WO2018181444A1 - Heat-shielding heat insulating substrate - Google Patents

Abstract

Provided is a heat-shielding heat insulating substrate that has excellent scratch resistance. This heat-shielding heat insulating substrate comprises a transparent substrate layer and an infrared reflection layer, and is provided with: a topcoat layer and a protective topcoat layer on the opposite side of the transparent substrate layer of the infrared reflection layer. The topcoat layer is any one of an oxide or a nitride, an oxynitride, or a non-oxynitride containing one or more of Group 13 or 14 of the periodic table as a main component, and includes one or more components of Group 3 or 4 of the periodic table, wherein the protective topcoat layer includes a coordination-coupled material.

Description

Thermal insulation board

The present invention relates to a heat insulating and heat insulating substrate.

The heat insulating and heat insulating substrate is a substrate having both a heat insulating function and a heat insulating function. For example, when such a heat-insulating and heat-insulating substrate is attached to a window glass, the infrared reflection function allows the inflow of solar heat (near infrared light) from the outside to the room and the heating heat (far away from the room to the outside). Infrared) can be suppressed, and indoor comfort and energy saving effect can be improved throughout the year.

As such a heat insulating and heat insulating substrate, in recent years, a heat insulating and heat insulating substrate including a transparent substrate layer and an infrared reflecting layer has been proposed (Patent Documents 1 and 2). The infrared reflecting layer has, for example, a configuration including a metal oxide layer on both sides of the metal layer, and can achieve both improved heat shielding by reflection of near infrared rays and improved heat insulation by reflection of far infrared rays.

The surface of the heat-insulating / insulating substrate itself or the heat-insulating / insulating substrate attached to the window glass is likely to be scratched by scratches during normal use or wiping operations during cleaning.

JP 2016-93892 A JP 2016-94012 A

An object of the present invention is to provide a heat insulating and heat insulating substrate excellent in scratch resistance.

The heat insulating and heat insulating substrate of the present invention is
A heat insulating and heat insulating substrate including a transparent substrate layer and an infrared reflective layer,
A top coat layer and a protective top coat layer are provided on the opposite side of the infrared reflective layer to the transparent substrate layer,
The topcoat layer is an oxide or nitride, oxynitride, or non-oxynitride mainly composed of one or more of Group 13 or Group 14 of the Periodic Table, Group 3 or Group 4 of the Periodic Table Including one or more ingredients of
The protective topcoat layer includes a coordination bond material.

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

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

In one embodiment, the infrared reflective layer, the top coat layer, and the protective top coat layer are directly laminated in this order.

In one embodiment, the top coat layer has a thickness of 0.5 nm to 500 nm.

In one embodiment, the protective topcoat layer has a thickness of 5 nm to 500 nm.

In one embodiment, the topcoat layer is selected from an oxide or oxynitride containing Si and Zr, an oxide or oxynitride containing Si and Y, an oxide or oxynitride containing Si and Ti. Including at least one selected from the group consisting of

In one embodiment, the top coat layer is a layer formed by a dry process, and the protective top coat layer is a layer formed by coating.

According to the present invention, it is possible to provide a heat insulating and heat insulating substrate excellent in scratch resistance.

It is a schematic sectional drawing which shows one embodiment of the thermal insulation heat insulation board | substrate of this invention. It is a schematic sectional drawing which shows one embodiment of the thermal insulation heat insulation board | substrate of this invention. It is sectional drawing which represents typically an example of the usage condition of the heat insulation heat insulation board | substrate of this invention. It is a figure which shows the measurement result of the softening temperature of the protective topcoat layer obtained in Example 26.

<< 1. Overview of thermal insulation board >>
The heat-insulating and heat-insulating substrate of the present invention includes a transparent substrate layer and an infrared reflective layer, and includes a top coat layer and a protective top coat layer on the opposite side of the infrared reflective layer to the transparent substrate layer.

In the heat insulating and heat insulating substrate of the present invention, preferably, the top coat layer is a layer formed by a dry process, and the protective top coat layer is a layer formed by coating. When the heat-insulating and heat-insulating substrate of the present invention includes such a topcoat layer and a protective topcoat layer, the adhesion between the topcoat layer and the protective topcoat layer is further improved, and the heat-insulating and heat-insulating substrate of the present invention has a high resistance. The scratch resistance is further improved, and the durability of the infrared reflecting layer can be further increased.

As the arrangement of the top coat layer and the protective top coat layer, the top coat layer may be arranged between the infrared reflective layer and the protective top coat layer, or the protective top coat layer is disposed between the infrared reflective layer and the top coat layer. May be arranged. The arrangement of the topcoat layer and the protective topcoat layer is preferably a form in which the topcoat layer is arranged between the infrared reflective layer and the protective topcoat layer in that the effect of the present invention can be further expressed. More preferably, the infrared reflection layer, the top coat layer, and the protective top coat layer are directly laminated in this order.

FIG. 1 is a schematic cross-sectional view showing one embodiment of a heat insulating and heat insulating substrate of the present invention. In FIG. 1, the heat insulating and heat insulating substrate 100 includes a transparent substrate layer 10, an infrared reflecting layer 20, a top coat layer 30, and a protective top coat layer 40.

The heat-insulating and heat-insulating substrate of the present invention includes a transparent substrate layer opposite to the infrared reflective layer, between the transparent substrate layer and the infrared reflective layer, between the infrared reflective layer and the top coat layer, and a top coat layer and a protective top coat. Any appropriate other layer may be provided between the layers and on the side of the protective topcoat layer opposite to the topcoat layer, if necessary. Such other layers may be one layer or two or more layers. Moreover, such other layers may be only 1 type, and may be 2 or more types.

