JP7171211B2 - Thermal insulation board - Google Patents

Description

The present invention relates to a heat insulating substrate.

A heat shielding and heat insulating substrate is a substrate having both a heat shielding function and a heat insulating function. For example, when such a heat shielding and insulating substrate is attached to a window glass, the infrared reflection function prevents the inflow of solar heat (near infrared rays) from the outdoors into the room and the heating heat (far infrared rays) from the room to the outside. It is possible to suppress the outflow of infrared rays), and it is possible to improve indoor comfort and energy saving effect throughout the year.

As such a heat shielding and heat insulating substrate, a heat shielding and heat insulating substrate including a transparent substrate layer and an infrared reflecting layer has been proposed in recent years (Patent Documents 1 and 2). The infrared reflective layer has, for example, a structure in which metal oxide layers are provided on both sides of a metal layer, and both improved heat shielding properties due to reflection of near-infrared rays and improved heat insulation properties due to reflection of far-infrared rays can be achieved.

In addition to the infrared reflection function, the heat shield and heat insulation substrate has a high crack resistance that does not cause cracks when it is bent during handling or storage, and it can withstand repeated wiping with weak force during cleaning. High scratch resistance is required to suppress scratches caused by rubbing.

JP 2016-93892 A JP 2016-94012 A

An object of the present invention is to provide a heat shielding and heat insulating substrate having excellent scratch resistance. Another object of the present invention is to provide a heat-shielding and insulating substrate which is excellent in scratch resistance and crack resistance when the substrate is in the form of a film.

The heat shield and heat insulation substrate of the present invention is
A thermal insulation substrate comprising a transparent substrate layer and an infrared reflective layer,
An undercoat layer is provided between the transparent substrate layer and the infrared reflective layer,
a protective topcoat layer on the side of the infrared reflective layer opposite the transparent substrate layer;
The undercoat layer has a thickness of 0.01 μm to 5 μm,
The protective topcoat layer has a thickness of 5 nm to 500 nm,
The undercoat layer has a hardness of 0.50 GPa or more,
The protective topcoat layer has a hardness of 0.50 GPa or more.

In one embodiment, the protective topcoat layer has a contact angle of 90 degrees or greater.

In one embodiment, the protective topcoat layer comprises a coordination type material.

In one embodiment, the protective topcoat layer does not have a softening temperature within the range of 30°C to 75°C.

In one embodiment, the transparent substrate layer has a visible light transmittance of 10% or more.

In one embodiment, a topcoat layer is positioned between the protective topcoat layer and the infrared reflective layer.

In one embodiment, the protective topcoat layer is a resin layer formed from a resin composition containing an organic resin.

In one embodiment, the organic resin is an acrylic resin.

In one embodiment, the undercoat layer is a resin layer formed from a resin composition containing an organic resin.

In one embodiment, the organic resin is an acrylic resin.

In one embodiment, the elastic modulus of the undercoat layer is 8.25 GPa or less.

In one embodiment, the elastic modulus of the protective topcoat layer is 10.0 GPa or less.

ADVANTAGE OF THE INVENTION According to this invention, the thermal insulation board|substrate excellent in abrasion resistance can be provided. Furthermore, when the substrate is in the form of a film, it is possible to provide a heat-shielding and insulating substrate that is excellent in scratch resistance and crack resistance.

1 is a schematic cross-sectional view showing one embodiment of a heat shielding and heat insulating substrate of the present invention; FIG. 1 is a schematic cross-sectional view showing one embodiment of a heat shielding and heat insulating substrate of the present invention; FIG. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically an example of the type of usage of the thermal insulation board|substrate of this invention. 4 is a diagram showing the measurement results of the softening temperature of the protective topcoat layer obtained in Example 1. FIG.

≪1. Overview of thermal insulation substrates≫
The heat shielding and insulating substrate of the present invention comprises a transparent substrate layer and an infrared reflective layer, an undercoat layer is provided between the transparent substrate layer and the infrared reflective layer, and the infrared reflective layer is provided on the opposite side of the transparent substrate layer. With a protective topcoat layer on the side.

FIG. 1 is a schematic cross-sectional view showing one embodiment of the heat shielding and heat insulating substrate of the present invention. In FIG. 1, the heat shielding and insulating substrate 100 comprises a transparent substrate layer 10, an undercoat layer 60, an infrared reflective layer 20 and a protective topcoat layer 40. As shown in FIG.

The heat shielding and insulating substrate of the present invention includes: the side of the transparent substrate layer opposite to the undercoat layer; between the transparent substrate layer and the undercoat layer; between the undercoat layer and the infrared reflective layer; Between the layers, the side of the protective topcoat layer opposite the infrared reflective layer, respectively, may be provided with any other suitable layer, as desired. Such other layer may be one layer, or two or more layers. Moreover, such other layers may be of only one type, or may be of two or more types.

FIG. 2 is a schematic cross-sectional view showing one embodiment of the heat insulating substrate of the present invention. In FIG. 2, the heat shielding and heat insulating substrate 100 includes a transparent substrate layer 10, an undercoat layer 60, an infrared reflective layer 20, a protective topcoat layer 40, and a protective film . In FIG. 2, the infrared reflective layer 20 consists of three layers, a first metal oxide layer 22a, a metal layer 21, and a second metal oxide layer 22b.

The heat shielding and heat insulating substrate of the present invention may include a topcoat layer. The topcoat layer is a layer formed by a dry process, and the protective topcoat layer is a layer formed by coating.

As for the arrangement of the topcoat layer and the protective topcoat layer, the topcoat layer may be arranged between the infrared reflective layer and the protective topcoat layer, or the protective topcoat layer may be arranged between the infrared reflective layer and the topcoat layer. may be placed in

The heat shielding and heat insulating substrate of the present invention may have an adhesive layer on the opposite side of the transparent substrate layer to the infrared reflecting layer. Furthermore, a separator film may be provided on the surface of such an adhesive layer.

The visible light transmittance of the heat shielding and insulating substrate of the present invention is preferably 30% or more, more preferably 30% to 85%, still more preferably 45% to 80%, and particularly preferably 55% to 85%. 80%, most preferably 55% to 75%. The visible light transmittance is measured according to JIS-A5759-2008 (film for architectural window glass).

In the heat shielding and heat insulating substrate of the present invention, the hardness of the undercoat layer is preferably 0.50 GPa or more, and the hardness of the protective topcoat layer is preferably 0.50 GPa or more. The heat shielding and heat insulating substrate of the present invention can have excellent scratch resistance by satisfying such characteristics. Conversely, if even one of these properties is not satisfied, there is a risk that a heat shielding and heat insulating substrate with excellent scratch resistance cannot be provided.

In the heat shielding and insulating substrate of the present invention, the hardness of the undercoat layer is preferably 0.50 GPa or more, more preferably 0.50 GPa to 1.00 GPa, and still more preferably 0.50 GPa to 0.90 GPa. , particularly preferably 0.50 GPa to 0.80 GPa, most preferably 0.50 GPa to 0.70 GPa. If the hardness of the undercoat layer is lower than 0.50 GPa, the heat shielding and insulating substrate of the present invention may be damaged by repeated rubbing with a weak force during wiping during cleaning.

In the heat shielding and insulating substrate of the present invention, the elastic modulus of the undercoat layer is preferably 8.25 GPa or less, more preferably 4.00 GPa to 8.25 GPa, still more preferably 5.00 GPa to 8.25 GPa. , particularly preferably 5.50 GPa to 8.25 GPa, most preferably 6.00 GPa to 8.25 GPa. If the modulus of elasticity of the undercoat layer exceeds 8.25 GPa, the heat shielding and insulating substrate of the present invention may crack when bent during handling or storage.

In the heat shield and heat insulation film of the present invention, the hardness of the protective topcoat layer is preferably 0.50 GPa or more, more preferably 0.50 GPa to 1.40 GPa, and still more preferably 0.50 GPa to 1.30 GPa. , particularly preferably 0.50 GPa to 1.20 GPa, most preferably 0.50 GPa to 1.00 GPa. If the hardness of the protective topcoat layer is lower than 0.50 GPa, the heat shielding and insulating substrate of the present invention may be damaged by repeated rubbing with a weak force during cleaning or the like.

In the thermal insulation substrate of the present invention, the elastic modulus of the protective topcoat layer is preferably 10.0 GPa or less, more preferably 4.00 GPa to 10.0 GPa, still more preferably 5.00 GPa to 10.0 GPa. , particularly preferably 5.50 GPa to 10.0 GPa, most preferably 6.00 GPa to 10.0 GPa. If the elastic modulus of the protective topcoat layer exceeds 10.0 GPa, the heat shielding and insulating substrate of the present invention may crack when bent during handling or storage.

≪2. Transparent substrate layer≫
The transparent substrate layer is preferably a transparent plate member, a transparent film, or a composite of these. Examples of transparent plate members include glass, acrylic plates, and polycarbonate plates. The transparent film is preferably a flexible transparent film. The visible light transmittance of the transparent substrate layer is preferably 10% or more, more preferably 80% or more, still more preferably 85% or more, particularly preferably 88% or more, most preferably 90%. That's it. The visible light transmittance is measured according to JIS-A5759-2008 (film for architectural window glass).

The thickness of the transparent substrate layer is preferably 0.2 mm to 40 mm, more preferably 0.5 mm to 30 mm, still more preferably 1 mm to 24 mm, particularly preferably when the transparent substrate layer is a transparent plate member. is between 1.5 mm and 18 mm, most preferably between 2 mm and 12 mm.

When the transparent substrate layer is a film, the thickness of the transparent substrate layer is preferably 5 μm to 500 μm, more preferably 10 μm to 300 μm, still more preferably 20 μm to 200 μm, and particularly preferably 30 μm to 100 μm. .

When the transparent substrate layer is a film, examples of materials constituting the transparent substrate layer include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK), polycarbonate (PC), and the like. Polyethylene terephthalate (PET) is preferable from the viewpoint of excellent heat resistance.

