy group, and may have a group such as an alkyl group, an amide group, a urethane group, a urea group, an ester group, a hydroxy group, or a carboxyl group. Good.

  Examples of the epoxy group-free alkoxysilane include tetraalkoxysilane, trialkoxysilane, and a mixture thereof, and tetraalkoxysilane is preferable. By having tetraalkoxysilane, sufficient hardness can be obtained when the protective layer is formed.

  Tetraalkoxysilane is a tetrafunctional alkoxysilane, more preferably having 1 to 4 carbon atoms in each alkoxy group. Of these, tetramethoxysilane and tetraethoxysilane are particularly preferably used. By setting the number of carbon atoms to 4 or less, the hydrolysis rate of tetraalkoxysilane when mixed with acidic water does not become too slow, and the time required for dissolution until a uniform aqueous solution is shortened. Thereby, the manufacturing efficiency at the time of forming a protective layer can be improved. Examples of commercially available products include KBE-04 (manufactured by Shin-Etsu Chemical Co., Ltd.).

The trialkoxysilane is a trifunctional alkoxysilane represented by the following general formula (1).
RSi (OR ¹ ) ₃ (1)
Here, R represents an organic group having 1 to 15 carbon atoms that does not contain an amino group, and R ¹ represents an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group.

  The trifunctional alkoxysilane represented by the general formula (1) does not contain an amino group as a functional group. That is, this trifunctional alkoxysilane has an organic group R having no amino group. When R has an amino group, if it is mixed with a tetrafunctional alkoxysilane and hydrolyzed, dehydration condensation is promoted between the produced silanols. For this reason, when adjusting the aqueous composition for protective layer formation and forming a protective layer, an aqueous composition becomes unstable and is not preferable.

  R in the general formula (1) may be an organic group having a molecular chain length in the range of 1 to 15 carbon atoms, such as a vinyl group, methacryloxypropyl, methacryloxypropylmethyl group, acryloxy A propyl group, a mercaptopropyl group, a mercaptopropylmethyl group, etc. can be mentioned. By setting the number of carbon atoms to 15 or less, the flexibility when the protective layer is formed is not excessively increased, and sufficient hardness can be obtained. By setting the carbon number of R within the above range, a protective layer with improved brittleness can be obtained. Moreover, the adhesiveness with the layer (for example, support body) adjacent to a protective layer can be improved.

  Furthermore, the organic group represented by R may have a heteroatom such as oxygen, nitrogen, or sulfur. When the organic group has a hetero atom, adhesion with an adjacent layer can be further improved.

  As trialkoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, propyltrimethoxysilane, Phenyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-ureidopropyltriethoxysilane, methyltriethoxysilane, methyl Trimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, phenyltriethoxysilane, phenol It can be exemplified Le trimethoxysilane. Of these, methyltriethoxysilane and methyltrimethoxysilane are particularly preferably used. Examples of commercially available products include KBE-13 (manufactured by Shin-Etsu Chemical Co., Ltd.).

(Metal complex)
The protective layer preferably contains a metal complex as a curing agent. As the metal complex, a metal complex containing a metal element selected from aluminum, magnesium, manganese, titanium, copper, cobalt, zinc, hafnium and zirconium is preferable, and these may be used in combination.

  These metal complexes can be easily obtained by reacting a metal alkoxide with a chelating agent. Examples of chelating agents include β-diketones such as acetylacetone, benzoylacetone, and dibenzoylmethane; β-keto acid esters such as ethyl acetoacetate and ethyl benzoylacetate, and aluminum chelates are preferred.

  Preferable specific examples of the metal complex include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetate bis (ethyl acetoacetate), aluminum tris (acetyl) Magnesium chelate compounds such as ethyl acetoacetate magnesium monoisopropylate, magnesium bis (ethylacetoacetate), alkyl acetoacetate magnesium monoisopropylate, magnesium bis (acetylacetonate), zirconium tetraacetylacetate Narate, zirconium tributoxyacetylacetonate, zirconium acetate Le acetonate bis (ethyl acetoacetate), manganese acetylacetonate, cobalt acetylacetonate, copper acetylacetonate, titanium acetylacetonate and titanium oxy acetylacetonate. Of these, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), magnesium bis (acetylacetonate), magnesium bis (ethylacetoacetate), and zirconium tetraacetylacetonate are preferred, and storage stability Considering the availability, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), aluminum bisethylacetoacetate, monoacetylacetonate and the like, which are aluminum chelate complexes, are particularly preferable. Examples of commercially available products include aluminum chelate A (W), aluminum chelate D, aluminum chelate M (manufactured by Kawaken Fine Chemical Co., Ltd.), and the like.

The metal complex is preferably used in an amount of 20% by mass to 70% by mass, more preferably 30% by mass to 60% by mass, and more preferably 40% by mass to 50% by mass with respect to the total amount of the alkoxysilane described above. More preferably, it is used in an amount of%.
When the protective layer contains the metal complex in the above lower limit or more, the reaction rate of silanol dehydration condensation can be set to an appropriate rate, and the protective layer can have a uniform thickness and high alkali resistance.

(Other additives)
The protective layer may contain a surfactant for the purpose of improving surface slipperiness and reducing friction on the surface of the layer.
As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

  Examples of the fluorosurfactant include MegaFace (registered trademark) F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, and F475. , F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon (registered trademark) S -382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393, KH-40 (above, Asahi Glass Co., Ltd.) Manufactured), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), and the like.

  Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl. Ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5 manufactured by BASF) , 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Pio D-6512, D-6414, D-6112, D-6115, D-6120, D-6131, D-6108-W, D-6112-W, D-6115-W, D-6115-X, D -6120-X (manufactured by Takemoto Yushi Co., Ltd.), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NAROACTY (registered trademark) CL-95, HN-100 (manufactured by Sanyo Chemical Industries, Ltd.), etc. It is done.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

  Specific examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sanded (registered trademark) BL (manufactured by Sanyo Chemical Industries, Ltd.), and the like.

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 ”,“ KP341 ”,“ KF6001 ”,“ KF6002 ”manufactured by Shin-Etsu Chemical Co., Ltd.,“ BYK307 ”,“ BYK323 ”,“ BYK330 ”manufactured by BYK Chemie.
Only one type of surfactant may be used, or two or more types may be combined.

  The addition amount of the surfactant is preferably 0.001% by mass to 10.0% by mass, more preferably 0.005% by mass to 10.0% by mass, and still more preferably with respect to the total mass of the protective layer. Is 1% by mass to 8% by mass.

For the surfactant, a pH adjuster may be added to an aqueous composition (aqueous composition for forming a protective layer) to be adjusted to form a protective layer, and the pH may be adjusted to be in a desired range. .
The pH adjuster is not particularly limited as long as it changes the pH. Specifically, as the acid (organic acid, inorganic acid), for example, nitric acid, oxalic acid, acetic acid, formic acid, hydrochloric acid, etc., as alkali Examples thereof include ammonia, triethylamine, ethylenediamine, sodium hydroxide, potassium hydroxide and the like. The pH adjusting agent may be added directly or as a solution such as an aqueous solution. The amount of the pH adjuster to be used is not particularly limited as long as the pH satisfies a desired range.
It is preferable to adjust so that pH of an aqueous composition may be set to 2-6. As the pH adjuster, nitric acid, oxalic acid, acetic acid, formic acid, and hydrochloric acid are preferable, and acetic acid is particularly preferable.

~ Formation of protective layer ~
The protective layer may be formed by preparing an aqueous composition and applying it to the surface of the support. Although the preparation procedure of the aqueous composition for forming the protective layer is not particularly limited, a method of hydrolyzing an epoxy group-containing alkoxysilane and an epoxy-free alkoxysilane in this order, and adding inorganic particles and an aluminum chelate complex to the hydrolyzed solution in this order Is preferable from the viewpoints of solubility and storage stability.

Application | coating of the aqueous composition for protective layer formation can be performed by a well-known method. For example, a coating method using a spin coater, roll coater, bar coater, curtain coater or the like can be used.
It is preferable that a step of drying the coating solution is provided after the coating. In the drying step, it is preferable to perform heat drying. In heat drying, it is preferable to heat so that the temperature of the coating film is 160 ° C. or higher, more preferably 170 ° C. or higher, and more preferably 180 ° C. or higher. Further, the temperature of the coating film is preferably 220 ° C. or lower, and more preferably 210 ° C. or lower. By setting the heating and drying temperature within the above range, the coating film can be sufficiently cured, and deformation of the protective layer can be prevented. The heating time is preferably 10 seconds to 5 minutes.

  The thickness of the protective layer can be controlled by adjusting the coating amount of the composition for forming the protective layer. From the viewpoint of the hardness of the protective layer to be obtained, the thickness is more preferably constant in the range of 0.6 μm to 1.8 μm. If the thickness is 0.6 μm or more, sufficient hardness can be easily obtained and a sufficient function as a protective layer can be obtained. On the other hand, if the thickness is 1.8 μm or less, the internal stress of the protective layer does not become too large, curling Is prevented from being deformed.