FIG. 2 is a schematic cross-sectional view showing one embodiment of the heat insulating and heat insulating substrate of the present invention. In FIG. 2, the heat insulating and heat insulating substrate 100 includes a transparent substrate layer 10, an undercoat layer 60, an infrared reflective layer 20, a topcoat layer 30, a protective topcoat layer 40, and a protective film 70. In FIG. 2, the infrared reflective layer 20 is composed of three layers, a first metal oxide layer 22a, a metal layer 21, and a second metal oxide layer 22b. In one embodiment shown in FIG. 2, preferably, the heat-insulating and heat-insulating substrate of the present invention includes a transparent substrate layer 10, an undercoat layer 60, an infrared reflecting layer 20, a topcoat layer 30, a protective topcoat layer 40 and a protection. The film 70 is directly laminated in this order.

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

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

≪2. Transparent substrate layer >>
The transparent substrate layer is preferably a transparent plate member, a transparent film, or a composite thereof. Examples of the transparent plate member include glass, an acrylic plate, and a polycarbonate plate. 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, and 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 1.5 mm to 18 mm, and most preferably. Is 2 mm to 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 the material constituting the transparent substrate layer include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK), and polycarbonate (PC). From the standpoint of excellent heat resistance, polyethylene terephthalate (PET) is preferable.

≪3. Undercoat layer >>
An undercoat layer may be provided on the surface of the transparent substrate layer on the infrared reflective layer side. By providing the undercoat layer on the surface of the transparent substrate layer, the mechanical strength of the heat-insulating and heat-insulating substrate of the present invention can be increased, and the scratch resistance of the heat-insulating and heat-insulating substrate of the present invention can be improved. .

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, and particularly preferably 0.5 μm to 3 μm. Most preferably, it is 1 μm to 2 μm. If the thickness of the undercoat layer is within the above range, the mechanical strength of the heat-insulating and heat-insulating substrate of the present invention can be increased, and the scratch resistance of the heat-insulating and heat-insulating substrate of the present invention can be further improved.

The undercoat layer is preferably a cured film of a curable resin, and can be formed, for example, by a method in which a suitable cured film of an ultraviolet curable resin is provided on the transparent substrate 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 an ultraviolet curable resin. Examples of the ultraviolet curable resin as the organic resin include acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, epoxy resins, oxetane resins, and the like.

Corona treatment, plasma treatment, flame treatment, ozone treatment, primer treatment, glow treatment, saponification treatment, coupling agent on the surface of the undercoat layer (on the opposite side of the transparent substrate layer) Surface modification treatment such as treatment by the above may be performed.

<< 4. Antireflection layer >>
An antireflection layer may be provided between the transparent substrate layer and the infrared reflective layer. By providing the antireflection layer, the transparency of the heat insulating and heat insulating substrate of the present invention can be improved. Moreover, the adhesiveness of the heat insulation heat insulation board | substrate of this invention can be improved by providing the antireflection layer.

The thickness of the antireflection layer is preferably 30 nm or less, more preferably 1 nm to 30 nm, still more preferably 1 nm to 20 nm, and 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 by a dry process such as a sputtering method, a vacuum evaporation method, a CVD method, and an electron beam evaporation method. As a film forming method of the antireflection layer, a film forming method by a direct current sputtering method is preferable. In the case of adopting a film forming method by a direct current sputtering method, it is possible to form these plural layers in one pass by using a winding type sputtering apparatus provided with a plurality of film forming chambers. For this reason, not only the productivity of the antireflection layer can be greatly improved, but also the productivity of the heat-insulating and heat-insulating substrate of the present invention can be greatly improved.

≪5. Infrared reflective layer >>
As the infrared reflection layer, any appropriate layer can be adopted as long as it is a layer that can achieve both a heat shield improvement by reflection of near infrared rays and a heat insulation improvement by reflection of far infrared rays.

One embodiment of the infrared reflective layer includes a first metal oxide layer, a metal layer, and a second metal oxide layer in this order, and the first metal oxide layer and the second metal oxide layer are directly laminated on the metal layer. Being done. In this embodiment, the infrared reflecting layer is preferably composed of three layers, a first metal oxide layer, a metal layer, and a second metal oxide layer, and the first metal oxide layer, the metal layer, and the second metal oxide layer. The material layers are provided in this order. One embodiment of such an infrared reflecting layer can use, for example, embodiments described in JP-A-2016-93892 and JP-A-2016-94012.

The metal layer has a central role of infrared reflection. From the viewpoint of increasing the visible light transmittance and the near infrared reflectance without increasing the number of layers, the metal layer is preferably a silver alloy layer mainly composed of silver or a gold alloy layer mainly composed of gold. For example, since silver has a high free electron density, it is possible to realize a high reflectance of near infrared rays and far infrared rays. Therefore, even when the number of layers constituting the infrared reflection layer is small, it is possible to achieve both improvement in heat shielding by reflection of near infrared rays and improvement of heat insulation by reflection of far infrared rays.

When the metal layer is a silver alloy layer containing silver as a main component, the silver content in the metal layer is preferably 85% by weight to 99.9% by weight, more preferably 90% by weight to 99.8%. % By weight, more preferably 95% by weight to 99.7% by weight, and particularly preferably 97% by weight to 99.6% by weight. The higher the silver content in the metal layer, the higher the wavelength selectivity of the transmittance and reflectance, and the visible light transmittance. On the other hand, when silver is exposed to an environment where moisture, oxygen, chlorine, or the like is present, or when irradiated with 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. Specifically, as described above, the silver content in the metal layer is 99. It is preferable that it is 9 weight% or less.