≪3. Undercoat layer≫
An undercoat layer is provided between the transparent substrate layer and the infrared reflective layer. Preferably, the undercoat layer is laminated directly with the transparent substrate layer. By providing the undercoat layer on the surface of the transparent substrate layer, the mechanical strength of the heat shielding and insulating substrate of the present invention can be enhanced, and the scratch resistance of the heat shielding and insulating substrate of the present invention can be enhanced. .

As described above, the hardness of the undercoat layer is preferably 0.50 GPa or more, more preferably 0.50 GPa to 1.00 GPa, still more preferably 0.50 GPa to 0.90 GPa, and particularly preferably 0.50 GPa to 0.80 GPa, most preferably 0.50 GPa to 0.70 GPa. If the hardness of the undercoat layer is lower than 0.50 GPa, the heat shielding and insulating substrate of the present invention may be damaged by repeated rubbing with a weak force during wiping during cleaning.

As described above, the elastic modulus of the undercoat layer is preferably 8.25 GPa or less, more preferably 4.00 GPa to 8.25 GPa, still more preferably 5.00 GPa to 8.25 GPa, and particularly preferably is between 5.50 GPa and 8.25 GPa, most preferably between 6.00 GPa and 8.25 GPa. If the modulus of elasticity of the undercoat layer exceeds 8.25 GPa, the heat shielding and insulating substrate of the present invention may crack when bent during handling or storage.

The thickness of the undercoat layer is preferably 0.01 μm to 5 μm, more preferably 0.2 μm to 5 μm, still more preferably 0.2 μm to 3 μm, particularly preferably 0.5 μm to 3 μm, Most preferably it is between 1 μm and 2 μm. If the thickness of the undercoat layer is within the above range, the mechanical strength of the heat shielding and insulating substrate of the present invention can be enhanced, and the scratch resistance of the heat shielding and insulating substrate of the present invention can be further enhanced.

The undercoat layer is preferably a cured film of a curable resin, and can be formed, for example, by applying a cured film of any suitable UV-curable resin on the transparent substrate layer.

Corona treatment, plasma treatment, flame treatment, ozone treatment, primer treatment, glow treatment, saponification treatment, and coupling agent are applied to the surface of the undercoat layer (the side opposite to the transparent substrate layer) for the purpose of improving adhesion. A surface modification treatment such as treatment with may be performed.

As the material for the undercoat layer, the hardness of the undercoat layer is preferably 0.50 GPa or more, and more preferably the elastic modulus of the undercoat layer is 8.25 GPa or less. Any appropriate material can be adopted as long as the effects of the invention are not impaired. Examples of such materials include the following.

Any appropriate configuration can be adopted as the undercoat layer. The undercoat layer is preferably a resin layer formed from a resin composition containing an organic resin, and examples of the organic resin include ultraviolet curable resins. Examples of ultraviolet curable resins as organic resins include acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, epoxy resins, and oxetane resins. By using a resin composition containing such an ultraviolet curable resin for forming an undercoat layer, it is possible to obtain an undercoat layer that can effectively exhibit excellent scratch resistance. Acrylic resins are particularly preferable as the ultraviolet curable resin as the organic resin in terms of scratch resistance, handling properties, and the like.

Any appropriate acrylic resin may be employed as the acrylic resin as long as it is a resin having repeating units derived from various monofunctional or polyfunctional (meth)acrylates. Examples of the monofunctional (meth)acrylates include isobornyl acrylate, tetrahydrofurfuryl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, butoxyethyl acrylate, lauryl acrylate, stearyl acrylate, benzyl acrylate, hexyl diglycol acrylate, 2-hydroxyethyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenoxyethyl acrylate, dicyclopentadiene acrylate, polyethylene glycol acrylate, polypropylene glycol acrylate, nonylphenoxyethyl cellosolve acrylate and the like. Examples of polyfunctional (meth)acrylates include polyfunctional (meth)acrylates such as polyethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, and pentaerythritol triacrylate; oligourethane (meth)acrylates and oligoesters; Polyfunctional (meth)acrylate oligomers such as (meth)acrylate; and the like. These monofunctional or polyfunctional various (meth)acrylates may be used alone or in combination of two or more.

The undercoat layer may contain any appropriate additive as needed. Representative examples of such additives include photopolymerization initiators, silane coupling agents, release agents, curing agents, curing accelerators, diluents, antioxidants, modifiers, surfactants, dyes, pigments, Inorganic particles, discoloration inhibitors, ultraviolet absorbers, softeners, stabilizers, plasticizers, antifoaming agents and the like. The type, number and amount of additives contained in the resin composition can be appropriately set according to the purpose.

≪4. Antireflection layer≫
An antireflection layer may be provided between the undercoat layer and the infrared reflective layer. By providing the antireflection layer, the transparency of the heat shielding and heat insulating substrate of the present invention can be improved.

The thickness of the antireflection layer is preferably 30 nm or less, more preferably 1 nm to 30 nm, even more preferably 1 nm to 20 nm, particularly preferably 1 nm to 15 nm.

Any appropriate method can be adopted as a method for forming the antireflection layer. Examples of such a film forming method include a film forming method using a dry process such as a sputtering method, a vacuum deposition method, a CVD method, and an electron beam deposition method. As a film forming method for the antireflection layer, a film forming method using a DC sputtering method is preferable. When a direct-current sputtering method is employed, it is possible to form these multiple layers in one pass by using a roll-up type sputtering apparatus having a plurality of film-forming chambers. Therefore, not only can the productivity of the antireflection layer be greatly improved, but also the productivity of the heat shielding and insulating substrate of the present invention can be greatly improved.

≪5. Infrared reflective layer≫
Any appropriate layer can be adopted as the infrared reflective layer as long as it is a layer capable of improving heat shielding properties by reflecting near-infrared rays and improving heat insulating properties by reflecting far-infrared rays.

One embodiment of the infrared reflective layer comprises a first metal oxide layer, a metal layer, a second metal oxide layer in that order, wherein the first metal oxide layer and the second metal oxide layer are laminated directly to the metal layer. become. In this embodiment, the infrared reflective layer preferably consists of three layers: a first metal oxide layer, a metal layer and a second metal oxide layer. Prepare the layers in this order. One embodiment of such an infrared reflective layer may refer to the embodiments described in, for example, JP-A-2016-93892, JP-A-2016-94012, and the like.

The metal layer has a central role in infrared reflection. From the viewpoint of increasing visible light transmittance and near-infrared reflectance without increasing the number of layers, the metal layer is preferably a silver alloy layer containing silver as a main component or a gold alloy layer containing gold as a main component. For example, since silver has a high free electron density, high reflectance of near-infrared rays and far-infrared rays can be realized. Therefore, even when the number of laminated layers constituting the infrared reflective layer is small, it is possible to achieve both an improvement in heat shielding properties due to reflection of near-infrared rays and an improvement in heat insulating properties due to reflection of far-infrared rays.

When the metal layer is a silver alloy layer containing silver as a main component, the content of silver in the metal layer is preferably 85% by weight to 99.9% by weight, more preferably 90% by weight to 99.8% by weight. % by weight, more preferably 95% to 99.7% by weight, particularly preferably 97% to 99.6% by weight. The higher the silver content in the metal layer, the higher the wavelength selectivity of transmittance and reflectance, and the higher the visible light transmittance. On the other hand, when silver is exposed to an environment containing moisture, oxygen, chlorine, or the like, or when exposed to ultraviolet light or visible light, deterioration such as oxidation or corrosion may occur. For this reason, the metal layer is preferably a silver alloy layer containing a metal other than silver for the purpose of enhancing durability. .9% by weight or less is preferred.

When the metal layer is a silver alloy layer containing silver as a main component, the metal layer preferably contains a metal other than silver for the purpose of enhancing durability, as described above. The content of metals other than silver in the metal layer is preferably 0.1% by weight to 15% by weight, more preferably 0.2% by weight to 10% by weight, and still more preferably 0.3% by weight. to 5% by weight, particularly preferably 0.4% to 3% by weight. Metals other than silver include, for example, palladium (Pd), gold (Au), copper (Cu), bismuth (Bi), germanium (Ge), gallium (Ga), etc., from the viewpoint of imparting high durability. , palladium (Pd) is preferred.

The metal oxide layer (first metal oxide layer and second metal oxide layer) controls the amount of visible light reflected at the interface with the metal layer, achieving both high visible light transmittance and high infrared reflectance. It is provided for the purpose of The metal oxide layer can also function as a protective layer to prevent deterioration of the metal layer. From the viewpoint of enhancing the wavelength selectivity of reflection and transmission in the infrared reflective layer, the refractive index of the metal oxide layer for visible light is preferably 1.5 or more, more preferably 1.6 or more, and still more preferably 1.7 or more.

The metal oxide layers (the first metal oxide layer and the second metal oxide layer) are preferably oxides of metals such as Ti, Zr, Hf, Nb, Zn, Al, Ga, In, Tl, Sn, Alternatively, it contains composite oxides of these metals. The metal oxide layer more preferably contains a composite metal oxide containing zinc oxide. The metal oxide layer is preferably amorphous. When the metal oxide layer is an amorphous layer containing zinc oxide, the durability of the metal oxide layer itself is enhanced, and the action of the metal layer as a protective layer increases, so deterioration of the metal layer is suppressed. can be

The metal oxide layers (the first metal oxide layer and the second metal oxide layer) are particularly preferably composite metal oxides containing zinc oxide. In this case, the content of zinc oxide in the metal oxide layer (in each of the first metal oxide layer and the second metal oxide layer) is preferably 3 parts by weight with respect to the total 100 parts by weight of the metal oxide. parts or more, more preferably 5 parts by weight or more, and still more preferably 7 parts by weight or more. When the content of zinc oxide is within the above range, the metal oxide layer tends to be amorphous, and the durability tends to be enhanced. On the other hand, if the content of zinc oxide is excessively high, the durability may be lowered and the visible light transmittance may be lowered. Therefore, the content of zinc oxide in the metal oxide layer is preferably 60 parts by weight or less, more preferably 50 parts by weight or less, and still more preferably 40 parts by weight with respect to the total 100 parts by weight of the metal oxides. It is below the department.