The arithmetic average surface roughness Ra on the surface of the protective layer can be controlled by the particle diameter and solid content concentration of the inorganic particles contained. From the viewpoint of the antiblocking property of the protective layer to be obtained, Ra is preferably 1.0 nm to 4.0 nm. When Ra is 1.0 nm or more, sufficient anti-blocking property is easily developed, and when the heat shielding materials are stacked, they are not attached, and the appearance can be kept good. On the other hand, when Ra is 4.0 nm or less, the transparency of the protective layer can be kept good.
The arithmetic average surface roughness Ra on the surface of the protective layer can be measured using an AFM (atomic force microscope) or the like.

[Layer structure of heat shielding material]
The heat shielding material of the present invention is not particularly limited in form as long as it has the above-mentioned support, the above-mentioned metal-containing layer, and the above-mentioned organic particle-containing layer. The aspect which is a film from a viewpoint of transparency and productivity to a heat-shielding material is preferable. That is, the heat shield material of the present invention is preferably a heat shield film.
As an example of the layer structure of the heat-shielding material of the present invention, as shown in FIG. 1, an embodiment in which the support 3, the metal-containing layer 2, and the organic particle-containing layer 1 are laminated in this order is given. It is done.
Moreover, as another example, as shown in FIG. 2, the aspect by which the protective layer 4, the support body 3, the metal containing layer 2, and the organic-particle containing layer 1 are laminated | stacked in this order is mentioned. .

[Method of manufacturing heat shielding material]
The heat shielding material can be produced by forming the aforementioned metal-containing layer on the aforementioned support and forming the aforementioned organic particle-containing layer on the metal-containing layer. The method for forming each layer is as described above.
Moreover, you may manufacture a heat-shielding material by forming the above-mentioned protective layer in the opposite side to the side which has a metal content layer of a support body. The method for forming the protective layer is as described above.

  The heat shielding material may be manufactured using a roll-shaped support, or may be manufactured using a sheet-shaped support. After forming each layer, it may be wound into a roll or cut into a sheet.

<Insulation material>
The heat insulation material of this invention has the above-mentioned heat insulation material, and the heat insulation layer containing the fibrous conductive particle arrange | positioned on the opposite side to the side which has a metal containing layer of the support body of a heat insulation material.
Since the heat insulating material has a heat insulating layer containing fibrous conductive particles, the heat insulating effect can be exhibited in addition to the above-described heat shielding effect.

[Insulation layer]
The heat insulating layer contains at least one kind of fibrous conductive particles.
For example, the heat insulating layer preferably has a small void size to reflect far infrared rays. For example, in the cross-sectional photograph of the heat insulating layer, the void size is 80% or more and the void size is 25 μm ² or less. preferable.

(Fibrous conductive particles)
The fibrous conductive particles are particles having fibrous conductivity.
Here, the “fibrous” includes particles having a wire shape, a linear shape, or a rod shape. In addition, the term “particles having conductivity” refers to the case where pellets having a thickness of 0.01 mm or more are produced by molding the fibrous particles with a tablet molding machine or dispersing the fibrous particles in a liquid and then drying. The particle | grains from which the resistance value between the one end surface and other end surface of a pellet becomes 10 ohms or less are pointed out. The resistance value is a value measured by a two-point tester (MR-4060, manufactured by MONOTARO).
Examples of the fibrous conductive particles include fibrous metal particles such as metal nanowires and rod-shaped metal particles, carbon nanotubes, and fibrous conductive resins. As the fibrous conductive particles, metal nanowires are preferable. Hereinafter, metal nanowires may be described as representative examples of the fibrous conductive particles, but descriptions regarding the metal nanowires can be used as general descriptions of the fibrous conductive particles.
“Metal nanowires” are conductive and have a long axis length longer than the diameter (short axis length) and a short axis length (that is, the length of a cross section perpendicular to the longitudinal direction) in the nano order. Metal particles with a size shape. It may be a solid fiber or a hollow fiber.

  The heat insulating layer preferably contains metal nanowires having an average minor axis length of 150 nm or less as fibrous conductive 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 conductive particles such as metal nanowires preferably have a solid structure.

From the viewpoint of easily forming a more transparent heat insulating layer, for example, the fibrous conductive 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 the fibrous conductive particles such as metal nanowires is preferably 100 nm or less, more preferably 60 nm or less, and more preferably 50 nm or less because of ease of handling during production. More preferably, it is particularly preferably 25 nm or less, since a further excellent haze is obtained. By setting the average minor axis length to 1 nm or more, a heat insulating 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.
The average minor axis length of the fibrous conductive particles such as metal nanowires is preferably 1 nm to 100 nm, more preferably 5 nm to 60 nm, more preferably 10 nm to 10 nm from the viewpoints of haze value, oxidation resistance, and weather resistance. More preferably, it is 60 nm, and it is especially preferable that it is 15 nm-50 nm.

The average major axis length of the fibrous conductive 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 the fibrous conductive 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 μm to 50 μm, more preferably 10 μm to 40 μm, and even more preferably 15 μm to 40 μm. . When the average long axis length of the metal nanowire is 50 μm or less, it becomes easy to synthesize the metal nanowire without forming an aggregate, and when the average long axis length is 5 μm or more, it is easy to obtain sufficient heat insulation. It becomes.
The average minor axis length (average diameter) and average major axis length of the fibrous conductive particles such as metal nanowires are determined by observing a TEM image or an optical microscope image using a transmission electron microscope (TEM) and an optical microscope, for example. Can be sought.
Specifically, the average minor axis length (average diameter) and the average major axis length of the fibrous conductive particles such as metal nanowires are determined using a transmission electron microscope (manufactured by JEOL Ltd., trade name: JEM-2000FX). About 300 metal nanowires selected at random, the short axis length and the long axis length are measured, respectively, and the average short axis length and the average long axis length of the fibrous conductive particles such as metal nanowires can be obtained from the average value. .
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. In addition, when fibrous conductive particles such as metal nanowires are bent, a value calculated from the radius and the curvature is taken as the major axis length in consideration of a circle having an arc.

Inclusion of fibrous conductive particles such as metal nanowires having a minor axis length (diameter) of 150 nm or less and a major axis length of 5 μm or more and 500 μm or less with respect to the content of fibrous conductive particles such as all metal nanowires in the heat insulating layer The amount of metal is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 75% by mass or more.
The short axis length (diameter) is 150 nm or less and the ratio of the fibrous conductive particles such as metal nanowires having a length of 5 μm or more and 500 μm or less is 50% by mass or more, so that sufficient conductivity can be obtained. This is preferable because voltage concentration is unlikely to occur and a decrease in durability due to voltage concentration can be suppressed. In a configuration in which conductive particles other than the fibrous conductive particles are substantially not included in the heat insulating layer, 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 conductive particles such as metal nanowires used for the heat insulating 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 μm to 50 μm increases, which is preferable in terms of transparency and heat insulation.
The coefficient of variation of the short axis length (diameter) of the fibrous conductive particles such as metal nanowires 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.

  The aspect ratio of the fibrous conductive particles such as metal nanowires 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.

The aspect ratio of the fibrous conductive 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, and more preferably 50 to 100,000. Preferably, 100 to 100,000 is more preferable.
When the aspect ratio is 10 or more, a network in which fibrous conductive particles such as metal nanowires are in contact with each other is easily formed, and a heat insulating layer having high heat insulating properties can be easily obtained. Further, when the aspect ratio is 100,000 or less, for example, in a coating liquid when a heat insulating layer is provided on a support by coating, it is suppressed that fibrous conductive particles such as metal nanowires are entangled to form an aggregate. In addition, since a stable coating solution can be obtained, the heat insulating layer can be easily manufactured.
The content of the fibrous conductive particles such as metal nanowires having an aspect ratio with respect to the mass of the fibrous conductive particles such as all metal nanowires included in the heat insulating layer is not particularly limited. For example, it is preferably 70% by mass or more, more preferably 75% by mass or more, and further preferably 80% by mass or more.

The shape of the fibrous conductive particles 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 conductive particles such as metal nanowires is detected by applying an aqueous dispersion of fibrous conductive particles such as metal nanowires on a support and observing the cross-section with a transmission electron microscope (TEM). Can do.

The metal forming the fibrous conductive particles such as metal nanowire is not particularly limited and may be any metal. In addition to one metal, two or more metals may be used in combination, or an alloy may be used. Among these, those formed from simple metals or metal compounds are preferable, and those formed from simple metals are more preferable.
The metal is preferably at least one metal selected from the group consisting of the fourth period, the fifth period, and the sixth period of the periodic table (IUPAC 1991), and at least one metal selected from Groups 2-14 More preferably, at least one metal selected from Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, Group 13, and Group 14 is more preferable. It is particularly preferable to contain a metal as a main component.

  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 More preferred is an alloy containing silver, and particularly preferred is silver or an alloy containing silver. 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. .

  From the viewpoint of realizing high heat insulation properties, the fibrous conductive particles such as metal nanowires contained in the heat insulating layer preferably contain silver nanowires, the average minor axis length is 1 nm to 150 nm, and the average major axis length is 1 μm. More preferably, silver nanowires of ˜100 μm are included, and silver nanowires having an average minor axis length of 5 nm to 30 nm and an average major axis length of 5 μm to 30 μm are further preferred. The content of silver nanowires relative to the mass of fibrous conductive particles such as all metal nanowires contained in the heat insulating 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 conductive particles such as all metal nanowires contained in the heat insulating layer is preferably 50% by mass or more, more preferably 80% by mass or more, and all metal nanowires and the like. It is further preferable that the fibrous conductive particles are substantially silver nanowires. Here, “substantially” means that metal atoms other than silver inevitably mixed are allowed.