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 the metal 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 further preferably 0.3% by weight. It is ˜5% by weight, particularly preferably 0.4% by weight to 3% by weight. Examples of metals other than silver include palladium (Pd), gold (Au), copper (Cu), bismuth (Bi), germanium (Ge), gallium (Ga), and the like, which can impart high durability. From the above, palladium (Pd) is preferable.

The metal oxide layer (first metal oxide layer and second metal oxide layer) controls the amount of visible light reflection at the interface with the metal layer to achieve both high visible light transmittance and high infrared reflectance. It is provided for the purpose. The metal oxide layer can also function as a protective layer for preventing deterioration of the metal layer. From the viewpoint of enhancing the wavelength selectivity of reflection and transmission in the infrared reflection layer, the refractive index of the metal oxide layer with respect to 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 (first metal oxide layer and second metal oxide layer) are preferably oxides of metals such as Ti, Zr, Hf, Nb, Zn, Al, Ga, In, Tl, Sn, Alternatively, a composite oxide of these metals is included. More preferably, the metal oxide layer includes 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 function as a protective layer for the metal layer is increased, so that the deterioration of the metal layer is suppressed. Can be done.

The metal oxide layer (first metal oxide layer and second metal oxide layer) is particularly preferably a composite metal oxide 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 weights with respect to a total of 100 parts by weight of the metal oxide. Part or more, more preferably 5 parts by weight or more, and still more preferably 7 parts by weight or more. If the content ratio of zinc oxide is within the above range, the metal oxide layer tends to be an amorphous layer, and the durability tends to be improved. On the other hand, if the content ratio of zinc oxide is excessively large, the durability may be reduced, or the visible light transmittance may be reduced. Therefore, the content ratio 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 100 parts by weight of the metal oxide. Or less.

As composite metal oxides containing zinc oxide, indium-zinc composite oxide (IZO) and zinc-tin composite oxide (ZTO) are used from the viewpoint of satisfying all visible light transmittance, refractive index, and durability. Indium-tin-zinc composite oxide (ITZO) is preferable. 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 reflecting layer transmits the visible light and selectively reflects the near infrared light. It can be set appropriately considering 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, and still 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, and even more preferably 1 nm to 40 nm. It is particularly preferably 2 nm to 30 nm. In the heat-insulating and heat-insulating substrate of the present invention, since the mechanical strength can be preferably increased, the thickness of the metal oxide layer (the thickness of each of the first metal oxide layer and the second metal oxide layer) is higher than that of the conventional product Can also 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 by a dry process such as a sputtering method, a vacuum evaporation method, a CVD method, and an electron beam evaporation method. The method for forming the metal layer and the metal oxide layer is preferably a film forming method by a direct current sputtering method. In the case of adopting a film forming method by a direct current sputtering method, it is possible to form these plural layers in one pass by using a winding type sputtering apparatus provided with a plurality of film forming chambers. For this reason, not only the productivity of the infrared reflecting layer can be greatly improved, but also the productivity of the heat-insulating and heat-insulating substrate of the present invention can be greatly improved. In addition, a target to be DC sputtered may be added with a conductive impurity in order to impart conductivity, and a part thereof may be reducible. Therefore, the impurity may be mixed in the antireflection layer to be formed or the composition of the layer may be different from the stoichiometric composition, but this is not a problem as long as the effect of the present invention is exhibited.

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

≪6. Topcoat layer >>
In the heat insulating and heat insulating substrate of the present invention, the top coat layer is preferably a layer formed by a dry process. Examples of the dry process include dry processes such as sputtering, vacuum vapor deposition, CVD, and electron beam vapor deposition. The film formation method for the topcoat layer is preferably a film formation method by a sputtering method, and more preferably a film formation method by a direct current sputtering method. In the case of adopting a film forming method by a direct current sputtering method, it is possible to form these plural layers in one pass by using a winding type sputtering apparatus provided with a plurality of film forming chambers. For this reason, not only the productivity of the topcoat layer can be greatly improved, but also the productivity of the heat-insulating and heat-insulating substrate of the present invention can be greatly improved. By providing such a topcoat layer, the heat-insulating and heat-insulating substrate of the present invention improves the adhesion between the topcoat layer and the protective topcoat layer, and improves the scratch resistance of the heat-insulating and heat-insulating substrate of the present invention. The durability of the infrared reflective layer can be increased. In particular, it is possible to improve both the cotton scratch resistance and the steel wool scratch resistance of the heat-insulating and heat-insulating substrate of the present invention.

The heat-insulating and heat-insulating substrate of the present invention preferably has high transparency by having a specific topcoat layer.

The topcoat layer is preferably an oxide or nitride, oxynitride, or non-oxynitride mainly composed of one or more members of Group 13 or Group 14 of the Periodic Table. Contains one or more of Group 4 components. More preferably, the topcoat layer is an oxide or nitride, oxynitride, non-nitride, or non-oxide mainly composed of one or more members of Group 14, and Group 3 or Group 4 of the periodic table. Of one or more ingredients. The topcoat layer is more preferably at least one selected from an oxide or oxynitride containing Si and Zr, an oxide or oxynitride containing Si and Y, and an oxide or oxynitride containing Si and Ti. including. The topcoat layer particularly preferably contains at least one selected from an oxide containing Si and Zr, an oxide containing Si and Y, and an oxide containing Si and Ti.