As the composite metal oxide containing zinc oxide, indium-zinc composite oxide (IZO) and zinc-tin composite oxide (ZTO) are used from the viewpoint of satisfying all of visible light transmittance, refractive index and durability. , indium-tin-zinc composite oxide (ITZO). These composite oxides may further contain metals such as Al and Ga, and oxides of these metals.

The thickness of the metal layer and the metal oxide layer (the first metal oxide layer and the second metal oxide layer) is such that the infrared reflective layer transmits visible light and selectively reflects near infrared light. It can be appropriately set in consideration of the rate and the like. The thickness of the metal layer is preferably 5 nm to 50 nm, more preferably 5 nm to 25 nm, even more preferably 10 nm to 18 nm. The thickness of the metal oxide layer (the thickness of each of the first metal oxide layer and the second metal oxide layer) is preferably 1 nm to 80 nm, more preferably 1 nm to 50 nm, still more preferably 1 nm to 30 nm. and particularly preferably 2 nm to 10 nm. Since the heat shielding and heat insulating substrate of the present invention can preferably have an increased mechanical strength, the thickness of the metal oxide layer (thickness of each of the first metal oxide layer and the second metal oxide layer) is reduced from the level of conventional products. can be made thinner.

Any appropriate method can be adopted as a method for forming the metal layer and the metal oxide layer. Examples of such a film forming method include a film forming method using a dry process such as a sputtering method, a vacuum deposition method, a CVD method, and an electron beam deposition method. As a film forming method for the metal layer and the metal oxide layer, a direct current sputtering method is preferably used. When a direct-current sputtering method is employed, it is possible to form these multiple layers in one pass by using a roll-up type sputtering apparatus having a plurality of film-forming chambers. Therefore, not only can the productivity of the infrared reflective layer be greatly improved, but also the productivity of the heat shielding and insulating substrate of the present invention can be greatly improved. A target for direct-current sputtering may be doped with conductive impurities to impart conductivity, or may be partly reducing. Therefore, the antireflection layer to be formed may be mixed with the impurity, or the composition of the layer may differ from the stoichiometric composition.

As another embodiment of the infrared reflective layer, for example, the embodiment of the base layer described in JP-A-2014-30910 can be used.

≪6. Protective topcoat layer≫
A protective topcoat layer is provided on the side of the infrared reflective layer opposite the transparent substrate layer. Preferably, the protective topcoat layer is laminated directly to the topcoat layer described below.

As described above, the hardness of the protective topcoat layer is preferably 0.50 GPa or more, more preferably 0.50 GPa to 1.40 GPa, still more preferably 0.50 GPa to 1.30 GPa, and particularly preferably. is between 0.50 GPa and 1.20 GPa, most preferably between 0.50 GPa and 1.00 GPa. If the hardness of the protective topcoat layer is lower than 0.50 GPa, the heat shielding and insulating substrate of the present invention may be damaged by repeated rubbing with a weak force during cleaning or the like.

As described above, the elastic modulus of the protective topcoat layer is preferably 10.0 GPa or less, more preferably 4.00 GPa to 10.0 GPa, still more preferably 5.00 GPa to 10.0 GPa, and particularly It is preferably 5.50 GPa to 10.0 GPa, most preferably 6.00 GPa to 10.0 GPa. If the elastic modulus of the protective topcoat layer exceeds 10.0 GPa, the heat shielding and insulating substrate of the present invention may crack when bent during handling or storage.

The contact angle of the protective topcoat layer is preferably 90 degrees or more, more preferably 90 degrees to 160 degrees, still more preferably 90 degrees to 140 degrees, particularly preferably 90 degrees to 120 degrees, Most preferably it is 100 to 120 degrees. If the contact angle of the protective topcoat layer is within the above range, it is possible to provide a heat shielding and heat insulating substrate that is superior in both antifouling property and scratch resistance.

The protective topcoat layer is preferably a layer formed by coating. Formation of the protective topcoat layer by coating is performed, for example, by dissolving a material as described later in a solvent to prepare a solution, coating this solution on the infrared reflective layer, drying the solvent, and then exposing to ultraviolet rays or electron beams. Formation by curing such as by irradiation or application of heat energy can be exemplified. When the heat shielding and insulating substrate of the present invention is provided with such a protective topcoat layer, for example, the adhesion between the topcoat layer and the protective topcoat layer, which will be described later, is enhanced, and the scratch resistance of the heat shielding and insulating substrate of the present invention is improved. It is possible to improve the durability of the infrared reflective layer.

The protective topcoat layer preferably has a high visible light transmission.

The protective topcoat layer preferably has low far-infrared absorption. If the absorption of far-infrared rays in the protective topcoat layer is small, far-infrared rays in the room are reflected into the room by the infrared reflective layer, so that the heat insulating effect can be enhanced. Examples of methods for reducing the amount of far-infrared absorption by the protective topcoat layer include a method of using a material with a low far-infrared absorption rate as a material for the protective topcoat layer, and a method of reducing the thickness of the protective topcoat layer. On the other hand, if the protective topcoat layer absorbs far-infrared rays to a large extent, the far-infrared rays in the room are absorbed by the protective topcoat layer and are not reflected by the infrared-reflecting layer, but are radiated to the outside through heat conduction, resulting in heat insulation. may decrease.

If a material with low far-infrared absorption rate is used as the material for the protective topcoat layer, the amount of far-infrared absorption can be kept small even if the thickness of the protective topcoat layer is large, and the effect of protecting the infrared reflective layer can be enhanced. can be done. As a material for the protective topcoat layer with low absorption of far-infrared rays, a compound having a small content of C=C bonds, C=O bonds, CO bonds, aromatic rings, etc. is preferably used. Examples of such compounds include polyolefins such as polyethylene and polypropylene, alicyclic polymers such as cycloolefin polymers, and rubber polymers.

The thickness of the protective topcoat layer is preferably 500 nm or less, more preferably 300 nm or less, still more preferably 200 nm or less, and still more preferably 150 nm or less, from the viewpoint of reducing far-infrared absorption. , particularly preferably 120 nm or less, and most preferably 100 nm or less. When the optical thickness (product of refractive index and physical thickness) of the protective topcoat layer overlaps with the wavelength range of visible light, multiple reflection interference at the interface causes the surface of the heat shielding and insulating substrate of the present invention to have a rainbow pattern. It may cause "iris phenomenon" that looks like Since the refractive index of general resin is about 1.5, the thickness of the protective topcoat layer is more preferably 200 nm or less from the viewpoint of suppressing the iris phenomenon.

The thickness of the protective topcoat layer is preferably 5 nm or more, more preferably 15 nm or more, from the viewpoint of imparting mechanical strength and chemical strength to it and enhancing the durability of the heat shielding and heat insulating substrate of the present invention. , more preferably 30 nm or more, and particularly preferably 50 nm or more.

If the thickness of the protective topcoat layer is within the above range, the reflected light on the surface side of the protective topcoat layer and the reflected light on the interface on the infrared reflective layer side will reduce the reflectance of visible light due to multiple reflection interference. be able to. Therefore, in addition to the effect of lowering the reflectance due to light absorption by the infrared reflective layer, the antireflection effect of the protective topcoat layer can be obtained, and the visibility of the heat shielding and insulating substrate of the present invention can be further enhanced.

The material for the protective topcoat layer is preferably a curable composition containing a polyfunctional (meth)acrylic monomer. Only one kind of polyfunctional (meth)acrylic monomer may be used, or two or more kinds thereof may be used. The protective topcoat layer is formed, for example, by curing a curable composition containing a polyfunctional (meth)acrylic monomer. Examples of curing methods include photocuring and heat curing, and photocuring is preferred.

The content of the polyfunctional (meth)acrylic monomer in the curable composition containing the polyfunctional (meth)acrylic monomer is such that the effects of the present invention can be further expressed, and the solid content 1 excluding the solvent etc. When it is 100% by weight, it is preferably 10% to 70% by weight, more preferably 20% to 60% by weight, still more preferably 25% to 55% by weight, and particularly preferably is 30% to 50% by weight.

Polyfunctional (meth)acrylic monomers include, for example, monomers having a plurality of (meth)acrylic groups in the molecule and capable of being photo-cured or heat-cured. Examples of such monomers include polyfunctional (meth)acrylates, urethane (meth)acrylates, epoxy (meth)acrylates, polyester (meth)acrylates, etc., and polyfunctional (meth)acrylates are preferred.

Examples of polyfunctional (meth)acrylates include hexanediol di(meth)acrylate, octanediol di(meth)acrylate, decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and ethylene glycol di(meth)acrylate. Acrylate, polyethylene glycol (number of repeating units (hereinafter referred to as "n") = 2 to 15) di (meth) acrylate, polypropylene glycol (n = 2 to 15) di (meth) acrylate, polybutylene glycol (n = 2 15) di(meth)acrylate, 2,2-bis(4-(meth)acryloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, trimethylolpropane di Acrylates, bis(2-(meth)acryloxyethyl)-hydroxyethyl-isocyanurate, trimethylolpropane tri(meth)acrylate, tris(2-(meth)acryloxyethyl)isocyanurate, pentaerythritol tri(meth)acrylate , pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A type diepoxy and (meth) acrylic acid are reacted. Epoxy poly (meth) acrylate such as epoxy di (meth) acrylate, urethane tri (meth) acrylate obtained by reacting a trimer of 1,6-hexamethylene diisocyanate with 2-hydroxyethyl (meth) acrylate, isophorone diisocyanate and 2 - urethane di(meth)acrylate reacted with hydroxypropyl (meth)acrylate, urethane hexa(meth)acrylate reacted with isophorone diisocyanate and pentaerythritol tri(meth)acrylate, dicyclomethane diisocyanate and 2-hydroxyethyl ( Urethane di(meth)acrylate reacted with meth)acrylate, urethanized reaction product of dicyclomethane diisocyanate and poly(n=6-15) tetramethylene glycol reacted with 2-hydroxyethyl (meth)acrylate Urethane poly(meth)acrylate such as urethane di(meth)acrylate, polyester (meth)acrylate obtained by reacting trimethylolethane with succinic acid and (meth)acrylic acid Polyester poly(meth)acrylate such as polyester (meth)acrylate obtained by reacting acrylate, trimethylolpropane with succinic acid, ethylene glycol and (meth)acrylic acid.