The content of the fibrous conductive particles such as metal nanowires contained in the heat insulating layer is within the desired ranges of the resistivity, total light transmittance and haze value of the heat insulating layer depending on the type of the fibrous conductive particles such as metal nanowires. The amount is preferably such that
At this time, it is preferable from the viewpoint of controlling the resistivity of the heat insulating layer to reduce the amount of the fibrous conductive particles with respect to the heat insulating layer. When the amount of the fibrous conductive particles is within the above range, the mass per unit area of the heat insulating layer (the coating amount of the total solid content of the coating liquid during layer formation) is preferably 0.110 g / m ² to 1. in the range of 000 g / ^{m 2,} more preferably in the range of ^{0.150g / m 2 ~0.600g / m 2} , and particularly preferably ^{0.200g / m 2 ~0.500g / m 2} .
The amount of the fibrous conductive particles with respect to the heat insulating layer is preferably 1% by mass to 35% by mass, more preferably 3% by mass to 30% by mass, and particularly preferably 5% by mass to 25% by mass. preferable.

-Manufacturing method of fibrous conductive particles-
The fibrous conductive 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. In addition, after forming fibrous conductive particles such as metal nanowires, it is preferable to perform a desalting treatment by a conventional method from the viewpoint of dispersibility and stability over time of the heat insulating layer.
As methods for producing fibrous conductive 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 conductive 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 alcohol solvents include methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, and the like.
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 conductive particles such as metal nanowires to be formed is in a preferable range in which dispersion stability can be ensured, 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.

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.

The production of fibrous conductive 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 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 the fibrous conductive particles such as metal nanowires, and the fibrous conductive particles such as the metal nanowires may be added in the presence of a dispersing agent. 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 used as a dispersant are compounds included in the polymer described later.

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. 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 has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of preferably 3000 or more and 300000 or less, and more preferably 5000 or more and 100000 or less.
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 Shoin 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.

The halogen compound is not particularly limited as long as it is a compound containing bromine, chlorine, and 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.

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. Dodecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, stearyltrimethylammonium bromide, stearyltrimethylammonium chloride, decyltrimethylammonium bromide, decyltrimethylammonium chloride, dimethyldistearylammonium bromide, dimethyldistearylammonium chloride, Lauryldimethylammonium bromide, dilauryldimethylammonium chloride Chloride, dimethyl dipalmityl ammonium bromide, dimethyl dipalmityl ammonium chloride.
In the method for producing metal nanowires, it is preferable to perform a desalting treatment after forming the metal nanowires. The desalting treatment after the formation of the metal nanowires can be performed by techniques such as ultrafiltration, dialysis, gel filtration, decantation, and centrifugation.

It is preferable that fibrous conductive 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 an aqueous 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 conductive 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.
The electrical conductivity and viscosity are measured with a concentration of fibrous conductive particles such as metal nanowires in the aqueous dispersion being 0.45% by mass. When the concentration of fibrous conductive 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 average thickness of the heat insulation layer is usually selected in the range of 0.005 μm to 2 μm. For example, by setting the average thickness to 0.001 μm to 0.5 μm, sufficient durability and film strength can be obtained. In particular, when the average thickness is in the range of 0.01 μm to 0.1 μm, it is preferable because an allowable range in manufacturing can be secured.
The present invention can maintain high heat insulation and transparency by using a heat insulating layer satisfying at least one of the following conditions (i) or (ii), and can be a metal nanowire or the like due to a sol-gel cured product. It is preferable that the fibrous conductive particles can be stably fixed and can achieve high strength and durability. For example, even when the thickness of the heat insulating layer is 0.005 μm to 0.5 μm, it is possible to obtain a heat insulating layer having wear resistance, heat resistance, moist heat resistance, and bending resistance that has no practical problem. For this reason, a heat insulation material is used suitably for various uses. In an aspect that requires a thin layer, the 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 0.01 μm to 0.1 μm is most preferable. Thus, the transparency of a heat insulation layer can further improve by making a heat insulation layer into a thinner layer.

  The average thickness of the heat insulation layer is calculated as an arithmetic average value of five thicknesses of the heat insulation layer measured by direct observation of the cross section of the heat insulation layer with an electron microscope. In addition, the thickness of the heat insulation layer is measured as, for example, a level difference between a portion where the heat insulation layer is formed and a portion where the heat insulation layer is removed using a stylus type surface shape measuring instrument (Dektak (registered trademark) 150, manufactured by Bruker AXS). You can also However, when removing the heat insulating layer, there is a possibility that a part of the support may be removed, and an error is likely to occur because the formed heat insulating layer is a thin film. Therefore, in the examples described later, the average thickness measured using an electron microscope is described.

(matrix)
The heat insulating layer may include a matrix. Here, the “matrix” is a general term for resin components that are fixed in a state where fibrous conductive particles such as metal nanowires are dispersed and form a layer. By including the matrix, the dispersion of the fibrous conductive particles such as metal nanowires in the heat insulating layer is stably maintained, and even when the heat insulating layer is directly formed on the surface of the support, the support and the heat insulating layer are strong. There is a tendency to ensure adhesion.
Examples of the matrix include a sol-gel cured product and a non-photosensitive resin.

-Hardened sol-gel-
The heat insulating layer preferably contains a sol-gel cured product that also has a function as a matrix, and is obtained by hydrolysis and polycondensation of an alkoxide compound of an element (b) selected from the group consisting of silicon, titanium, zirconium and aluminum. More preferably, it contains a cured product.
The heat-insulating layer hydrolyzes the metal nanowire containing the metal element (a) and having an average minor axis length of 150 nm or less, and the alkoxide compound of the element (b) selected from the group consisting of silicon, titanium, zirconium, and aluminum. More preferably, it contains at least a sol-gel cured product obtained by polycondensation.

The heat insulating layer preferably satisfies at least one of the following conditions (i) or (ii), more preferably satisfies at least the following condition (ii), and particularly preferably satisfies the following conditions (i) and (ii): preferable.
(I) Ratio of the amount of the element (b) contained in the heat insulating layer and the amount of the metal element (a) contained in the heat insulating layer [(number of moles of the element (b)) / (metal element (a) In the range of 0.10 / 1 to 22/1.
(Ii) The ratio [(alkoxide compound content) / (metal nanowire content)] of the mass of the alkoxide compound used for forming the sol-gel cured product in the heat insulation layer to the mass of the metal nanowires contained in the heat insulation layer is It is in the range of 0.25 / 1 to 30/1.

In the heat insulating layer, the ratio of the amount of the alkoxide compound to the amount of the metal nanowire used, that is, the ratio of [(mass of alkoxide compound) / (mass of metal nanowire)] is 0.25 / 1 to 30/1. Preferably, it can be formed in a range. When the mass ratio is 0.25 / 1 or more, the heat insulation (which is considered to be due to the high conductivity of the fibrous conductive particles) and the transparency are excellent, and at the same time, the wear resistance, heat resistance, and heat and humidity resistance In addition, all of the bending resistance can be an excellent heat insulating layer. When the said mass ratio is 30/1 or less, it can become a heat insulation 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 a preferable range, the obtained heat insulating layer has high heat insulating properties and high transparency (visible light transmittance and haze), and is excellent in wear resistance, heat resistance, and heat and moisture resistance, And it will be excellent in bending resistance, and the heat insulating material which has a suitable physical property can be obtained stably.

As an optimal aspect, in the heat insulation layer, the ratio of the amount of the element (b) to the amount of the metal element (a) [(number of moles of the element (b)) / (number of moles of the metal element (a)) ] Is in the range of 0.10 / 1 to 22/1. The molar ratio is more preferably in the range of 0.20 / 1 to 18/1, particularly preferably 0.45 / 1 to 15/1, more particularly preferably 0.90 / 1 to 11/1, and even more. Especially preferably, it is the range of 1.5 / 1-10/1.
When the molar ratio is in the above range, the heat insulating layer has both heat insulating properties and transparency, and from the viewpoint of physical properties, it is excellent in wear resistance, heat resistance, moist heat resistance, and flex resistance. It can be excellent.
The alkoxide compound that can be used when forming the heat insulating layer is exhausted by hydrolysis and polycondensation, and the alkoxide compound is substantially absent in the heat insulating layer. Element (b). By adjusting the mass ratio of the element (b) such as silicon and the metal element (a) derived from the metal nanowire to the above range, a heat insulating layer having excellent characteristics is formed.

The element (b) component selected from the group consisting of silicon, titanium, zirconia and aluminum derived from the alkoxide compound in the heat insulating layer and the metal element (a) component derived from the metal nanowire can be analyzed by the following method.
That is, by subjecting the heat insulating layer to X-ray photoelectron analysis (ESCA), the substance amount ratio, that is, (element (b) component mol number) / (metal element (a) component mol number) However, in the ESCA analysis method, since the measurement sensitivity differs depending on the element, the obtained value does not necessarily indicate the molar ratio of the element component immediately. It is possible to create a calibration curve using a known heat insulation layer, and calculate the mass ratio of the actual heat insulation layer from the calibration curve. The calculated value is used.