The group 14 element is difficult to be an ion because it has four outermost electrons. Group 13 elements are less likely to become anions due to three outermost electrons. Therefore, it is considered that the hardness of nitride, oxynitride, non-nitride, or non-oxide increases.

Addition of elements of Group 3 or Group 4 of the periodic table increases strength, improves corrosion resistance, and heat resistance by densifying the main component elements and densifying the molecular structure.

The amount of the Group 3 or Group 4 element added is preferably from 0.01 atm% to 49.9 atm%, more preferably from 0.05 atm% to the point where the effects of the present invention can be more manifested. It is 40.0 atm%, more preferably 0.1 atm% to 40.0 atm%, particularly preferably 0.5 atm% to 35.0 atm%. When the addition amount of the Group 3 or Group 4 element is small, the element is not uniformly inserted into the entire matrix, and thus the effects of the present invention may not be exhibited. On the other hand, when the amount of the Group 3 or Group 4 element added is too large, the compatibility with the main component is deteriorated and the effects of the present invention may not be exhibited. The compatibility can be confirmed by a phase diagram.

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

≪7. Protective topcoat layer >>
In the heat insulating and heat insulating substrate of the present invention, the protective top coat layer is preferably a layer formed by coating. The protective topcoat layer is formed by coating, for example, by dissolving a material as described below in a solvent, preparing a solution, applying this solution on the topcoat layer, drying the solvent, and then applying ultraviolet rays or electron beams. The formation by making it harden | cure by application | coating of irradiation etc. or provision of a thermal energy is mentioned. When the heat-insulating and heat-insulating substrate of the present invention is provided with such a protective topcoat layer, the adhesion between the topcoat layer and the protective topcoat layer is enhanced, and the scratch-resistance of the heat-insulating and heat-insulating substrate of the present invention is improved. In addition, the durability of the infrared reflective layer can be increased. In particular, it is possible to improve both the cotton scratch resistance and the steel wool scratch resistance of the heat-insulating and heat-insulating substrate of the present invention.

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

The protective top coat layer preferably has little absorption of far infrared rays. If the far-infrared absorption in the protective topcoat layer is small, the far-infrared rays in the room are reflected into the room by the infrared-reflecting layer, so that the heat insulation effect can be enhanced. Examples of a method for reducing the far-infrared absorption amount by the protective topcoat layer include a method using a material having a low far-infrared absorptivity as a material for the protective topcoat layer, a method for reducing the thickness of the protective topcoat layer, and the like. On the other hand, if the far-infrared absorption in the protective topcoat layer is large, the far-infrared rays in the room are absorbed by the protective topcoat layer, and are not reflected by the infrared reflective layer, but are radiated to the outside by heat conduction. May decrease.

If a material having a low far-infrared absorptivity is used as the material of the protective topcoat layer, the far-infrared absorption can be kept small even when the thickness of the protective topcoat layer is large, and the protective effect on the infrared reflective layer is enhanced. Can do. As a material for the protective topcoat layer having a small far-infrared absorption, a compound having a small content such as a C═C bond, a C═O bond, a C—O bond or an aromatic ring 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 even more preferably 150 nm or less, from the viewpoint of reducing far-infrared absorption. Particularly preferably, it is 120 nm or less, and most preferably 100 nm or less. When the optical film thickness (product of refractive index and physical film thickness) of the protective topcoat layer overlaps the visible light wavelength range, the surface of the heat-insulating and heat-insulating substrate of the present invention is rainbow-patterned due to multiple reflection interference at the interface. "Iris phenomenon" may appear. Since the refractive index of a 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 the protective topcoat layer and enhancing the durability of the heat-insulating and heat-insulating substrate of the present invention. More preferably, it is 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 reflectance of visible light is reduced due to multiple reflection interference between the reflected light on the surface side of the protective topcoat layer and the reflected light on the infrared reflective layer side interface. be able to. Therefore, in addition to the reflectance lowering effect due to the light absorption of the infrared reflecting layer, the antireflection effect by the protective topcoat layer can be obtained, and the visibility of the heat insulating and heat insulating substrate of the present invention can be further enhanced.

As a material for the protective top coat layer, a material having high visible light transmittance and excellent mechanical strength and chemical strength is preferable. Examples of the material for the protective topcoat layer include organic resins, inorganic materials, and organic-inorganic hybrid materials in which an organic component and an inorganic component are chemically bonded. Only one type of organic resin may be used, or two or more types may be used. Only one type of inorganic material may be used, or two or more types may be used. Only one type of organic-inorganic hybrid material may be used, or two or more types may be used.

Examples of the organic resin include an actinic ray curable or thermosetting organic resin. Specifically, for example, a fluorine resin, an acrylic resin, a urethane resin, an ester resin, an epoxy resin, a silicone Based resins and the like. The organic resin is preferably an acrylic resin from the viewpoint that the effects of the present invention can be further exhibited.

Examples of the inorganic material 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, and more preferably contains an organic resin. A resin layer formed from the resin composition may be mentioned.

The protective topcoat layer preferably contains a coordination bond type material. As the coordination bond type material, any appropriate coordination bond type material can be adopted as long as it can form a coordination bond with another compound as long as the effects of the present invention are not impaired. The coordination bond type material may be only one kind or two or more kinds. When the protective topcoat layer contains a coordination bond type material, for example, when the topcoat layer is directly laminated with the protective topcoat layer, the coordination bond strength between these two layers May develop and adhesion may be improved. In particular, when the topcoat layer contains a metal oxide, the acidic group in the protective topcoat layer can express an affinity having a high coordination bond with the metal oxide in the topcoat layer. Moreover, since the adhesiveness of a topcoat layer and a protective topcoat layer improves, the intensity | strength of a surface protective layer can improve, Therefore The durability of an infrared reflective layer can be improved.