As the polyfunctional (meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(2-(meth)acrylic oxyethyl)isocyanurate, polyurethane poly(meth)acrylate having radically polymerizable unsaturated double bonds such as at least 5 (meth)acrylic groups in one molecule, at least 5 (meth)acryl in one molecule Examples include polyester poly(meth)acrylates having radically polymerizable unsaturated double bonds such as groups, more preferably dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate, and still more preferably , dipentaerythritol penta(meth)acrylate.

A curable composition containing a polyfunctional (meth)acrylic monomer may contain inorganic particles or inorganic particles modified with an organic group (organic-inorganic hybrid particles). Examples of such organic-inorganic hybrid particles include hydrolyzate/condensate of (meth)acryloyloxyalkoxysilane, organic-inorganic hybrid obtained by hydrolytic condensation of colloidal silica and (meth)acryloyloxyalkoxysilane ( meth) acrylate and the like. Specific examples of organic-inorganic hybrid particles include vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxy propyltrimethoxysilane, 2-(meth)acryloxyethyltrimethoxysilane, 2-(meth)acryloxyethyltriethoxysilane, (meth)acryloxymethyltrimethoxysilane, (meth)acryloxymethyltriethoxysilane, 3 - (meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, 8-(meth)acryloxyoctyltriethoxysilane alone Examples include organic-inorganic hybrid vinyl compounds and organic-inorganic hybrid (meth)acrylate compounds obtained by (co)hydrolytic condensation of silane or mixed silane with other silanes, optionally in the presence of colloidal silica.

The content of inorganic particles or organic-inorganic hybrid particles in the curable composition containing a polyfunctional (meth)acrylic monomer is such that the effects of the present invention can be more expressed, and the solid content excluding solvents and the like is 1. When 100% by weight, it is preferably 5% to 150% by weight, more preferably 10% to 100% by weight, still more preferably 15% to 60% by weight, particularly preferably 20% by weight. % to 50% by weight. Only one kind of organic-inorganic hybrid particles may be used, or two or more kinds thereof may be used.

A curable composition containing a polyfunctional (meth)acrylic monomer preferably contains a polymerization initiator. Examples of the polymerization initiator include photopolymerization initiators and thermal polymerization initiators, preferably photopolymerization initiators. As the polymerization initiator, any appropriate polymerization initiator can be employed as long as the effects of the present invention are not impaired. Only one polymerization initiator may be used, or two or more polymerization initiators may be used.

The content of the polymerization initiator in the curable composition containing the polyfunctional (meth)acrylic monomer is 100% by weight for the solid content 1 excluding the solvent, etc., in order to further express the effects of the present invention. is preferably 1% to 35% by weight, more preferably 2% to 30% by weight, still more preferably 3% to 25% by weight, and particularly preferably 4% to 25% by weight. % by weight.

A curable composition containing a polyfunctional (meth)acrylic monomer may contain a solvent for the purpose of viscosity adjustment and the like. Examples of solvents include aqueous solvents, organic solvents, mixed solvents thereof, and the like. Examples of solvents include aromatic hydrocarbons such as toluene and xylene; aliphatic esters such as ethyl acetate, butyl acetate and isobutyl acetate; alicyclic hydrocarbons such as cyclohexane; and aliphatic hydrocarbons such as hexane and pentane. hydrogens; aliphatic ketones such as methyl ethyl ketone and methyl isobutyl ketone; alcohols such as isopropanol and 1-butanol; Only one kind of solvent may be used, or two or more kinds thereof may be used.

A curable composition containing a polyfunctional (meth)acrylic monomer may optionally contain other appropriate components within a range that does not impair the effects of the present invention. Other components include, for example, ultraviolet absorbers, antifouling agents, water repellents, leveling agents, coloring agents, pigments, antioxidants, anti-yellowing agents, bluing agents, antifoaming agents, thickeners, and sedimentation agents. Antistatic agents, antistatic agents, surfactants, adhesion promoters, infrared absorbers, light stabilizers, curing catalysts, metal oxide fine particles, and the like. Only one kind of other component may be used, or two or more kinds thereof may be used.

As a material for the protective topcoat layer, for example, an organic resin, an inorganic material, an organic-inorganic hybrid material in which an organic component and an inorganic component are chemically bonded, or the like may be used. Only one kind of organic resin may be used, or two or more kinds thereof may be used. Only one kind of inorganic material may be used, or two or more kinds thereof may be used. Only one kind of organic-inorganic hybrid material may be used, or two or more kinds thereof may be used.

Examples of organic resins include actinic radiation-curable or thermosetting organic resins, and specific examples include fluorine-based resins, acrylic-based resins, urethane-based resins, ester-based resins, epoxy-based resins, and silicone resins. system resins, and the like. The organic resin is preferably an acrylic resin in that the effects of the present invention can be exhibited more effectively.

Examples of inorganic materials include silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, titanium oxide, zirconium oxide, and sialon (SiAlON).

The protective topcoat layer preferably includes a resin layer formed from a resin composition containing an organic resin and a resin layer formed from a composition containing an organic-inorganic hybrid material, more preferably containing an organic resin. A resin layer formed from a resin composition is mentioned.

The protective topcoat layer preferably comprises a coordination type material. As the coordinate bond type material, any appropriate coordinate bond type material can be adopted as long as it is a material capable of forming a coordinate bond with another compound, as long as it does not impair the effects of the present invention. Only one kind of coordination bond type material may be used, or two or more kinds thereof may be used. The inclusion of a coordinative material in the protective topcoat layer provides coordinative bonding forces between the two layers, for example, when an infrared reflective layer is laminated directly to the protective topcoat layer. can be expressed and the adhesion can be improved. In particular, when the infrared reflective layer contains a metal oxide, the acidic groups in the protective topcoat layer can develop a high affinity for coordination bonding with the metal oxide in the infrared reflective layer. Moreover, since the strength of the surface protective layer can be improved by improving the adhesion between the infrared reflective layer and the protective topcoat layer, the durability of the infrared reflective layer can be enhanced.

The coordination bond type material is preferably a compound having a group having a lone electron pair. A group having an atom is included, and specific examples include a phosphate group, a sulfate group, a thiol group, a carboxyl group, an amino group, and the like.

Coordination type materials are preferably able to enhance adhesion through interaction with metal ions. The coordination bond type material may have a reactive group in order to enhance adhesion with other resin materials and the like.

The coordination bond type material is preferably an ester compound having an acidic group and a polymerizable functional group in the same molecule.

Ester compounds having an acidic group and a polymerizable functional group in the same molecule include polyvalent acids such as phosphoric acid, sulfuric acid, oxalic acid, succinic acid, phthalic acid, fumaric acid, and maleic acid, and ethylenically unsaturated Examples include esters of compounds having a polymerizable functional group such as a group, a silanol group, an epoxy group, and a hydroxyl group in the molecule. Such an ester compound may be a polyvalent ester such as a diester or triester, but it is preferable that at least one acidic group of the polyvalent acid is not esterified.

From the viewpoint of increasing the mechanical strength and chemical strength of the protective topcoat layer, the ester compound having an acidic group and a polymerizable functional group in the same molecule may contain a (meth)acryloyl group as the polymerizable functional group. preferable. An ester compound having an acidic group and a polymerizable functional group in the same molecule may have a plurality of polymerizable functional groups in the molecule. The ester compound having an acidic group and a polymerizable functional group in the same molecule is preferably a phosphate monoester compound or a phosphate diester compound represented by general formula (A). In addition, a phosphoric acid monoester and a phosphoric acid diester can also be used together. When a phosphate monoester compound or a phosphate diester compound represented by the general formula (A) is employed as an ester compound having an acidic group and a polymerizable functional group in the same molecule, the phosphate hydroxy group is a metal oxide Because of its excellent affinity with can be better.

In general formula (A), X represents a hydrogen atom or a methyl group, and (Y) represents a -OCO(CH ₂ ) ₅ - group. n is 0 or 1 and p is 1 or 2;

The content of the coordination type material in the protective topcoat layer is preferably 1 wt% to 20 wt%, more preferably 1.5 wt% to 17.5 wt%, and even more preferably 2 wt%. % to 15% by weight, particularly preferably 2.5% to 12.5% by weight. If the content of the coordination bond type material in the protective topcoat layer is too small, there is a risk that the effect of improving strength and adhesion may not be sufficiently obtained. If the content of the coordination bond-type material in the protective topcoat layer is excessively high, the curing speed during formation of the protective topcoat layer may decrease and the hardness may decrease. may decrease and the scratch resistance may decrease.

The protective topcoat layer preferably does not have a softening temperature within the range of 30°C to 75°C. The protective topcoat layer more preferably does not have a softening temperature within the range of 25°C to 75°C, more preferably does not have a softening temperature within the range of 20°C to 80°C, and most preferably It does not have a softening temperature within the range of 15°C to 85°C and most preferably does not have a softening temperature within the range of 10°C to 90°C. If the protective topcoat layer does not have a softening temperature within the above temperature range, the physical properties of the protective topcoat layer are unlikely to change in the actual use environment, and stable scratch resistance and dent resistance can be obtained. effect can be expressed. A method for measuring the softening temperature will be described later.

When an organic resin or an organic-inorganic hybrid material is used as the material of the protective topcoat layer, it is preferable to introduce a crosslinked structure. The formation of the crosslinked structure enhances the mechanical strength and chemical strength of the protective topcoat layer and increases the protective function for the infrared reflective layer. Among such crosslinked structures, it is preferable to introduce a crosslinked structure derived from an ester compound having an acidic group and a polymerizable functional group in the same molecule.