  It is preferable that the heat insulating material has high heat insulating properties and high transparency, and also has an effect of being excellent in wear resistance, heat resistance and moist heat resistance and excellent in bending resistance. These effects are considered to be manifested when the heat-insulating layer contains a metal nanowire and a matrix that is a sol-gel cured product obtained by hydrolysis and polycondensation of an alkoxide compound. That is, the ratio of the matrix contained in the heat insulating layer is small compared to the case of the heat insulating layer containing a general organic polymer resin (for example, (meth) acrylic resin, vinyl polymerization resin, etc.) as a matrix. However, since a dense heat insulating layer with few voids and high crosslink density is formed, a heat insulating material having excellent wear resistance, heat resistance and heat and moisture resistance can be obtained. And the content molar ratio of the alkoxide compound-derived element (b) / metal nanowire-derived metal element (a) is in the range of 0.10 / 1 to 22/1, and 0.10 / 1 to 22 In relation to the fact that the mass ratio of alkoxide compound / metal nanowire is in the range of 0.25 / 1 to 30/1, the above-mentioned action It is presumed that this increases the balance, maintains the heat insulation and transparency, and has the effect of being excellent in abrasion resistance, heat resistance and moist heat resistance, and at the same time being excellent in bending resistance.

-Non-photosensitive resin-
The non-photosensitive resin includes a polymer. Specific examples of the polymer include polyacrylic acid such as polymethacrylic acid, polymethacrylate (eg, poly (methyl methacrylate)), polyacrylate, and polyacrylonitrile, polyvinyl alcohol, polyester (eg, polyethylene terephthalate (PET), polyester) Naphthalate and polycarbonate), phenol or cresol-formaldehyde (Novolacs (registered trademark)), polystyrene, polyvinyl toluene, polyvinyl xylene, polyimide, polyamide, polyamide imide, polyether imide, polysulfide, polysulfone, polyphenylene, polyphenyl ether, etc. Highly aromatic polymer, polyurethane (PU), epoxy, polyolefin (eg, polypropylene, polymethyl) Pentene and cyclic olefin), acrylonitrile-butadiene-styrene copolymer (ABS), cellulose, silicone and other silicon-containing polymers (eg, polysilsesquioxane and polysilane), polyvinyl chloride (PVC), polyvinyl acetate , Polynorbornene, synthetic rubber (eg, EPR, SBR, EPDM), and fluorocarbon polymers (eg, polyvinylidene fluoride, polytetrafluoroethylene (TFE), or polyhexafluoropropylene), fluoro-olefins Copolymers, and hydrocarbon olefins (for example, LUMIFLON (registered trademark) manufactured by Asahi Glass Co., Ltd.), and amorphous fluorocarbon polymers or copolymers (for example, CYTOP (registered trademark) manufactured by Asahi Glass Co., Ltd. or DuPont) Made Eflon (TM) AF) although are not limited to much.

(Other additives)
The heat insulating layer may contain additives such as a crosslinking agent, a dispersant, a solvent, a metal antioxidant, and other conductive materials as necessary.

-Crosslinking agent-
The crosslinking agent is a compound capable of forming a chemical bond by free radical or acid and heat, for example, a melamine compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, a guanamine type Ethylene, including compounds, glycoluril compounds, urea compounds, phenolic compounds or phenol ether compounds, epoxy compounds, oxetane compounds, thioepoxy compounds, isocyanate compounds, or azide compounds, methacryloyl groups or acryloyl groups And compounds having an unsaturated group. Among these, an epoxy compound, an oxetane compound, and a compound having an ethylenically unsaturated group are particularly preferable in terms of film properties, heat resistance, and solvent resistance.
Moreover, oxetane resin can be used individually by 1 type or in mixture with an epoxy resin. In particular, when used in combination with an epoxy resin, the reactivity is high, which is preferable from the viewpoint of improving film properties.
The content of the crosslinking agent in the heat insulating layer is preferably 1 part by mass to 250 parts by mass, and preferably 3 parts by mass to 200 parts when the total mass of the solid content of the fibrous conductive particles such as the above-described metal nanowires is 100 parts by mass. Part by mass is more preferable.

-Dispersant-
The dispersant is used to disperse the fibrous conductive particles such as the above-mentioned metal nanowires in the heat insulating layer forming composition while preventing aggregation. 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 a polymer dispersing agent include polyvinylpyrrolidone, BYK (registered trademark) series (manufactured by Big Chemie), Solsperse (registered trademark) series (manufactured by Nihon Lubrizol, etc.), and Ajisper (registered trademark) series (Ajinomoto Co., Inc.). Company-made).
The content of the dispersant in the heat insulating layer is preferably 0.1 part by mass to 50 parts by mass, more preferably 0.5 part by mass to 40 parts by mass with respect to 100 parts by mass of the resin component, and 1 part by mass to 30 parts by mass. Part is particularly preferred.
By setting the content of the dispersant to the binder to 0.1 parts by mass or more, aggregation of fibrous conductive 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.

-Solvent-
The solvent is a component used to form a coating liquid for forming a composition containing fibrous conductive particles such as the above-described metal nanowires and an alkoxide compound in the form of a film on the surface of the support, depending on the purpose. For example, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl lactate, 3-methoxybutanol, water, 1-methoxy-2- Examples include propanol, isopropyl acetate, methyl lactate, N-methylpyrrolidone (NMP), γ-butyrolactone (GBL), propylene carbonate, and the like. 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 concentration of the coating solution containing such a solvent is preferably in the range of 0.1% by mass to 20% by mass.

-Metal corrosion inhibitor-
The heat insulating layer preferably contains a metal corrosion inhibitor for fibrous conductive 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 and azoles 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 heat insulation layer over time. The metal corrosion inhibitor can be added to the composition for forming a heat insulation layer by adding it in a state dissolved in a suitable solvent or in powder form.
When adding a metal corrosion inhibitor, it is preferable that the content in a heat insulation layer is 0.5 mass%-10 mass% with respect to content of fibrous conductive particles, such as a metal nanowire.

  In addition, as the matrix, a polymer compound as a dispersant used in the production of the fibrous conductive particles such as the above-described metal nanowires can be used as at least a part of the components constituting the matrix.

-Other conductive materials-
In addition to fibrous conductive particles such as metal nanowires, the heat insulating layer can be used in combination with other conductive materials such as conductive fine particles as long as the effects of the present invention are not impaired. From the viewpoint of the effect, the content ratio of fibrous conductive 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 conductive 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 conductive particles such as metal nanowires to 50%, a dense network of fibrous conductive particles such as metal nanowires is formed, and a heat-insulating layer having high conductivity can be easily obtained. .
In addition, conductive particles having a shape other than the fibrous conductive particles such as metal nanowires may not significantly contribute to the conductivity in the heat insulating layer and may have absorption in the visible light region. In particular, it is preferable from the viewpoint of preventing the transparency of the heat-insulating layer from deteriorating, that the conductive particles are metal and are not in a shape such as a sphere with strong plasmon absorption.

Here, the ratio of the fibrous conductive particles such as metal nanowires can be obtained as follows. For example, when the fibrous conductive particles are silver nanowires and the conductive particles are silver particles, the silver nanowire aqueous dispersion is filtered to separate the silver nanowires from the other conductive particles and induce The ratio of 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 (ICP) emission spectrometer. The aspect ratio of the fibrous conductive particles such as metal nanowires is determined by observing the fibrous conductive particles such as metal nanowires remaining on the filter paper with a TEM, and the short axis length and long axis of the fibrous conductive particles such as 300 metal nanowires. Calculated by measuring each length.
The method for measuring the average minor axis length and the average major axis length of fibrous conductive particles such as metal nanowires is as described above.

(Formation of heat insulation layer)
There is no restriction | limiting in particular in the formation method of a heat insulation layer. At the time of forming the heat insulating layer, a method of forming the layer by reducing the amount of the fibrous conductive particles as compared with the total solid content is preferable. In another preferred embodiment, as a method of forming the heat insulating layer on the support, the above-mentioned metal nanowire having an average minor axis length of 150 nm or less and the above-mentioned alkoxide compound are mixed in a mass ratio (that is, (the alkoxide compound of Content) / (content of metal nanowires)) is in the range of 0.25 / 1 to 30/1, or the element (b) derived from the alkoxide compound and the metal element derived from the metal nanowire (a) The coating composition is coated with a liquid composition (hereinafter also referred to as “sol-gel coating liquid”) so that the molar ratio of 0.10 / 1 to 22/1. Adiabatic by forming and causing a hydrolysis and polycondensation reaction of the alkoxide compound in this liquid film (hereinafter, the hydrolysis and polycondensation reaction is also referred to as “sol-gel reaction”). Preferably it is formed. This method may or may not include the evaporation (drying) of water that can be contained as a solvent in the composition for forming a heat insulation layer by heating as necessary.
In one embodiment, the sol-gel coating solution may be prepared by preparing an aqueous dispersion of metal nanowires and mixing this with an alkoxide compound. In one embodiment, an aqueous solution containing an alkoxide compound is prepared, the aqueous solution is heated to hydrolyze and polycondensate at least a part of the alkoxide compound to form a sol state, and the aqueous solution in the sol state and the water dispersion of the metal nanowires A sol-gel coating solution may be prepared by mixing the solution.
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.