The coordination bond material is preferably a compound having a group having a lone electron pair. Examples of the group having a lone electron pair include coordination of a phosphorus atom, a sulfur atom, an oxygen atom, a nitrogen atom, and the like. Examples thereof include groups having atoms, and specific examples include a phosphoric acid group, a sulfuric acid group, a thiol group, a carboxyl group, and an amino group.

The coordination bond type material can preferably increase the adhesion by the action of metal ions. The coordination bond type material may have a reactive group in order to enhance the adhesion with other resin materials and the like.

Preferred examples of the coordinate bond material include ester compounds having an acidic group and a polymerizable functional group in the same molecule.

Examples of 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, maleic acid, and ethylenically unsaturated compounds. And an ester of a compound having a polymerizable functional group such as a group, silanol group or epoxy group and a hydroxyl group in the molecule. Such an ester compound may be a polyester 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. The 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 phosphoric monoester compound or a phosphoric diester compound represented by the general formula (A). In addition, phosphoric acid monoester and phosphoric acid diester can also be used together. When the phosphoric acid monoester compound or phosphoric acid diester compound represented by the general formula (A) is employed as the ester compound having an acidic group and a polymerizable functional group in the same molecule, the phosphoric acid hydroxy group is converted into a metal oxide. When the top coat layer is directly laminated with the protective top coat layer and the top coat layer contains a metal oxide, the adhesion between these two layers is excellent. It can be improved.

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

The content of the coordination bond type material in the protective topcoat layer is preferably 1% by weight to 20% by weight, more preferably 1.5% by weight to 17.5% by weight, and further preferably 2% by weight. % 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, 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 large, the curing rate at the time of forming the protective topcoat layer may decrease and the hardness may decrease, or the surface of the protective topcoat layer may slip. May decrease and scratch resistance may decrease.

The protective topcoat layer preferably does not have a softening temperature in the range of 30 ° C to 75 ° C. More preferably, the protective topcoat layer does not have a softening temperature in the range of 25 ° C. to 75 ° C., more preferably does not have a softening temperature in the range of 20 ° C. to 80 ° C., and particularly 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 hardly change in an actual use environment, and stable scratch resistance and dent resistance can be obtained. An 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 for the protective topcoat layer, it is preferable that a crosslinked structure be introduced. By forming the crosslinked structure, the mechanical strength and chemical strength of the protective topcoat layer are increased, and the protective function for the infrared reflective layer is increased. Among such crosslinked structures, a crosslinked structure derived from an ester compound having an acidic group and a polymerizable functional group in the same molecule is preferably introduced.

Protective topcoat layer materials include silane coupling agents, coupling agents such as titanium coupling agents, leveling agents, UV absorbers, antioxidants, thermal stabilizers, lubricants, plasticizers, anti-coloring agents, flame retardants In addition, additives such as an antistatic agent may be contained. As content of these additives, arbitrary appropriate content can be employ | adopted in the range which does not impair the effect of this invention.

As a method for forming the protective topcoat layer, any appropriate forming method can be adopted as long as the effects of the present invention are not impaired. As such a forming method, for example, a method of applying a raw material solution of a protective topcoat layer on the topcoat layer, drying the solvent, and then curing by irradiation with ultraviolet rays or electron beams, or application of thermal energy Is mentioned.

≪8. Protective film >>
A protective film may be provided on the side of the protective topcoat layer opposite to the topcoat 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, and 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. An adhesive bond layer can be used for bonding with a window glass etc., for example.

As the adhesive layer, those having a high visible light transmittance and a small refractive index difference from the transparent substrate layer are preferable. As a material for the adhesive layer, any appropriate material can be adopted as long as the effects of the present invention are not impaired. An example of such a material is an acrylic pressure-sensitive adhesive (acrylic pressure-sensitive adhesive). Acrylic pressure-sensitive adhesive (acrylic pressure-sensitive adhesive) has excellent optical transparency, moderate wettability, cohesiveness and adhesion, and 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, it is possible to suppress deterioration of the infrared reflective layer due to ultraviolet rays such as sunlight. From the viewpoint of reducing the ultraviolet transmittance of the adhesive layer, the adhesive layer preferably contains an ultraviolet absorber. In addition, degradation of the infrared reflective layer resulting from the ultraviolet rays from the outdoors can also be suppressed by using a transparent substrate layer containing an ultraviolet absorber.

The exposed surface of the adhesive layer is preferably covered with a separator temporarily for the purpose of preventing contamination of the exposed surface until the heat-insulating and heat-insulating substrate of the present invention is put to practical use. Such a separator can prevent contamination due to contact with the outside of the exposed surface of the adhesive layer in a usual handling state.

<< 10. Applications of thermal insulation board
The heat-insulating and heat-insulating substrate of the present invention can be used for windows such as buildings and vehicles, transparent cases for storing plants, frozen and refrigerated showcases, etc., and has the effect of improving the heating and cooling effect and preventing sudden temperature changes. Can do.