Materials for the protective topcoat layer include coupling agents such as silane coupling agents and titanium coupling agents, leveling agents, UV absorbers, antioxidants, heat stabilizers, lubricants, plasticizers, anti-coloring agents, and flame retardants. and additives such as antistatic agents. Any appropriate content can be adopted as the content of these additives as long as the effects of the present invention are not impaired.

≪7. Top coat layer≫
In the heat shielding and heat insulating substrate of the present invention, a top coat layer may be provided on the side of the infrared reflecting layer opposite to the transparent substrate layer.

The topcoat layer is preferably an oxide or nitride, an oxynitride, or a non-oxynitride containing at least one member of Group 13 or Group 14 of the periodic table as a main component. Contains one or more Group 4 components. The topcoat layer is more preferably an oxide or nitride, an oxynitride, a non-nitride or a non-oxide containing at least one member of Group 14 as a main component; containing one or more components of The topcoat layer is more preferably at least one selected from oxides or oxynitrides containing Si and Zr, oxides or oxynitrides containing Si and Y, and oxides or oxynitrides containing Si and Ti. including. The topcoat layer particularly preferably contains at least one selected from oxides containing Si and Zr, oxides containing Si and Y, and oxides containing Si and Ti.

Group 14 elements have four outermost shell electrons, so they are unlikely to become ions. Group 13 elements have three outermost shell electrons, so they are unlikely to become anions. Therefore, it is considered that the hardness of nitrides, oxynitrides, non-nitrides or non-oxides increases.

Addition of elements of Groups 3 and 4 of the periodic table increases the strength and improves corrosion resistance and heat resistance by densifying the crystals of the main component elements and making the molecular structure the most dense.

The addition amount of the element of Group 3 or 4 of the periodic table is preferably 0.01 atm% to 49.9 atm%, more preferably 0.05 atm% to 49.9 atm%, in that the effect of the present invention can be more expressed. It is 40.0 atm %, more preferably 0.1 atm % to 40.0 atm %, and particularly preferably 0.5 atm % to 35.0 atm %. If the addition amount of the Group 3 or 4 element of the periodic table is small, the effect of the present invention may not be exhibited because the element is not uniformly inserted in the entire matrix. On the other hand, when the addition amount of the element of Group 3 or 4 of the periodic table is too large, the compatibility with the main component is deteriorated, and the effect of the present invention may not be exhibited. Compatibility can be confirmed by a phase diagram.

The thickness of the topcoat layer is preferably 0.5 nm to 30 nm, more preferably 1 nm to 25 nm, even more preferably 2 nm to 20 nm, particularly preferably 3 nm to 15 nm. If the thickness of the topcoat layer is within the above range, the heat shielding and heat insulating substrate of the present invention can exhibit more excellent scratch resistance.

Any appropriate method can be adopted as a method for forming the topcoat layer. Examples of such a film forming method include a film forming method using a dry process such as a sputtering method, a vacuum deposition method, a CVD method, and an electron beam deposition method. As a film forming method for the top coat layer, a direct current sputtering method is preferably used. When a direct-current sputtering method is employed, it is possible to form these multiple layers in one pass by using a roll-up type sputtering apparatus having a plurality of film-forming chambers. Therefore, not only can the productivity of the topcoat layer be greatly improved, but also the productivity of the heat shielding and heat insulating substrate of the present invention can be greatly improved.

≪8. Protective film≫
A protective film may be provided on the side of the protective topcoat layer opposite the infrared reflective layer.

The thickness of the protective film is preferably 10 μm to 150 μm, more preferably 25 μm to 100 μm, still more preferably 30 μm to 75 μm, particularly preferably 35 μm to 65 μm, most preferably 35 μm to 50 μm.

≪9. Other components≫
An adhesive layer may be provided on the side of the transparent substrate layer opposite to the infrared reflective layer. The adhesive layer can be used, for example, for bonding with window glass or the like.

The adhesive layer preferably has a high visible light transmittance and a small difference in refractive index from the transparent substrate layer. Any appropriate material can be used as the material for the adhesive layer as long as the effects of the present invention are not impaired. Examples of such materials include acrylic adhesives (acrylic pressure-sensitive adhesives). Acrylic adhesives (acrylic pressure-sensitive adhesives) have excellent optical transparency, moderate wettability, cohesiveness, and adhesiveness, as well as excellent weather resistance and heat resistance. It is suitable as

The adhesive layer preferably has a high visible light transmittance and a low ultraviolet transmittance. By reducing the ultraviolet transmittance of the adhesive layer, deterioration of the infrared reflective layer caused by ultraviolet rays such as sunlight can be suppressed. From the viewpoint of reducing the ultraviolet transmittance of the adhesive layer, the adhesive layer preferably contains an ultraviolet absorber. Deterioration of the infrared reflective layer caused by ultraviolet rays from the outdoors can also be suppressed by using a transparent substrate layer or the like containing an ultraviolet absorber.

The exposed surface of the adhesive layer is preferably covered by temporarily attaching a separator for the purpose of preventing contamination of the exposed surface until the heat shielding and insulating substrate of the present invention is put into practical use. Such a separator can prevent the exposed surface of the adhesive layer from being contaminated by contact with the outside under normal handling conditions.

<<10. Applications of thermal insulation substrates≫
The heat-shielding and insulating substrate of the present invention can be used for windows of buildings and vehicles, transparent cases for storing plants, freezer or refrigerated showcases, etc., and has the effect of improving the cooling and heating effect and preventing sudden temperature changes. can.

FIG. 3 is a cross-sectional view schematically showing an example of usage of the heat shielding and heat insulating substrate of the present invention. In this mode of use, the heat shielding and heat insulating substrate 100 of the present invention is arranged with the transparent substrate layer 10 side thereof adhered to the interior side of the window 1000 of a building or automobile via any appropriate adhesive layer 80 . As schematically shown in FIG. 3, the heat-shielding and insulating substrate 100 of the present invention transmits visible light (VIS) from the outdoors and introduces it into the room, and near-infrared rays (NIR) from the outdoors pass through the infrared reflective layer. Reflect at 20. The reflection of near-infrared rays suppresses the inflow of heat from the outside due to sunlight or the like into the room (exhibits a heat shielding effect), so that, for example, it is possible to increase the cooling efficiency in summer. Furthermore, since the infrared reflective layer 20 reflects indoor far infrared rays (FIR) radiated from the heater 90, a heat insulation effect is exhibited, and heating efficiency in winter can be improved. In addition, since the heat shielding and heat insulating substrate 100 of the present invention is provided with the infrared reflective layer 20, the reflectance of visible light is reduced. It is possible to provide heat shielding and heat insulating properties without

The heat shielding and heat insulating substrate of the present invention can also be used by being fitted into a frame or the like, as disclosed in JP-A-2013-61370, for example. In such a form, since there is no need to provide an adhesive layer, far-infrared rays are not absorbed by the adhesive layer. Therefore, by using a material (for example, cyclic polyolefin) having a low content of functional groups such as C=C bonds, C=O bonds, CO bonds, aromatic rings, etc., as the transparent substrate layer, transparency can be improved. Far-infrared rays from the substrate layer side can be reflected by the infrared reflecting layer, and heat insulating properties can be imparted to both sides of the heat-shielding and heat-insulating substrate of the present invention. Such a configuration is particularly useful, for example, in refrigerated showcases, freezer showcases, and the like.

In the heat-shielding and insulating substrate of the present invention, when the transparent substrate layer is, for example, a transparent plate-like member (for example, glass, acrylic plate, polycarbonate plate, etc.), or a composite of the transparent plate-like member and a transparent film, For example, it can be applied as it is to windows of buildings and automobiles.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. The tests and evaluation methods used in Examples and the like are as follows. "Parts" means "parts by weight" unless otherwise specified, and "%" means "% by weight" unless otherwise specified.

<Film thickness of each layer>
The film thickness of the metal oxide layer and the metal layer is obtained by processing a sample by a focused ion beam (FIB) method using a focused ion beam processing observation device (manufactured by Hitachi, Ltd., product name “FB-2100”), and measuring the cross section of the sample. was obtained by observation with a field emission transmission electron microscope (manufactured by Hitachi, Ltd., product name "HF-2000").
The film thickness of the protective topcoat layer and undercoat layer is measured using an instantaneous multi-photometry system (manufactured by Otsuka Electronics, product name "MCPD3000"), and the interference pattern of visible light reflectance when light is incident from the measurement target side. was obtained by calculation.

<Emissivity>
A heat shielding and insulating substrate for measurement is left at room temperature for 24 hours, and a 25 μm thick adhesive layer (manufactured by Nitto Denko, product name “HJ-9150W”) is applied to the surface of the heat shielding and insulating substrate on the transparent substrate layer side. A float plate glass with a thickness of 3 mm (manufactured by Matsunami Glass) is used as a sample, and an emissometer (Model AE1, manufactured by Devices and Services) is used to measure the side opposite to the transparent substrate layer of the infrared reflective layer. It was measured. The measured values of temperature and humidity during the actual test were a temperature of 23° C. and a humidity of 50% RH.
O: Emissivity is 0.20 or less.
Δ: The emissivity is 0.20 or more and less than 0.40.
x: The emissivity is 0.40 or more.

<Cotton scratch resistance test>
A heat shielding and insulating substrate for measurement is left at room temperature for 24 hours, and a 25 μm thick adhesive layer (manufactured by Nitto Denko, product name “HJ-9150W”) is applied to the surface of the heat shielding and insulating substrate on the transparent substrate layer side. A sample was used which was attached to an aluminum plate with an intervening hole. Using a Gakushin abrasion tester, while applying a load of 500 g with a cotton cloth for testing (Kanaha No. 3), the outermost surface of the thermal insulation substrate on the aluminum plate on the side opposite to the transparent substrate layer of the infrared reflective layer. , rubbed 1000 times. After the test, the sample was visually evaluated for damage and peeling, and evaluated according to the following evaluation criteria. The measured values of temperature and humidity during the actual test were a temperature of 23° C. and a humidity of 50% RH.
⊚: After 2,000 reciprocating rubbings, no scratch is observed on the surface.
◯: After 1,000 reciprocating rubbings, no scratches were observed on the surface.
Δ: Slight scratches on the surface after 1000 reciprocating rubbings.
x: After 1000 reciprocating rubbings, a large number of scratches are observed on the surface.