  There is no restriction | limiting in particular in the method of forming a heat insulation layer on a support body, It can carry out with a general apply | coating method, and can select suitably according to the objective. 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.

-Organic solvent-
Said composition for heat insulation layer formation may contain the organic solvent as needed. By containing the organic solvent, a more uniform liquid film can be formed on the support.
Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol, chloroform, and methylene chloride. Chlorine solvents, aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, ethylene glycol monomethyl ether and ethylene glycol dimethyl ether And glycol ether solvents.
When the composition for heat insulation layer contains the organic solvent, the range of 50 mass% or less is preferable with respect to the total mass of the composition, and the range of 30 mass% or less is more preferable.

  In the coating film of the sol-gel coating solution formed on the support, hydrolysis and condensation reactions of the alkoxide compound occur. In order to accelerate the reaction, it is preferable to heat and dry the coating film. 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.

[Layer structure of heat insulating material]
If the heat insulating material of the present invention has the above-described heat insulating material and the above-mentioned heat insulating layer disposed on the side opposite to the side having the metal-containing layer of the support of the heat insulating material, the form is particularly Not limited. The heat insulating material is preferably in the form of a film from the viewpoints of transparency and productivity. That is, the heat insulating material of the present invention is preferably a heat insulating film.
As an example of the layer structure of the heat insulating material of the present invention, as shown in FIG. 3, the heat insulating layer 5, the support 3, the metal-containing layer 2, and the organic particle-containing layer 1 are laminated in this order. The aspect which is mentioned is mentioned.

[Method of manufacturing heat insulating material]
The heat insulating material can be manufactured by forming the above heat insulating layer on the side opposite to the side having the metal-containing layer of the support in the above heat shielding material. The method for forming the heat insulating layer is as described above.
Moreover, the heat insulation layer in a heat insulation material may be formed on the surface of the support body of the above-mentioned heat shielding material, and when a heat insulation material has a protective layer, it may be formed on the surface of a protective layer.

  The heat insulating material may be manufactured in a roll shape or a sheet shape. After forming the heat insulation layer, it may be wound into a roll or cut into a sheet.

<Window glass>
The window glass of this invention has the above-mentioned heat shielding material or the above-mentioned heat insulation material, an adhesive layer, and a glass base material in this order.
It is preferable that the heat shielding material or the heat insulating material in the window glass is disposed with the side having the organic particle-containing layer facing the pressure-sensitive adhesive layer.

(Glass substrate)
The glass substrate of the window glass preferably has a thickness of 0.5 mm or more, more preferably 1 mm or more. From the viewpoint of suppressing the heat conduction due to the thickness of the glass substrate and increasing the warmth. A glass substrate having a thickness of 2 mm or more is particularly preferable.
A glass substrate is generally used in the form of a plate.
Examples of the glass substrate include transparent glass such as white plate glass, blue plate glass, and silica-coated blue plate glass.
The glass substrate preferably has a smooth surface, and is particularly preferably float glass.

  When determining the visible light transmittance of the window glass, it is preferable to measure by attaching the heat insulating material of the present invention to a 3 mm blue plate glass. About 3 mm blue plate glass, it is preferable to use the glass described in JIS A5759: 2008.

<Adhesive layer>
The window glass has an adhesive layer. The pressure-sensitive adhesive layer in the window glass is preferably disposed in contact with the above-described heat shielding material or the organic particle-containing layer of the above-described heat insulating material.
There is no restriction | limiting in particular as a material which can be utilized for formation of an adhesive layer, According to the objective, it can select suitably, For example, polyvinyl butyral (PVB) resin, (meth) acrylic resin, styrene / (meth) acrylic Examples thereof include resins, urethane resins, polyester resins, and silicone resins. Of these, (meth) acrylic resins are preferred from the viewpoint of refractive index.
These may be used individually by 1 type and may use 2 or more types together.

The pressure-sensitive adhesive layer made of these materials can be formed by coating.
Further, an antistatic agent, a lubricant, an antiblocking agent and the like may be added to the pressure-sensitive adhesive layer.
The thickness of the pressure-sensitive adhesive layer is preferably 0.1 μm to 10 μm.

  Moreover, you may use a commercially available double-sided tape as an adhesive layer. Examples of the double-sided tape include Panaclean PD-S1 (manufactured by Panac Co., Ltd.).

The heat shielding material or heat insulating material in the window glass is preferably attached to the inside of the window, that is, the indoor side of the window glass, from the viewpoint of heat shielding or heat insulation efficiency.
When the window glass has a heat insulating layer, the heat insulating layer preferably has a distance between the heat insulating layer and the outermost surface on the indoor side of 5 μm or less, although it depends on the thickness of the layer. The thickness is more preferably 5 μm or less, and further preferably 2 μm or more and 4 μm or less.
In addition, the outermost layer on the indoor side or the layer next to the outermost layer is preferable from the viewpoint of improving heat insulation, and more preferably the outermost layer on the indoor side.

  The window glass is preferably provided with an organic particle-containing layer on the sunlight side as much as possible because it can reflect in advance infrared rays that are to enter the room. Specifically, a pressure-sensitive adhesive layer is provided on the organic particle-containing layer, and is bonded to the glass substrate via the pressure-sensitive adhesive layer.

When pasting a heat shielding material or heat insulating material on a window glass, an adhesive layer is applied on the organic particle-containing layer of the heat shielding material or heat insulating material, or an adhesive layer is provided by laminating, and the glass substrate surface in advance After spraying an aqueous solution containing a surfactant (mainly anionic) on the surface of the pressure-sensitive adhesive layer, a heat shielding material or a heat insulating material is placed on the glass substrate through the pressure-sensitive adhesive layer.
Until the moisture evaporates, the adhesive force of the pressure-sensitive adhesive layer is low, and the position of the heat shielding material or heat insulating material of the present invention can be adjusted on the surface of the glass substrate. After the heat shielding material or heat insulating material is attached to the glass substrate, the remaining moisture between the glass substrate and the heat insulating material or heat insulating material is swept from the glass center toward the edge using a squeegee. Thus, the heat shielding material or the heat insulating material can be fixed to the surface of the glass substrate. In this way, it is possible to install a heat shielding material or a heat insulating material on the window glass.

[Configuration of window glass]
As an example of the configuration of the window glass of the present invention, as shown in FIG. 4, a glass substrate 7, an adhesive layer 6, an organic particle-containing layer 1, a metal-containing layer 2, and a support 3 are The aspect laminated | stacked in this order is mentioned.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “parts” are based on mass.

<Preparation of flat metal particles>
-Preparation of silver tabular grain dispersion A-
Ion exchange water 13L (liter) is weighed in a reaction vessel made of high Cr-Ni-Mo stainless steel (NTKR-4, manufactured by Nippon Metal Industry Co., Ltd.), and NTKR-4 is made on a stainless steel (SUS316L) shaft. While stirring ion-exchanged water at 100 rpm using a chamber equipped with four propellers and four NTKR-4 paddles, 1.0 L of 10 g / L trisodium citrate (anhydride) aqueous solution was added. It was added and kept at 35 ° C. To this solution, 0.68 L of 8.0 g / L polystyrene sulfonic acid aqueous solution was added, and 0.041 L of sodium borohydride aqueous solution prepared to 23 g / L using 0.04 N sodium hydroxide aqueous solution was further added. Further, 13 L of a 0.10 g / L silver nitrate aqueous solution was added at 5.0 L / min.
Thereafter, 1.0 L of 10 g / L trisodium citrate (anhydride) aqueous solution and 11 L of ion exchange water were added, and 0.68 L of 80 g / L potassium hydroquinone sulfonate aqueous solution was further added. The stirring speed was increased to 800 rpm, 8.1 L of a 0.10 g / L silver nitrate aqueous solution was added at 0.95 L / min, and then the temperature was lowered to 30 ° C.
A 44 g / L methylhydroquinone aqueous solution (8.0 L) was added, and then a 40 ° C. gelatin aqueous solution described later was added in its entirety. The stirring speed was increased to 1200 rpm, and a total amount of a silver sulfite white precipitate mixture described later was added to obtain a preparation.
When the pH change of the preparation solution stopped, 5.0 L of 1N (1 mol / L) aqueous sodium hydroxide (NaOH) was added at 0.33 L / min. Thereafter, 2.0 g / L of 1- (m-sulfophenyl) -5-mercaptotetrazole sodium aqueous solution (NaOH and citric acid (anhydride) was used to adjust to pH = 7.0 ± 1.0 and dissolve. 0.18 L) 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, a silver tabular grain dispersion liquid A was prepared.

-Preparation of gelatin aqueous 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. Further, 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.

-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 140 g / L sodium sulfite aqueous solution was added in a short time to prepare a mixed solution containing a silver sulfite white precipitate. This mixture was prepared immediately before use.

The silver tabular grain dispersion liquid A 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 silver tabular grain dispersion A were measured at 25 ° C. with pH = 9.4 (measured with KR5E manufactured by ASONE Co., Ltd.) and electrical conductivity of 8.1 mS / cm (measured with CM-25R manufactured by TOA DK Corporation). ) 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 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.