FIG. 3 is a cross-sectional view schematically showing an example of a usage pattern of the heat-insulating and heat-insulating substrate of the present invention. In this usage pattern, the heat-insulating and heat-insulating substrate 100 of the present invention is disposed by bonding the transparent substrate layer 10 side to the indoor side of a window 1000 of a building or an automobile via any appropriate adhesive layer 80. As schematically shown in FIG. 3, the heat-insulating and heat-insulating substrate 100 of the present invention transmits visible light (VIS) from the outside and introduces it into the room, and transmits near-infrared light (NIR) from the outside to the infrared reflection layer. Reflected at 20. The near-infrared reflection suppresses the inflow of heat from the outside into the room due to sunlight or the like (a heat shielding effect is exhibited), so that, for example, the cooling efficiency in summer can be increased. Furthermore, since the infrared reflective layer 20 reflects indoor far infrared rays (FIR) radiated from the heating appliance 90, a heat insulating effect is exhibited, and heating efficiency in winter can be enhanced. Moreover, since the thermal insulation heat insulation board | substrate 100 of this invention is provided with the infrared reflective layer 20, the reflectance of visible light is reduced, When used for a showcase, a show window, etc., the visibility of goods etc. falls. Without making it possible, it is possible to impart heat insulation and heat insulation.

The heat-insulating and heat-insulating substrate of the present invention can be used by being fitted into a frame or the like as disclosed in, for example, Japanese Patent Application Laid-Open No. 2013-61370. In such a form, since it is not necessary to provide an adhesive layer, far-infrared absorption by the adhesive layer does not occur. For this reason, for example, a material having a low content of functional groups such as C═C bond, C═O bond, C—O bond, and aromatic ring (for example, cyclic polyolefin) is used as the transparent substrate layer. Far infrared rays from the substrate layer side can be reflected by the infrared reflective layer, and heat insulation can be imparted to both sides of the heat-insulating and heat-insulating substrate of the present invention. Such a configuration is particularly useful, for example, in a refrigerated showcase or a frozen showcase.

When the transparent substrate layer is, for example, a transparent plate member (for example, glass, acrylic plate, polycarbonate plate, etc.) or a composite of the transparent plate member and a transparent film, For example, it can be applied to a building or a car window as it is.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In addition, the test and evaluation method in an Example etc. are as follows. Note that “parts” means “parts by weight” unless otherwise noted, and “%” means “% by weight” unless otherwise noted.

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

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

<Cotton scratch resistance test>
The measurement thermal insulation board is left at room temperature for 24 hours, and the surface of the thermal insulation board on the transparent substrate layer side is coated with an adhesive layer with a thickness of 25 μm (product name “HJ-9150W” manufactured by Nitto Denko Corporation). A sample bonded to an aluminum plate was used as a sample. Using the Gakushin Abrasion Tester, applying the load of 500g with a test cotton cloth (gold width 3), the outermost surface of the thermal insulation board on the aluminum plate opposite to the transparent substrate layer of the infrared reflective layer 1000 rubbing. The sample after the test was visually evaluated for scratches and peeling, and evaluated according to the following evaluation criteria. The actual measured values of temperature and humidity during the actual test were a temperature of 23 ° C. and a humidity of 50% RH.
○: No scratches were observed on the surface and no peeling occurred.
Δ: Some scratches are observed on the surface, but no peeling occurs.
X: Many scratches and peelings are observed on the surface.

<Steel wool (SW) scratch resistance test>
After leaving the heat-insulating / insulating substrate for measurement at room temperature for 24 hours, the surface on the transparent substrate layer side has a thickness of 1 through an adhesive layer having a thickness of 25 μm (product name “HJ-9150W” manufactured by Nitto Denko Corporation). A sample bonded to a 3 mm glass plate was used as a sample. Using a ten-point pen tester, while applying a load of 1000 g with steel wool (Bonnster, # 0000), the outermost side of the infrared ray reflective layer on the side opposite to the transparent substrate layer of the heat-shielding heat insulating substrate on the glass plate. The surface was rubbed 10 times. The sample after the test was visually evaluated for scratches and peeling, and evaluated according to the following evaluation criteria. The actual measured values of temperature and humidity during the actual test were a temperature of 23 ° C. and a humidity of 50% RH.
◯: No scratches are observed on the surface and no peeling occurs.
Δ: Some scratches are observed on the surface, but no peeling occurs.
X: Many scratches and peelings are observed on the surface.

<Steel Wool (SW) Scratch Resistance Test after 180 Dew Cycles>
After leaving the heat-insulating / insulating substrate for measurement at room temperature for 24 hours, the surface on the transparent substrate layer side has a thickness of 1 through an adhesive layer having a thickness of 25 μm (product name “HJ-9150W” manufactured by Nitto Denko Corporation). A sample bonded to a 3 mm glass plate was used as a sample. After storing the sample in a condensation environment using a dew cycle tester, heat insulation on a glass plate while applying a load of 1000 g with steel wool (Bonnster, # 0000) using a 10-point pen tester The outermost surface of the heat insulating substrate on the side opposite to the transparent substrate layer of the infrared reflecting layer was rubbed 10 times. In the condensation test, one cycle was stored at −10 ° C. for 10 minutes, stored at 50 ° C. and 90% RH for 10 minutes, and stored at room temperature (temperature 23 ° C., humidity 50% RH) for 10 minutes. The above 1 cycle was repeated 180 times. The sample after the test was visually evaluated for scratches and peeling, and evaluated according to the following evaluation criteria.
◯: No scratches are observed on the surface and no peeling occurs.
Δ: Some scratches are observed on the surface, but no peeling occurs.
X: Many scratches and peelings are observed on the surface.