<Mandrel test (2 mmφ, 3 mmφ)>
When the transparent substrate layer is a film, the heat shielding and insulating substrate for measurement is left at room temperature for 24 hours, and a mandrel is used for the heat shielding and insulating substrate so that the protective topcoat layer of the heat shielding and insulating substrate is on the outside. A test (JIS K 5600-5-1) was conducted. A case where cracks did not occur with a diameter of 2 mm or more was evaluated as ◯, a case where cracks did not occur with a diameter of 3 mm or more was evaluated as Δ, and a case where cracks did not occur with a diameter of 4 mm or more was evaluated as ×. The measured values of temperature and humidity during the actual test were a temperature of 23° C. and a humidity of 50% RH.
○: No cracks with a diameter of 2 mm or more △: No cracks with a diameter of 3 mm or more ×: No cracks with a diameter of 4 mm or more

<Measurement of contact angle of protective topcoat layer>
Using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., product name "CA-X type"), 2 μL of distilled water is dropped on the surface of the protective topcoat layer in a 23 ° C. / 50% RH environment, and then dropped. The contact angle of the droplet was measured after 10 seconds. The average of measured values obtained by measuring three times was adopted.

<Measurement of hardness and elastic modulus of undercoat layer>
The hardness and elastic modulus of the constituent members of the heat insulating substrate can be measured as follows. The hardness and elastic modulus referred to here are obtained by a nanoindentation test using a nanoindenter "Triboindenter" manufactured by HYSITRON. The nanoindentation test includes a process of gradually applying a load P to a Berkovich indenter (triangular pyramidal diamond indenter) until it reaches a predetermined maximum load Pmax, a process of holding the maximum load Pmax for a certain period of time, a holding In this test, the properties of the test material are measured from the relationship between the load P of the indenter and the indentation depth h obtained in the process of gradually removing the load until the load P becomes zero. The indentation depth h means the distance between the tip of the indenter and the surface of the material to be tested in the initial state (the surface of the material to be tested before the indenter is pushed in), and is based on the position where the indenter first contacts the surface of the material to be tested. corresponds to the amount of displacement of the indenter. The hardness and elastic modulus of the undercoat layer were calculated by the following equations (1) and (2) based on the relationship between the load P of the indenter and the indentation depth h obtained by the nanoindentation test. Specifically, after the undercoat layer was embedded in the resin, it was measured at an indentation depth of 100 nm from a section prepared using a microtome. Here, in the following formulas (1) and (2), H is hardness, Er is elastic modulus, and β is a constant determined by the shape of the indenter. S represents the contact rigidity, π the circular constant, and A the projected contact area between the indenter and the surface of the material to be tested.
H=P/A (1)
Er=1/β·S/2·(π/A) 1/2 (2)

<Measurement of hardness and elastic modulus of protective topcoat layer>
The hardness and elastic modulus of the constituent members of the heat insulating substrate can be measured as follows. The hardness and elastic modulus referred to here are obtained by a nanoindentation test using a nanoindenter "Triboindenter" manufactured by HYSITRON. The nanoindentation test includes a process of gradually applying a load P to a Berkovich indenter (triangular pyramidal diamond indenter) until it reaches a predetermined maximum load Pmax, a process of holding the maximum load Pmax for a certain period of time, a holding In this test, the properties of the test material are measured from the relationship between the load P of the indenter and the indentation depth h obtained in the process of gradually removing the load until the load P becomes zero. The indentation depth h means the distance between the tip of the indenter and the surface of the material to be tested in the initial state (the surface of the material to be tested before the indenter is pushed in), and is based on the position where the indenter first contacts the surface of the material to be tested. corresponds to the amount of displacement of the indenter. The hardness and elastic modulus of the protective topcoat layer were calculated by the following equations (1) and (2) based on the relationship between the load P of the indenter and the indentation depth h obtained by the nanoindentation test. Specifically, it was measured at a depth of 20 nm from the surface on the side of the protective topcoat layer. Here, in the following formulas (1) and (2), H is hardness, Er is elastic modulus, and β is a constant determined by the shape of the indenter. S represents the contact rigidity, π the circular constant, and A the projected contact area between the indenter and the surface of the material to be tested.
H=P/A (1)
Er=1/β·S/2·(π/A) 1/2 (2)

<Measurement of softening temperature>
The softening temperature was measured by scanning 10 μm while changing the temperature of the cantilever from 10° C. to 300° C. in contact mode using AFM5300E/NanoNavi2/Nano-TA2 manufactured by Hitachi High-Tech Science. The softening temperature is the inflection point of the curve obtained in this measurement, and the inflection point was obtained as the intersection of the tangent lines of the curve before and after the inflection point.

[Example 1]
(Formation of undercoat layer on transparent substrate layer)
On one side of a 50 μm-thick polyethylene terephthalate film substrate (manufactured by Toray, trade name “Lumirror U48”, visible light transmittance of 93%), an acrylic UV-curable hard coat layer (Z7543, manufactured by JSR) is applied to a thickness of 2 μm. formed with Specifically, the solution for the hard coat layer is applied by a gravure coater, dried at 80° C., irradiated with ultraviolet rays with an accumulated light amount of 300 mJ/cm ² from an ultra-high pressure mercury lamp, cured, and underlaid onto the transparent substrate layer. A coat layer was formed.
(Formation of first metal oxide layer, metal layer and second metal oxide layer)
A zinc-tin composite oxide (ZTO) layer with a thickness of 10 nm and an Ag layer with a thickness of 16 nm are formed on the undercoat layer formed on the transparent substrate layer by DC magnetron sputtering using a winding-type sputtering apparatus. - A Pd alloy layer, a zinc-tin composite oxide (ZTO) layer with a thickness of 10 nm are formed in order, and a first metal oxide layer, a metal layer, and a second metal oxide layer are formed in this order on the undercoat layer. formed.
For forming the ZTO layer, a target obtained by sintering zinc oxide, tin oxide, and metal zinc powder at a weight ratio of 8.5:83:8.5 was used, and the power density was 2.67 W/cm ² . Process pressure: Sputtering was performed under the condition of 0.4 Pa. At this time, the amount of gas introduced into the sputtering deposition chamber was adjusted so that Ar:O ₂ would be 98:2 (volume ratio).
A metal target containing silver:palladium at a weight ratio of 96.4:3.6 was used to form the Ag—Pd alloy layer.
(Formation of protective topcoat layer)
On the second metal oxide layer, a protective topcoat layer of 60 nm thickness made of an acrylic UV-curable resin having a coordination bond type material was formed. Specifically, 150 parts by weight of silica particles (manufactured by Nissan Chemical Industries, trade name "PGM-AC-2140Y") are added to 100 parts by weight of the solid content of an acrylic hard coat resin solution (manufactured by Aica Kogyo, trade name "Z773"). 5 parts by weight of a phosphate ester compound (manufactured by Nippon Kayaku, trade name "KAYAMER PM-21"), and 10 parts by weight of a fluorine-based additive (manufactured by Daikin Industries, trade name "Optool DAC-HP"). The added solution was applied using a spin coater, dried at 100° C. for 1 minute, and then cured by irradiating ultraviolet light with an accumulated light intensity of 400 mJ/cm ² from an ultra-high pressure mercury lamp in a nitrogen atmosphere. The refractive index of the protective topcoat layer after curing was 1.5. The phosphate ester compound is a phosphate monoester compound having one acryloyl group in the molecule (in the above general formula (1), X is a methyl group, n = 0, and p = 1). and a phosphate diester compound having two acryloyl groups in the molecule (compound in which X is a methyl group, n=0 and p=2 in the above general formula (A)).
FIG. 4 shows the measurement results of the softening temperature of the resulting protective topcoat layer. The softening temperature was 95°C.
(Thermal insulation substrate)
As described above, transparent substrate layer (thickness 3 mm) / undercoat layer (thickness 2 μm) / first metal oxide layer (thickness 10 nm) / metal layer (thickness 16 nm) / second metal oxide layer (thickness 10 / A heat shielding and heat insulating substrate (1) having a structure of a protective topcoat layer (thickness: 60 nm) was obtained.
Table 1 shows the results.

[Example 2]
A heat insulating substrate (2) was obtained in the same manner as in Example 1, except that the amount of silica particles (A) used for forming the protective topcoat layer was changed to 50 parts.
Table 1 shows the results.

[Example 3]
A heat shielding and heat insulating substrate (3) was obtained in the same manner as in Example 1, except that the amount of silica particles (A) used for forming the protective topcoat layer was changed to 10 parts.
Table 1 shows the results.

[Example 4]
A heat shielding and heat insulating substrate (4) was obtained in the same manner as in Example 1, except that the silica particles (A) were not used to form the protective topcoat layer.
Table 1 shows the results.

[Example 5]
A heat insulating substrate (5) was obtained in the same manner as in Example 1, except that 50 parts of silica particles (B) were used instead of 150 parts of silica particles (A) used for forming the protective topcoat layer.
The silica particles (B) are manufactured by Nissan Chemical Industries under the trade name of "PMA-ST".
Table 1 shows the results.