-Desalting and redispersion of flat metal particle dispersion-
800 g of the above-described silver tabular grain dispersion A was collected in a centrifuge tube, and 1N (1 mol / L) sodium hydroxide (NaOH) and / or 1 N (1 mol / L) sulfuric acid was used at 25 ° C. and pH = 9. Adjusted to 2 ± 0.2. Using a centrifuge (HimacCR22GIII, angle rotor R9A, manufactured by Hitachi Koki Co., Ltd.), centrifugation was performed at 9000 rpm for 60 minutes at 35 ° C., and 784 g of the supernatant was discarded. A 0.2 mM (0.2 mg / mol) aqueous NaOH solution was added to the precipitated silver tabular grains to make a total of 400 g, and the mixture was hand-stirred using a stir bar to obtain a coarse dispersion. In the same manner as this, 24 coarse dispersions were prepared to a total of 9600 g, added to a SUS316L tank and mixed. Furthermore, 10 mL of a 10 g / L solution of Pluronic 31R1 (manufactured by BASF) (diluted with a mixed solution of methanol: ion-exchanged water = 1: 1 (volume ratio)) was added. Using an automixer type 20 (manufactured by homomixer MARKII) manufactured by Primix Co., Ltd., a batch dispersion treatment was performed on the crude dispersion mixture in the tank at 9000 rpm for 120 minutes. The liquid temperature during dispersion was kept at 50 ° C. After dispersion, the temperature was lowered to 25 ° C., and then single-pass filtration was performed using a profile II filter (manufactured by Nippon Pole Co., Ltd., product model MCY1001Y030H13).

In this way, the salt dispersion and redispersion treatment were applied to the dispersion to prepare a silver tabular grain dispersion B.
When the spectral transmittance of the tabular silver particle dispersion B was measured by the same method as that for the tabular silver particle dispersion A, the absorption peak wavelength and the half width were almost the same as those of the tabular silver particle dispersion A.
The physical properties of Dispersion B were pH = 7.6, electrical conductivity of 0.37 mS / cm, and viscosity of 1.1 mPa · s at 25 ° C. The obtained silver tabular grain dispersion liquid A was stored in a 20 L container of Union Container II type and stored at 30 ° C. In addition, pH, electrical conductivity, and a viscosity were measured by the same method as said silver tabular grain dispersion liquid A.

-Evaluation of flat metal particles-
In the silver tabular grain dispersion liquid A, it was confirmed that hexagonal or circular and triangular tabular grains were formed.
An image obtained by observing the silver tabular grain dispersion A with a transmission electron microscope (TEM) was taken into image processing software ImageJ and subjected to image processing. Image analysis was performed on 200 particles arbitrarily extracted from TEM images of several fields of view, and the equivalent circle diameter was calculated. As a result of statistical processing based on these populations, the average diameter was 120 nm.
The silver tabular particle dispersion A was measured using a laser diffraction / scattering particle diameter / particle size distribution measuring apparatus Microtrac MT3300II (manufactured by Nikkiso Co., Ltd., particle permeability set to reflection), and the median diameter D50 = 48 nm. , D10 = 33 nm, D90 = 70 nm, and average particle size (volume weighted) 51 nm. Further, the flat metal particles were measured and found to be 97% by number.
When the silver tabular grain dispersion liquid B was measured in the same manner, almost the same results as the silver tabular grain dispersion liquid A were obtained, including the shape of the particle size distribution.

  The silver tabular grain dispersion B was dropped onto a silicon substrate and dried, and the individual thickness of the silver tabular grains was measured by FIB-TEM (Focused Ion Beam-Transmission Electron Microscope) method. Ten silver tabular grains in the silver tabular grain dispersion B were measured, and the average thickness was 8 nm.

<Preparation of coating solution for metal-containing layer>
A coating solution for a metal-containing layer was prepared so as to have the composition shown below.
-Silver tabular grain-containing thermal barrier coating liquid-
Aqueous urethane resin 0.27 parts (Hydran HW350, manufactured by DIC Corporation, solid content 30% by mass)
Silver tabular grain dispersion B ... 16.24 parts 1- (methylureidophenyl) -5-mercaptotetrazole ... 0.61 parts (manufactured by Wako Pure Chemical Industries, Ltd., alkaline aqueous solution having a solid content of 2% by mass) Prepared)
Surfactant: 0.96 parts (Ripal 870P, manufactured by Lion Corporation, solid content 1% by mass, anionic surfactant)
Surfactant: 1.19 parts (Naroacty (registered trademark) CL-95, manufactured by Sanyo Chemical Industries, Ltd., solid content: 1.0% by mass, nonionic surfactant)
Methanol ... 30.00 parts Distilled water ... 50.73 parts

<Preparation of coating solution for organic particle-containing layer>
The coating solution 1 for organic particle content layers was prepared so that it might become the composition shown below.
-Composition of coating solution 1 for organic particle-containing layer-
Water: 52.7 parts Crosslinking agent: 6.0 parts (Carbodilite (registered trademark) V-02-L2, manufactured by Nisshinbo Chemical Co., Ltd., solid content: 20% by mass)
Acrylic binder: 1.7 parts (AS-563A, manufactured by Daicel Finechem Co., Ltd., solid content: 27.5% by mass)
Surfactant: 8.2 parts (Lapisol (registered trademark) A-90, manufactured by NOF Corporation, solid content: 1.0% by mass, anionic surfactant)
Surfactant: 11.4 parts (Naroacty (registered trademark) CL-95, manufactured by Sanyo Chemical Industries, Ltd., solid content: 1.0% by mass, nonionic surfactant)
Urethane binder: 18.6 parts (Takelac (registered trademark) WS5100, manufactured by Mitsui Chemicals, Inc., solid content: 30% by mass)
1.3 parts of organic particles (MP-300, average particle size 0.1 μm, manufactured by Soken Chemical Co., Ltd., polymethyl methacrylate particles)

-Measurement of average particle size of organic particles-
The average particle size of the organic particles was obtained by taking a scanning electron micrograph (SEM image) of 100 organic particles, measuring the particle size, and calculating the arithmetic average value. When the particle diameter is circular, the particle diameter is represented by the diameter. When the particle diameter is indefinite, the projected area is converted into a circle equivalent. (Manufactured by Nireco).

-Measurement of glass transition temperature of organic particles-
The glass transition temperature (Tg) of the organic particles was measured under the following conditions using a differential scanning calorimeter “X-DSC7000” (manufactured by SII Nanotechnology). The measurement was performed twice for the same sample, and the second measurement result was adopted.
Conditions / Atmosphere in measurement chamber: Nitrogen (50 mL / min)
・ Raising rate: 5 ° C / min
Measurement start temperature: -100 ° C
-Measurement end temperature: 200 ° C
・ Sample pan: Aluminum pan ・ Measurement sample mass: 5 mg
-Calculation of Tg: Tg was calculated by rounding off the decimal point of the intermediate temperature between the lowering start point and the lowering end point of the DSC chart.

<Preparation of coating solution for protective layer>
A coating solution for a protective layer (hard coat layer) was prepared so as to have the composition shown below.
-Composition of coating liquid for hard coat layer-
Epoxy group-containing alkoxysilane 8.8 parts (KBE-403 (3-glycidoxypropyltriethoxysilane), manufactured by Shin-Etsu Chemical Co., Ltd.)
Epoxy group-free alkoxysilane ... 2.7 parts (KBE-04 (tetraethoxysilane), manufactured by Shin-Etsu Chemical Co., Ltd.)
Acetic acid aqueous solution ... 18.3 parts (manufactured by Daicel Corporation, 1 mass% aqueous solution of industrial acetic acid)
Metal complex: 2.6 parts (aluminum chelate D, manufactured by Kawaken Fine Chemical Co., Ltd., 76% by mass isopropyl alcohol (IPA) solution)
23.4 parts of inorganic particles (Snowtex (registered trademark) OYL, average particle size 100 nm, manufactured by Nissan Chemical Industries, Ltd., solid content 35% by mass)
Surfactant: 3.3 parts (Lapisol (registered trademark) A-90, manufactured by NOF Corporation, solid content 1% by mass, anionic surfactant)
Surfactant: 2.3 parts (Naroacty (registered trademark) CL-95, manufactured by Sanyo Chemical Industries, Ltd., solid content: 1% by weight, nonionic surfactant)
Water 38.6 parts

The hard coat layer coating solution was prepared by the following procedure.
An epoxy group-containing alkoxysilane (KBE-403) was added to an acetic acid aqueous solution (1% by mass acetic acid) and sufficiently hydrolyzed, and then an epoxy group-free alkoxysilane (KBE-04) was added to obtain a mixed solution. . The ratio of KBE-403 to the total amount of alkoxysilane added at this time (total amount of KBE-403 and KBE-04) was 76.5% by mass. Next, a metal complex (aluminum chelate D) is added to the above mixed solution in a necessary mass part with respect to the epoxy group-containing alkoxysilane, and further, inorganic particles (Snowtex (registered trademark) OYL), surfactant (rapizole ( (Registered trademark) A-90), a surfactant (NAROACTY (registered trademark) CL-95), and water were added to obtain a coating solution for a hard coat layer.