<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 by 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)
An acrylic UV curable hard coat layer (JSR, Z7540) is 2 μm thick on one side of a 50 μm thick polyethylene terephthalate film substrate (trade name “Lumirror U48”, visible light transmittance 93%, manufactured by Toray Industries, Inc.) Formed with. Specifically, the hard coat layer solution is applied with a gravure coater, dried at 80 ° C., then irradiated with ultraviolet light with an integrated light amount of 300 mJ / cm ² with an ultra-high pressure mercury lamp, cured, and undercoated onto the transparent substrate layer. A coat layer was formed.
(Formation of first metal oxide layer, metal layer, second metal oxide layer, topcoat layer)
A zinc-tin composite oxide (ZTO) layer having a film thickness of 30 nm and an Ag film having a film thickness of 15 nm are formed on the undercoat layer formed on the transparent substrate layer by a direct current magnetron sputtering method using a winding type sputtering apparatus. A -Pd alloy layer, a 30 nm thick zinc-tin composite oxide (ZTO) layer, and a 10 nm thick SiZrO _x layer (Si: 66 atm%, Zr: 34 atm%) are sequentially formed on the undercoat layer. In addition, a first metal oxide layer, a metal layer, a second metal oxide layer, and a topcoat layer were formed in this order.
For the formation of 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, power density: 2.67 W / cm ² , Sputtering was performed at a process pressure of 0.4 Pa. At this time, the amount of gas introduced into the sputtering film forming chamber was adjusted so that Ar: O ₂ was 98: 2 (volume ratio).
For the formation of the Ag—Pd alloy layer, a metal target containing silver: palladium in a weight ratio of 96.4: 3.6 was used. The power density was 1.33 W / cm ² and the process pressure was 0.4 Pa. Sputtering was performed.
For the formation of the SiZrO _x layer, sputtering was performed under the conditions of power density: 2.67 W / cm ² and process pressure: 0.4 Pa using a target obtained by sintering Si: Zr at an atomic weight ratio of 67:33. At this time, the amount of gas introduced into the sputtering film forming chamber was adjusted so that Ar: O ₂ was 60:40 (volume ratio).
(Formation of protective topcoat layer)
On the topcoat layer, a protective topcoat layer made of a fluorine-based ultraviolet curable resin having a coordination bond material was formed to a thickness of 60 nm. Specifically, 5 phosphoric acid ester compounds (trade name “KAYAMER PM-21”, manufactured by Nippon Kayaku Co., Ltd.) are added to 100 parts by weight of the solid content of the fluorine-based hard coat resin solution (trade name “JUA204”, manufactured by JSR). The solution added with parts by weight was applied using a spin coater, dried at 60 ° C. for 1 minute, and then cured by irradiating with an ultra-high pressure mercury lamp with an ultra-high pressure mercury lamp with an integrated light amount of 400 mJ / cm ² . The phosphoric acid ester compound is a phosphoric acid monoester compound having one acryloyl group in the molecule (in the general formula (A), X is a methyl group, n = 0, p = 1). And a phosphoric acid diester compound having two acryloyl groups in the molecule (in the above general formula (A), X is a methyl group, n = 0, p = 2).
(Thermal insulation board)
As described above, transparent substrate layer (thickness 50 μm) / undercoat layer (thickness 2 μm) / first metal oxide layer (thickness 30 nm) / metal layer (thickness 15 nm) / second metal oxide layer (thickness 30 nm) A heat-insulating and heat-insulating substrate (1) having a structure of / topcoat layer (thickness 10 nm) / protective topcoat layer (thickness 60 nm) was obtained.
The results are shown in Table 1.

[Example 2]
SiZrO _x layer Si in formation of: Zr 97: except for using a target obtained by sintering at 3 atomic weight ratio were performed in the same manner as in Example 1 to obtain a thermal barrier thermal insulation board (2).
The results are shown in Table 1.

Example 3
SiZrO _x layer in place of the formation of siyo _x layer Si: Y 94: except for using a target in which sintered at 6 atomic weight ratio of, performed in the same manner as in Example 1, the thermal barrier insulation substrate (3) Obtained.

Example 4
Siyo _x layer Si in formation of: Y 97: except for using a target obtained by sintering at 3 atomic weight ratio were performed in the same manner as in Example 3, to obtain a thermal barrier thermal insulation board (4).
The results are shown in Table 1.

Example 5
Si in formation of SiTiO _x layer in place of the SiZrO _x layer 99 of Ti: except for using the targets sintered at 1 atomic weight ratio is performed in the same manner as in Example 1, the thermal barrier insulation substrate (5) Obtained.
The results are shown in Table 1.

Example 6
Si in formation of SiAlZrO _x layer in place of the SiZrO _x layer: Al: except for using a target obtained by sintering in atomic weight ratio of 60:30:10 to Zr were performed in the same manner as in Example 1, thermal barrier insulation board (6) was obtained.
The results are shown in Table 1.

Example 7
SiZrO _x layer place of the formation of SiAlYO _x layer Si: Al: Y 60: 37: except for using a target obtained by sintering at 3 atomic weight ratio is performed in the same manner as in Example 1, thermal barrier insulation board (7) was obtained.
The results are shown in Table 1.

Example 8
In place of the SiZrO _x layer, a SiAlZrN _x O _Y layer was formed in the same manner as in Example 1 except that a target obtained by sintering Si: Al: Zr at an atomic weight ratio of 60:30:10 was used. A heat insulating substrate (8) was obtained.
The results are shown in Table 1.

Example 9
In place of the SiZrO _x layer, a SiAlYN _x O _Y layer was formed in the same manner as in Example 1 except that a target obtained by sintering Si: Al: Y at an atomic weight ratio of 60: 39: 1 was used. A heat insulating substrate (9) was obtained.
The results are shown in Table 1.