[Example 6]
A heat shielding and heat insulating substrate (6) was obtained in the same manner as in Example 1, except that a protective topcoat layer was formed as follows.
Table 1 shows the results.
(Formation of protective topcoat layer)
On the second metal oxide layer, a 60 nm thick protective topcoat layer made of an acrylic UV curable resin having a coordination bond type material was formed. Specifically, 5 parts of a phosphate ester compound (manufactured by Nippon Kayaku, trade name "KAYAMER PM-21") is added to 100 parts by weight of solid content in an acrylic hard coat resin solution (manufactured by JSR, trade name "Z7543"). A solution in which 10 parts by weight of a fluorine-based additive (manufactured by Daikin Industries, trade name "Optool DAC-HP") is added is applied using a spin coater, dried at 100 ° C. for 1 minute, and then in a nitrogen atmosphere. Curing was carried out by irradiating ultraviolet light with an accumulated light quantity of 400 mJ/cm ² from an ultra-high pressure mercury lamp. The refractive index of the protective topcoat layer after curing was 1.5. The phosphate ester compound is a phosphate monoester compound having one acryloyl group in the molecule (in the above general formula (A), X is a methyl group, n = 0, and p = 1). and a phosphate diester compound having two acryloyl groups in the molecule (compound in which X is a methyl group, n=0 and p=2 in the above general formula (A)).

[Example 7]
In the formation of the undercoat layer, except that the acrylic UV-curable hard coat layer (JSR, Z7543) was changed to an acrylic UV-curable hard coat layer (DIC, ERS219 (70 parts) + V6841 (30 parts)). was carried out in the same manner as in Example 5 to obtain a heat insulating substrate (7).
Table 1 shows the results.

[Example 8]
In the formation of the undercoat layer, an acrylic UV-curable hard coat layer (DIC, ERS219 (70 parts) + V6841 (30 parts)) was replaced with an acrylic UV-curable hard coat layer (DIC, ERS219 (50 parts) + V6841 ( 50 parts)) was carried out in the same manner as in Example 7 to obtain a heat shielding and heat insulating substrate (8).
Table 1 shows the results.

[Example 9]
In the formation of the undercoat layer, an acrylic UV-curable hard coat layer (DIC, ERS219 (70 parts) + V6841 (30 parts)) was replaced with an acrylic UV-curable hard coat layer (DIC, ERS219 (60 parts) + V6841 ( A heat insulating substrate (9) was obtained in the same manner as in Example 7, except that the content was changed to 40 parts)).
Table 1 shows the results.

[Example 10]
In the formation of the undercoat layer, an acrylic UV-curable hard coat layer (DIC, ERS219 (70 parts) + V6841 (30 parts)) was replaced with an acrylic UV-curable hard coat layer (JSR, Z7537 (90 parts) + DIC , EPS1113 (10 parts)), the same procedure as in Example 5 was carried out to obtain a heat shielding and heat insulating substrate (10).
Table 1 shows the results.

[Example 11]
In forming the undercoat layer, an acrylic UV-curable hard coat layer (JSR, Z7537 (90 parts) + DIC, EPS1113 (10 parts)) is combined with an acrylic UV-curable hard coat layer (JSR, Z7537 (80 parts) )+EPS1113 (manufactured by DIC, 20 parts)) was carried out in the same manner as in Example 10 to obtain a heat insulating substrate (11).
Table 1 shows the results.

[Example 12]
In the formation of the undercoat layer, the acrylic UV-curable hard coat layer (JSR, Z7537 (90 parts) + DIC, EPS1113 (10 parts)) was changed to an acrylic UV-curable hard coat layer (JSR, Z7537). A heat shielding and heat insulating substrate (12) was obtained in the same manner as in Example 10 except for the above.
Table 1 shows the results.

[Example 13]
A heat shielding and heat insulating substrate (13) was obtained in the same manner as in Example 1, except that a protective topcoat layer was formed as follows.
Table 1 shows the results.
(Formation of protective topcoat layer)
On the second metal oxide layer, a 60 nm thick protective topcoat layer made of an acrylic UV curable resin having a coordination bond type material was formed. Specifically, 5 parts of a phosphate ester compound (manufactured by Nippon Kayaku, trade name "KAYAMER PM-21") is added to 100 parts by weight of the solid content of an acrylic hard coat resin solution (manufactured by JSR, trade name "Z7537"). A solution in which 10 parts by weight of a fluorine-based additive (manufactured by Daikin Industries, trade name "Optool DAC-HP") is added is applied using a spin coater, dried at 100 ° C. for 1 minute, and then in a nitrogen atmosphere. Curing was carried out by irradiating ultraviolet light with an accumulated light quantity of 400 mJ/cm ² from an ultra-high pressure mercury lamp. The refractive index of the protective topcoat layer after curing was 1.5. The phosphate ester compound is a phosphate monoester compound having one acryloyl group in the molecule (in the above general formula (A), X is a methyl group, n = 0, and p = 1). and a phosphate diester compound having two acryloyl groups in the molecule (compound in which X is a methyl group, n=0 and p=2 in the above general formula (A)).

[Example 14]
In the formation of the undercoat layer, except that the acrylic UV-curable hard coat layer (JSR, Z7543) was changed to an acrylic UV-curable hard coat layer (DIC, ERS219 (70 parts) + V6841 (30 parts)). was carried out in the same manner as in Example 13 to obtain a heat shielding and heat insulating substrate (14).
Table 1 shows the results.

[Example 15]
In the formation of the undercoat layer, an acrylic UV-curable hard coat layer (DIC, ERS219 (70 parts) + V6841 (30 parts)) was replaced with an acrylic UV-curable hard coat layer (DIC, ERS219 (50 parts) + V6841 ( 50 parts)) was carried out in the same manner as in Example 14 to obtain a heat insulating substrate (15).
Table 1 shows the results.

[Example 16]
In the formation of the undercoat layer, an acrylic UV-curable hard coat layer (DIC, ERS219 (70 parts) + V6841 (30 parts)) was replaced with an acrylic UV-curable hard coat layer (DIC, ERS219 (60 parts) + V6841 ( A heat insulating substrate (16) was obtained in the same manner as in Example 14, except that the content was changed to 40 parts)).
Table 1 shows the results.

[Example 17]
A heat shielding and heat insulating substrate (17) was obtained in the same manner as in Example 7, except that the amount of silica particles (B) used for forming the protective topcoat layer was changed to 100 parts.
Table 1 shows the results.

[Example 18]
As a transparent substrate layer, instead of a polyethylene terephthalate film substrate with a thickness of 50 μm (manufactured by Toray, trade name “Lumirror U48”, visible light transmittance of 93%), a float plate glass with a thickness of 3 mm (manufactured by Matsunami Glass, visible light transmittance of 91%) was used. %) was used in the same manner as in Example 1 to obtain a heat shielding and heat insulating substrate (18).
Table 1 shows the results.

[Example 19]
As a transparent substrate layer, instead of a polyethylene terephthalate film substrate with a thickness of 50 μm (manufactured by Toray, trade name “Lumirror U48”, visible light transmittance of 93%), a float plate glass with a thickness of 3 mm (manufactured by Matsunami Glass, visible light transmittance of 91%) was used. %) was used, and a heat insulating substrate (19) was obtained in the same manner as in Example 2.
Table 1 shows the results.

[Example 20]
As a transparent substrate layer, instead of a polyethylene terephthalate film substrate with a thickness of 50 μm (manufactured by Toray, trade name “Lumirror U48”, visible light transmittance of 93%), a float plate glass with a thickness of 3 mm (manufactured by Matsunami Glass, visible light transmittance of 91%) was used. %) was used, and a heat insulating substrate (20) was obtained in the same manner as in Example 3.
Table 1 shows the results.

[Example 21]
As a transparent substrate layer, instead of a polyethylene terephthalate film substrate with a thickness of 50 μm (manufactured by Toray, trade name “Lumirror U48”, visible light transmittance of 93%), a float plate glass with a thickness of 3 mm (manufactured by Matsunami Glass, visible light transmittance of 91%) was used. %) was used, and a heat shielding and insulating substrate (21) was obtained in the same manner as in Example 4.
Table 1 shows the results.

[Example 22]
As a transparent substrate layer, instead of a polyethylene terephthalate film substrate with a thickness of 50 μm (manufactured by Toray, trade name “Lumirror U48”, visible light transmittance of 93%), a float plate glass with a thickness of 3 mm (manufactured by Matsunami Glass, visible light transmittance of 91%) was used. %) was used, and a heat insulating substrate (22) was obtained in the same manner as in Example 5.
Table 1 shows the results.

[Example 23]
As a transparent substrate layer, instead of a polyethylene terephthalate film substrate with a thickness of 50 μm (manufactured by Toray, trade name “Lumirror U48”, visible light transmittance of 93%), a float plate glass with a thickness of 3 mm (manufactured by Matsunami Glass, visible light transmittance of 91%) was used. %) was used, and a heat insulating substrate (23) was obtained in the same manner as in Example 6.
Table 1 shows the results.

[Example 24]
As a transparent substrate layer, instead of a polyethylene terephthalate film substrate with a thickness of 50 μm (manufactured by Toray, trade name “Lumirror U48”, visible light transmittance of 93%), a float plate glass with a thickness of 3 mm (manufactured by Matsunami Glass, visible light transmittance of 91%) was used. %) was used, and a heat insulating substrate (24) was obtained in the same manner as in Example 7.
Table 1 shows the results.

[Example 25]
As a transparent substrate layer, instead of a polyethylene terephthalate film substrate with a thickness of 50 μm (manufactured by Toray, trade name “Lumirror U48”, visible light transmittance of 93%), a float plate glass with a thickness of 3 mm (manufactured by Matsunami Glass, visible light transmittance of 91%) was used. %) was used in the same manner as in Example 8 to obtain a heat shielding and heat insulating substrate (25).
Table 1 shows the results.

[Example 26]
As a transparent substrate layer, instead of a polyethylene terephthalate film substrate with a thickness of 50 μm (manufactured by Toray, trade name “Lumirror U48”, visible light transmittance of 93%), a float plate glass with a thickness of 3 mm (manufactured by Matsunami Glass, visible light transmittance of 91%) was used. %) was used, and a heat insulating substrate (26) was obtained in the same manner as in Example 9.
Table 1 shows the results.