Example 1
<Preparation of thermal barrier film>
Polyethylene terephthalate (PET) film (Cosmo Shine (registered trademark) A4300 manufactured by Toyobo Co., Ltd., width: 1320 mm, thickness: 75 μm, double-sided easy adhesion layer treatment, refractive index: 1.66) as a support is 15 m / The metal-containing layer coating solution was applied at 10.6 ml / m ² with a wire bar and dried at 140 ° C. to provide a metal-containing layer containing silver tabular grains. . The thickness after coating and drying was 10 nm.
Following the coating and drying of the metal-containing layer, the organic particle-containing layer coating solution 1 is applied onto the metal-containing layer so as to be 10.35 ml / m ² using a wire bar No. 6, and at 135 ° C. for 2 minutes. Then, a drying treatment was performed to provide an organic particle-containing layer. The thickness after coating and drying was 0.6 μm.
The surface of the support opposite to the side having the metal-containing layer is subjected to corona treatment, and the wire bar 7 so that the thickness of the layer after drying the aqueous solution for hard coat film prepared above is 1.0 μm. A hard coat layer was formed by coating using a number and drying at 150 ° C. for 2 minutes.
After application of the protective layer, the coated support was wound up under temperature and humidity conditions of 23 ± 2 ° C. and a relative humidity of 55 ± 5% to obtain a roll-shaped heat shield film. The winding length was 2200 m.

Thus, the sample of Example 1 which is a heat-shielding film was produced.
The thickness of each layer is calculated by observing the cross section of the thermal barrier film with a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and the cross-section cutting and observation are performed by the FIB-TEM method. The calculation method was used as appropriate. The average value of 10-point measurement was taken as the thickness of the target layer.

(Example 2 to Example 13, Comparative Example 1 to Comparative Example 6)
Each example and each comparison were carried out in the same manner as in Example 1 except that the coating solution 1 for organic particle-containing layer used in Example 1 was changed to a coating solution prepared to have the composition shown in Table 1 or 2 below. An example thermal barrier film was prepared.

Details of the components in Table 1 are as follows.
MP-300: average particle size 0.1 μm, glass transition temperature 128 ° C., manufactured by Soken Chemical Co., Ltd., polymethyl methacrylate particle MP-1451: average particle size 0.15 μm, glass transition temperature 128 ° C., Soken Chemical Co., Ltd. Manufactured, polymethyl methacrylate particles MP-2200: average particle size 0.35 μm, glass transition temperature 128 ° C., manufactured by Soken Chemical Co., Ltd., polymethyl methacrylate particles MP-1000: average particle size 0.4 μm, glass transition temperature 128 ° C. , Manufactured by Soken Chemical Co., Ltd., polymethyl methacrylate particles MX-80H3wT: average particle size 0.8 μm, glass transition temperature 200 ° C. or higher, manufactured by Soken Chemical Co., Ltd., polymethyl methacrylate particles MX-150: average particle size 1. 5 μm, glass transition temperature of 200 ° C. or higher, manufactured by Soken Chemical Co., Ltd., polymethyl methacrylate particles MX-18 TA: average particle size 1.8 μm, glass transition temperature 200 ° C. or higher, manufactured by Soken Chemical Co., Ltd., polymethyl methacrylate particle MX-300: average particle size 3.0 μm, glass transition temperature 200 ° C. or higher, Soken Chemical Co., Ltd. Manufactured, polymethyl methacrylate particle MX-500: average particle size 5.0 μm, glass transition temperature 200 ° C. or higher, manufactured by Soken Chemical Co., Ltd., polymethyl methacrylate particle MX-1000: average particle size 10 μm, glass transition temperature 200 ° C. or higher. , Manufactured by Soken Chemical Co., Ltd., polymethyl methacrylate particles MX-1500H: average particle size 15 μm, glass transition temperature 200 ° C. or higher, manufactured by Soken Chemical Co., Ltd., polymethyl methacrylate particles Chemipearl (registered trademark) W900: average particle size 0 .8 μm, glass transition temperature 132 ° C., manufactured by Mitsui Chemicals, polyolefin latex particles X-130H: average particle diameter of 1.3 .mu.m, a glass transition temperature of 200 ° C. or higher, Soken Chemical & Engineering Co., Ltd., styrene particles

Details of the components in Table 2 are as follows.
MX-2000: average particle size 20 μm, glass transition temperature 200 ° C. or higher, manufactured by Soken Chemical Co., Ltd., polymethyl methacrylate particle seahoster KE-W30: average particle size 0.3 μm, glass transition temperature 200 ° C. or higher, Japan Made of catalyst, silica particle sea host KE-P100: average particle diameter 1.0 μm, glass transition temperature 200 ° C. or higher, manufactured by Nippon Shokubai Co., Ltd., silica particle sea host KE-P250: average particle diameter 2.5 μm, glass transition temperature 200 ° C. Above, manufactured by Nippon Shokubai Co., Ltd., silica particle cellosol 524: manufactured by Chukyo Yushi Co., Ltd., glass transition temperature 82 ° C., organic wax

(Example 14 to Example 29)
The coating solution for the organic particle-containing layer used in Example 1 was changed to a coating solution prepared to have the composition shown in Table 3 or Table 4 below, and the thickness of the organic particle-containing layer or the content of the organic particles was changed. Except for the above, the heat-shielding film of each example was produced in the same manner as in Example 1.

(Example 30)
In the heat shielding film of Example 6, a heat insulating layer was provided on the hard coat layer to produce a heat insulating film.

<Preparation of silver nanowire aqueous dispersion>
The following additive solutions A, G and H were prepared in advance.
(Additive liquid A)
5.1 g of silver nitrate powder was dissolved in 500 mL of pure water. Then, 1N (1 mol / L) ammonia water was added until it became transparent. And pure water was added so that the whole quantity might be 100 mL.
(Additive liquid G)
1 g of glucose powder was dissolved in 280 mL of pure water to prepare additive solution G.
(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.

Next, a silver nanowire aqueous dispersion was prepared as follows.
410 mL of pure water was placed in a three-necked flask, and 82.5 mL of additive solution H and 206 mL of additive solution G were added using a funnel while stirring at 20 ° C. To this solution, 206 mL of additive solution A was added at a flow rate of 2.0 mL / min and at a stirring speed of 800 rpm. Ten minutes later, 82.5 mL of additive solution H was added. Thereafter, the internal temperature was raised to 73 ° C. at 3 ° C./min. Then, the stirring rotation speed was reduced to 200 rpm and heated for 4 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 mass% silver nanowire aqueous dispersion. About the silver nanowire contained in the obtained silver nanowire aqueous dispersion, the average minor axis length, the average major axis length, and the coefficient of variation of the minor axis length of the silver nanowire were measured by the following methods. As a result, it was found that a silver nanowire having an average minor axis length of 17.1 nm, an average major axis length of 25.1 μm, and a coefficient of variation of 17.9% was obtained.

<Measuring method of average minor axis length (average diameter) and average major axis length of metal nanowire>
Short axis length (diameter) and long axis of 300 metal nanowires randomly selected from metal nanowires enlarged and observed using a transmission electron microscope (TEM; manufactured by JEOL Ltd., trade name: JEM-2000FX) The length was measured, and the average minor axis length (average diameter) and average major axis length of the metal nanowires were determined from the average value.

<Measurement method of coefficient of variation of minor axis length (diameter) of metal nanowire>
The short axis length (diameter) of 300 nanowires randomly selected from the transmission electron microscope (TEM) image was measured, and the standard deviation and average value of the 300 nanowires were calculated. The coefficient of variation was determined by dividing the standard deviation value by the average value.

<Formation of heat insulation 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)
・ Tetraethoxysilane: 5.0 parts (Brand name: KBE-04, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ 1 mass% acetic acid aqueous solution ... 10.0 parts ・ Distilled water ... 4.0 parts

  The obtained sol-gel solution 8.1 parts and silver nanowire aqueous dispersion 32.70 parts were mixed and further diluted with distilled water to obtain a sol-gel coating liquid.

On the protective layer of the thermal barrier film of Example 6 above, the silver amount of 0.040 g / ^{m 2} by a bar coating method, the sol-gel coating solution so that the total solid coating amount is 0.280 g / ^{m 2} Applied. Then, it dried at 175 degreeC for 1 minute, the sol gel reaction was caused, and the heat insulation layer was formed. In this way, a heat insulating film was obtained.
It was 0.20 micrometer when the average thickness of the heat insulation layer was measured by the above-mentioned method.

<Evaluation of heat insulating film or heat insulating film>
The following evaluation was performed with respect to the heat shielding film of Examples 1 to 29 obtained above, the heat insulating film of Example 30, and the comparative films of Comparative Examples 1 to 6. The evaluation results are shown in Table 5.

<Measurement of haze>
The heat-shielding film of Example 1 to Example 29, the heat-insulating film of Example 30 and the comparative film of Comparative Examples 1 to 6 were bonded together with an adhesive, and the heat-shielding film, the heat-insulating film or the comparative film. An adhesive layer was formed on. Panaclean PD-S1 manufactured by Panac Co., Ltd. (adhesive layer thickness of 25 μm, light release separator on one side of the adhesive layer and heavy release separator on the other side) was used as the pressure sensitive adhesive. Silicone-coated PET) was peeled off and bonded to the surface of the organic particle-containing layer.
The laminate after the adhesive was bonded was cut to a size of 5 cm × 5 cm to obtain a sample for haze measurement.
The sample for haze measurement was immersed in a 2.0% by weight water diluted solution of Real Perfect (manufactured by Lintec Corporation, construction solution) for 3 hours.
The haze of the sample for haze measurement after 3 hours was measured with NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd. During the measurement, the pressure-sensitive adhesive layer of the sample was used as the measurement surface.

-Evaluation criteria-
5: Haze value is 5% or less.
4: The haze value is greater than 5% and 7.5% or less.
3: The haze value is greater than 7.5% and 10% or less.
2: The haze value is greater than 10% and 12.5% or less.
1: The haze value is greater than 12.5%.

<Evaluation of adhesion>
Panaclean PD-S1 manufactured by Panac Co., Ltd. cut to 75 mm x 25 mm size (adhesive film with a pressure-sensitive adhesive layer thickness of 25 μm) is peeled off and applied to 100 mm x 25 mm glass. It was. Under the present circumstances, it affixed so that the one end of the long side of an adhesive layer and the one end of the long side of glass might align.
Thereafter, the heavy release separator (silicone-coated PET) of Panaclean PD-S1 was peeled off.
The heat shielding film of Examples 1 to 29, the heat insulating film of Example 30, and the comparative films of Comparative Examples 1 to 6 were each cut into a size of 150 mm × 25 mm.
The organic particle-containing layer and the pana of the film so that one end of the long side of the film of each of the above examples and comparative examples is aligned with the end of the long side of the panaclean PD-S1 and glass. Clean PD-S1 (adhesive layer) was bonded to obtain a sample for adhesion evaluation. The obtained sample for evaluating adhesiveness has a configuration in which one end of the long side of the film, the pressure-sensitive adhesive layer, and the glass is aligned, and the film and the glass are laminated via a pressure-sensitive adhesive layer of 75 mm × 25 mm size. Have.
The part of the obtained adhesive evaluation sample where the glass adhesive layer is not laminated is fixed with a chuck of a tensile tester (Tensilon: manufactured by A & D Company), and the film adhesive layer is laminated. The part which is not folded was folded and fixed to the other chuck of the tensile tester.
Then, about said sample for adhesive evaluation, peeling force was measured by performing a tensile test at a speed | rate of 100 mm / min, and the organic-particle content layer of the film, the adhesive layer, and adhesiveness were evaluated according to the following evaluation criteria. .

-Evaluation criteria-
OK: Peeling force is 4 N / 25 mm or more.
NG: Peeling force is less than 4 N / 25 mm.

<Friction coefficient>
The heat shielding film of Example 1 to Example 29, the heat insulating film of Example 30, and the comparative film of Comparative Example 1 to Comparative Example 6 were cut into a size of 130 mm × 100 mm and a size of 75 mm × 35 mm, respectively.
Double-coated adhesive tape No. manufactured by Nitto Denko Corporation 532 (thickness 0.06 mm, double-sided release liner type) was cut into 75 mm × 35 mm, and one release liner was peeled off.
A double-sided pressure-sensitive adhesive tape was bonded to the surface of the hard coat layer (heat insulating layer in the case of Example 30) of the film cut to the size of 75 mm × 35 mm.
Thereafter, the other release liner of the double-sided pressure-sensitive adhesive tape was peeled off and attached to a flat indenter of a static friction coefficient measuring machine TYPE: 10 manufactured by Shinto Kagaku Co., Ltd.
Double-sided pressure-sensitive adhesive tapes were respectively attached to both ends in the short side direction of the surface on the organic particle-containing layer side of the film cut to the size of 130 mm × 100 mm, and attached to a rising plate of a static friction coefficient measuring machine.
The ascending plate of the static friction coefficient measuring machine was raised, the static friction coefficient of the organic particle-containing layer of the film of each example was measured, and evaluated according to the following criteria. In the following evaluation criteria, 5 is the best result.

-Evaluation criteria-
5: Static coefficient of friction is 0.4 or more and 0.7 or less.
4: The static friction coefficient is 0.3 or more and less than 0.4, or more than 0.7 and 0.8 or less.
3: The static friction coefficient is 0.2 or more and less than 0.3, or more than 0.8 and 0.9 or less.
2: The coefficient of static friction is 0.1 or more and less than 0.2, or more than 0.9 and 1.0 or less.
1: Static friction coefficient is less than 0.1 or exceeds 1.0.

  In Table 5, “PMMA particles” represent polymethyl methacrylate particles, and “200 or more” represents that the glass transition temperature is 200 ° C. or more.

  From Table 5, it can be seen that the evaluation results of haze and adhesion are good in any of the examples. That is, the heat-insulating film or heat-insulating film of the examples of the present invention is a heat-insulating material or heat-insulating material that has excellent adhesion to the pressure-sensitive adhesive layer and suppresses a decrease in transparency derived from the construction liquid during construction. I understand that.

<Production of window glass>
Panaclean PD-S1 (adhesive layer thickness 25 μm, adhesive layer) manufactured by Panac Co., Ltd. in the following manner using the heat shielding film of Examples 1 to 29 and the heat insulating film of Example 30 A window glass in which a heat insulating film or a heat insulating film is arranged is prepared by bonding to a window glass surface of a building via a structure having a light release separator on one side and a heavy release separator on the other side.
When bonding a heat-shielding film or a heat insulating film to a window glass, a surfactant (polyoxyethylene lauryl ether sodium sulfate) is added to the surface of the window glass and the pressure-sensitive adhesive layer previously bonded to the heat-shielding film or the heat insulating film. After spraying a 1% by mass aqueous solution, a heat insulating film or a heat insulating film was placed on the window glass through the adhesive layer.
Until the moisture evaporates, the adhesive strength of the pressure-sensitive adhesive layer is lowered, so the position of the heat shield film or heat insulating film was adjusted on the glass surface. After the heat shield film or heat insulation film is attached to the window glass, the moisture remaining between the window glass and the heat insulation film or heat insulation film is swept away from the center of the glass toward the edge using a squeegee. A heat insulating film or a heat insulating film was fixed on the glass surface.
Thus, the window glass which installed the heat insulation film or the heat insulation film was obtained.

  Since these windowpanes use the heat-shielding films of Examples 1 to 29 and the heat-insulating film of Example 30, they have excellent adhesion to the pressure-sensitive adhesive layer and are derived from the construction liquid at the time of construction. Was suppressed.

DESCRIPTION OF SYMBOLS 1 ... Organic particle content layer 2 ... Metal content layer 3 ... Support body 4 ... Protective layer 5 ... Heat insulation layer 6 ... Adhesive layer 7 ... Glass base material 10 ... Heat shielding material 20 ... heat insulating material 30 ... window glass a ... (average) thickness D of metal particles D ... (average) particle diameter or (average) equivalent circle diameter of metal particles

Claims (17)

A support;
A metal-containing layer containing a metal element;
An organic particle-containing layer containing organic particles having an average particle diameter of 0.1 μm to 15 μm and a glass transition temperature of 100 ° C. or higher;
In this order, a heat shielding material.   The heat shielding material according to claim 1, wherein the metal-containing layer includes flat metal particles.   The heat shielding material according to claim 2, wherein the flat metal particles are flat silver particles.   The heat shielding material according to any one of claims 1 to 3, wherein an average particle diameter of the organic particles is 0.35 µm to 5.0 µm.   The thickness of the said organic-particle content layer is 0.2 micrometer-1.5 micrometers, The heat insulation material of any one of Claims 1-4.   The heat shielding material according to any one of claims 1 to 5, wherein a ratio of an average particle diameter of the organic particles to a thickness of the organic particle-containing layer is 1.15 to 3.75.   The heat shielding material according to any one of claims 1 to 6, wherein the content of the organic particles is 0.5 mass% to 5.5 mass% with respect to the total solid content of the organic particle-containing layer. .   The heat shielding material according to any one of claims 1 to 7, wherein the content of the organic particles is 1.5% by mass to 3.5% by mass with respect to the total solid content of the organic particle-containing layer. .   The heat-shielding material according to any one of claims 1 to 8, wherein a glass transition temperature of the organic particles is 200 ° C or higher.   The heat shielding material according to any one of claims 1 to 9, wherein the organic particles are particles of a hydrophobic resin.   The heat shielding material according to any one of claims 1 to 10, wherein the organic particles are particles of poly (meth) acrylic acid ester.   The heat shielding material according to any one of claims 1 to 11, wherein the organic particles are polymethyl methacrylate particles.   The heat shielding material according to any one of claims 1 to 12, further comprising a protective layer containing inorganic particles on a side opposite to the side having the metal-containing layer of the support.   The heat shielding material according to any one of claims 1 to 13, wherein the organic particle-containing layer has an organic wax content of 1% by mass or less based on the total solid content of the organic particle-containing layer.   The heat insulation material of any one of Claims 1-14, and the heat insulation layer containing the fibrous electroconductive particle arrange | positioned on the opposite side to the side which has a metal containing layer of the support body of the said heat insulation material, , Having heat insulation material.   The window glass which has the heat-shielding material of any one of Claims 1-14, or the heat insulation material of Claim 15, an adhesive layer, and a glass base material in this order.   The window glass according to claim 16, wherein the heat shielding material or the heat insulating material is arranged with a side having the organic particle-containing layer facing the pressure-sensitive adhesive layer.