[Example 27]
In the formation of the protective topcoat layer, the same procedure as in Example 5 was carried out, except that the amount of the fluorine-based additive (manufactured by Daikin Industries, trade name "OPTOOL DAC-HP") was changed to 2 parts by weight. 27) was obtained.
Table 1 shows the results.

[Example 28]
Dipentaerythritol pentaacrylate-modified succinic acid (Kyoeisha Chemical A heat-shielding and heat-insulating substrate (28) was obtained in the same manner as in Example 5, except that the product name "Light Acrylate DPE-6A-MS" was used.
Table 1 shows the results.

[Example 29]
A heat shielding and heat insulating substrate (29) was obtained in the same manner as in Example 5, except that curing was performed by irradiating ultraviolet light with an accumulated light amount of 100 mJ/cm ² from an ultrahigh pressure mercury lamp.
Table 1 shows the results.

[Comparative Example 1]
In the formation of the undercoat layer, an acrylic UV-curable hard coat layer (DIC, ERS219 (70 parts) + V6841 (30 parts)) was replaced with an acrylic UV-curable hard coat layer (DIC, ERS219 (40 parts) + V6841 ( 60 parts)) was carried out in the same manner as in Example 7 to obtain a heat shielding and insulating substrate (C1).
Table 2 shows the results.

[Comparative Example 2]
In forming the undercoat layer, an acrylic UV-curable hard coat layer (manufactured by DIC, ERS219 (70 parts) + V6841 (30 parts)) is replaced by an acrylic UV-curable hard coat layer (manufactured by DIC, V6850 (50 parts) + V6841 ( 50 parts)) was carried out in the same manner as in Example 7 to obtain a heat shielding and heat insulating substrate (C2).
Table 2 shows the results.

[Comparative Example 3]
A heat shielding and heat insulating substrate (C3) was obtained in the same manner as in Example 1, except that a protective topcoat layer was formed as follows.
Table 2 shows the results.
(Formation of protective topcoat layer)
On the second metal oxide layer, a 60 nm thick protective topcoat layer made of an acrylic UV curable resin having a coordination bond type material was formed. Specifically, 5 parts of a phosphate ester compound (manufactured by Nippon Kayaku, trade name "KAYAMER PM-21") is added to 100 parts by weight of the solid content of an acrylic hard coat resin solution (manufactured by DIC, trade name "V6850"). A solution in which 10 parts by weight of a fluorine-based additive (manufactured by Daikin Industries, trade name "Optool DAC-HP") is added is applied using a spin coater, dried at 100 ° C. for 1 minute, and then in a nitrogen atmosphere. Curing was carried out by irradiating ultraviolet light with an accumulated light quantity of 400 mJ/cm ² from an ultra-high pressure mercury lamp. The refractive index of the protective topcoat layer after curing was 1.5. The phosphate ester compound is a phosphate monoester compound having one acryloyl group in the molecule (in the above general formula (A), X is a methyl group, n = 0, and p = 1). and a phosphate diester compound having two acryloyl groups in the molecule (compound in which X is a methyl group, n=0 and p=2 in the above general formula (A)).

[Comparative Example 4]
A heat shielding and heat insulating substrate (C4) was obtained in the same manner as in Comparative Example 3, except that the amount of fluorine-based additive (manufactured by Daikin Industries, trade name "Optool DAC-HP") was changed to 2 parts by weight.
Table 2 shows the results.

[Comparative Example 5]
A heat shielding and heat insulating substrate (C5) was obtained in the same manner as in Comparative Example 3, except that the formation of the protective topcoat layer was carried out without using the coordination bond type material.
Table 2 shows the results.

[Comparative Example 6]
A heat shielding and heat insulating substrate (C6) was obtained in the same manner as in Comparative Example 3, except that ultraviolet rays were irradiated with an accumulated light amount of 100 mJ/cm ² from an ultrahigh pressure mercury lamp for curing.
Table 2 shows the results.

[Comparative Example 7]
As a transparent substrate layer, instead of a polyethylene terephthalate film substrate with a thickness of 50 μm (manufactured by Toray, trade name “Lumirror U48”, visible light transmittance of 93%), a float plate glass with a thickness of 3 mm (manufactured by Matsunami Glass, visible light transmittance of 91%) was used. %) was used in the same manner as in Comparative Example 1 to obtain a heat insulating substrate (C7).
Table 2 shows the results.

[Comparative Example 8]
As a transparent substrate layer, instead of a polyethylene terephthalate film substrate with a thickness of 50 μm (manufactured by Toray, trade name “Lumirror U48”, visible light transmittance of 93%), a float plate glass with a thickness of 3 mm (manufactured by Matsunami Glass, visible light transmittance of 91%) was used. %) was used, and a heat shielding and heat insulating substrate (C8) was obtained in the same manner as in Comparative Example 2.
Table 2 shows the results.

[Comparative Example 9]
As a transparent substrate layer, instead of a polyethylene terephthalate film substrate with a thickness of 50 μm (manufactured by Toray, trade name “Lumirror U48”, visible light transmittance of 93%), a float plate glass with a thickness of 3 mm (manufactured by Matsunami Glass, visible light transmittance of 91%) was used. %) was used in the same manner as in Comparative Example 3 to obtain a heat insulating substrate (C9).
Table 2 shows the results.

[Comparative Example 10]
As a transparent substrate layer, instead of a polyethylene terephthalate film substrate with a thickness of 50 μm (manufactured by Toray, trade name “Lumirror U48”, visible light transmittance of 93%), a float plate glass with a thickness of 3 mm (manufactured by Matsunami Glass, visible light transmittance of 91%) was used. %) was used, and a heat shielding and heat insulating substrate (C10) was obtained in the same manner as in Comparative Example 4.
Table 2 shows the results.

[Comparative Example 11]
As a transparent substrate layer, instead of a polyethylene terephthalate film substrate with a thickness of 50 μm (manufactured by Toray, trade name “Lumirror U48”, visible light transmittance of 93%), a float plate glass with a thickness of 3 mm (manufactured by Matsunami Glass, visible light transmittance of 91%) was used. %) was used, and a heat shielding and heat insulating substrate (C11) was obtained in the same manner as in Comparative Example 5.
Table 2 shows the results.

[Comparative Example 12]
As a transparent substrate layer, instead of a polyethylene terephthalate film substrate with a thickness of 50 μm (manufactured by Toray, trade name “Lumirror U48”, visible light transmittance of 93%), a float plate glass with a thickness of 3 mm (manufactured by Matsunami Glass, visible light transmittance of 91%) was used. %) was used, and a heat shielding and heat insulating substrate (C12) was obtained in the same manner as in Comparative Example 6.
Table 2 shows the results.

[Comparative Example 13]
The procedure was carried out in the same manner as in Comparative Example 1 except that the thickness of the protective topcoat layer was changed to 800 nm. A heat shielding and heat insulating substrate (C13) having a structure of layer (thickness 16 nm)/second metal oxide layer (thickness 10 nm)/protective topcoat layer (thickness 800 nm) was obtained.
Table 2 shows the results.

[Comparative Example 14]
The procedure was carried out in the same manner as in Comparative Example 1, except that the protective topcoat layer was not provided. 16 nm)/second metal oxide layer (thickness: 10 nm).
Table 2 shows the results.

[Comparative Example 15]
The procedure was carried out in the same manner as in Comparative Example 1 except that the thickness of the undercoat layer was changed to 6 μm. (16 nm thick)/second metal oxide layer (10 nm thick)/protective topcoat layer (60 nm thick) was obtained.
Table 2 shows the results.

The heat-shielding and insulating substrate of the present invention can be used, for example, for windows of buildings and vehicles, transparent cases for storing plants and the like, freezer or refrigerated showcases, and the like.

10 Transparent substrate layer 20 Infrared reflective layer 21 Metal layer 22a First metal oxide layer 22b Second metal oxide layer 40 Protective topcoat layer 60 Undercoat layer 70 Protective film 80 Adhesive layer 90 Heating appliance 100 Thermal insulation substrate 1000 window

Claims (11)

A thermal insulation substrate comprising a transparent substrate layer and an infrared reflective layer,
An undercoat layer is provided between the transparent substrate layer and the infrared reflective layer,
a protective topcoat layer on the side of the infrared reflective layer opposite the transparent substrate layer;
wherein the protective topcoat layer comprises a coordination-type material;
The undercoat layer has a thickness of 0.01 μm to 5 μm,
The protective topcoat layer has a thickness of 5 nm to 500 nm,
The undercoat layer has a hardness of 0.50 GPa or more,
The protective topcoat layer has a hardness of 0.50 GPa or more ,
The elastic modulus of the undercoat layer is 8.25 GPa or less,
The elastic modulus of the protective topcoat layer is 10.0 GPa or less .
Thermal insulation board. 2. The thermal insulation substrate according to claim 1, wherein the protective topcoat layer has a contact angle of 90 degrees or more. 3. The thermal insulation substrate according to claim 1, wherein said protective topcoat layer does not have a softening temperature within the range of 30.degree. C. to 75.degree. 4. The heat shielding and insulating substrate according to claim 1 , wherein the transparent substrate layer has a visible light transmittance of 10% or more. 5. The heat shielding and insulating substrate according to any one of claims 1 to 4 , wherein a topcoat layer is arranged between said protective topcoat layer and said infrared reflecting layer. 6. The thermal insulation substrate according to any one of claims 1 to 5 , wherein said protective topcoat layer is a resin layer formed from a resin composition containing an organic resin. 7. The heat insulating substrate according to claim 6 , wherein said organic resin is an acrylic resin. 8. The thermal insulation substrate according to any one of claims 1 to 7 , wherein said undercoat layer is a resin layer formed from a resin composition containing an organic resin. 9. The heat insulating substrate according to claim 8 , wherein said organic resin is an acrylic resin. 10. The heat insulating substrate according to any one of claims 1 to 9 , wherein the undercoat layer has an elastic modulus of 8.25 GPa or less. 11. The thermal insulation substrate according to any one of claims 1 to 10 , wherein the protective topcoat layer has an elastic modulus of 10.0 GPa or less.

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