Example 10
Instead of a 50 μm thick polyethylene terephthalate film substrate (trade name “Lumirror U48”, visible light transmittance 93%) as a transparent substrate layer, a 3 mm thick float plate glass (manufactured by Matsunami Glass, visible light transmittance 91) %) Was carried out in the same manner as in Example 1 to obtain a heat insulating and heat insulating substrate (10).
The results are shown in Table 1.

Example 11
Instead of a 50 μm thick polyethylene terephthalate film substrate (trade name “Lumirror U48”, visible light transmittance 93%) as a transparent substrate layer, a 3 mm thick float plate glass (manufactured by Matsunami Glass, visible light transmittance 91) %) Was carried out in the same manner as in Example 2 to obtain a heat insulating and heat insulating substrate (11).
The results are shown in Table 1.

Example 12
Instead of a 50 μm thick polyethylene terephthalate film substrate (trade name “Lumirror U48”, visible light transmittance 93%) as a transparent substrate layer, a 3 mm thick float plate glass (manufactured by Matsunami Glass, visible light transmittance 91) %) Was carried out in the same manner as in Example 3 to obtain a heat insulating and heat insulating substrate (12).
The results are shown in Table 1.

Example 13
Instead of a 50 μm thick polyethylene terephthalate film substrate (trade name “Lumirror U48”, visible light transmittance 93%) as a transparent substrate layer, a 3 mm thick float plate glass (manufactured by Matsunami Glass, visible light transmittance 91) %) Was carried out in the same manner as in Example 4 to obtain a heat insulating and heat insulating substrate (13).
The results are shown in Table 1.

Example 14
Instead of a 50 μm thick polyethylene terephthalate film substrate (trade name “Lumirror U48”, visible light transmittance 93%) as a transparent substrate layer, a 3 mm thick float plate glass (manufactured by Matsunami Glass, visible light transmittance 91) %) Was carried out in the same manner as in Example 5 to obtain a heat insulating and heat insulating substrate (14).
The results are shown in Table 1.

Example 15
Instead of a 50 μm thick polyethylene terephthalate film substrate (trade name “Lumirror U48”, visible light transmittance 93%) as a transparent substrate layer, a 3 mm thick float plate glass (manufactured by Matsunami Glass, visible light transmittance 91) %) Was carried out in the same manner as in Example 6 to obtain a heat insulating and heat insulating substrate (15).
The results are shown in Table 1.

Example 16
Instead of a 50 μm thick polyethylene terephthalate film substrate (trade name “Lumirror U48”, visible light transmittance 93%) as a transparent substrate layer, a 3 mm thick float plate glass (manufactured by Matsunami Glass, visible light transmittance 91) %) Was carried out in the same manner as in Example 7 to obtain a heat insulating and heat insulating substrate (16).
The results are shown in Table 1.

Example 17
Instead of a 50 μm thick polyethylene terephthalate film substrate (trade name “Lumirror U48”, visible light transmittance 93%) as a transparent substrate layer, a 3 mm thick float plate glass (manufactured by Matsunami Glass, visible light transmittance 91) %) Was carried out in the same manner as in Example 8 to obtain a heat insulating and heat insulating substrate (17).
The results are shown in Table 1.

Example 18
Instead of a 50 μm thick polyethylene terephthalate film substrate (trade name “Lumirror U48”, visible light transmittance 93%) as a transparent substrate layer, a 3 mm thick float plate glass (manufactured by Matsunami Glass, visible light transmittance 91) %) Was carried out in the same manner as in Example 9 to obtain a heat insulating and heat insulating substrate (18).
The results are shown in Table 1.

Example 19
Except for changing the thickness of the protective topcoat layer to 100 nm, the same procedure as in Example 1 was performed, and the transparent substrate layer (thickness 50 μm) / undercoat layer (thickness 2 μm) / first metal oxide layer (thickness 30 nm) / metal A heat insulating and heat insulating substrate (19) having a structure of layer (thickness 15 nm) / second metal oxide layer (thickness 30 nm) / topcoat layer (thickness 10 nm) / protective topcoat layer (thickness 100 nm) was obtained.
The results are shown in Table 1.

Example 20
Except for changing the thickness of the protective topcoat layer to 400 nm, the same procedure as in Example 1 was performed, and the transparent substrate layer (thickness 50 μm) / undercoat layer (thickness 2 μm) / first metal oxide layer (thickness 30 nm) / metal A heat insulating and heat insulating substrate (20) having a structure of layer (thickness 15 nm) / second metal oxide layer (thickness 30 nm) / topcoat layer (thickness 10 nm) / protective topcoat layer (thickness 400 nm) was obtained.
The results are shown in Table 1.

Example 21
Except for changing the thickness of the protective topcoat layer to 800 nm, the same procedure as in Example 1 was performed, and the transparent substrate layer (thickness 50 μm) / undercoat layer (thickness 2 μm) / first metal oxide layer (thickness 30 nm) / metal A heat insulating and heat insulating substrate (21) having a structure of layer (thickness 15 nm) / second metal oxide layer (thickness 30 nm) / topcoat layer (thickness 10 nm) / protective topcoat layer (thickness 800 nm) was obtained.
The results are shown in Table 1.

[Example 22]
Except for changing the thickness of the topcoat layer to 100 nm, the same procedure as in Example 1 was performed, and the transparent substrate layer (thickness 50 μm) / undercoat layer (thickness 2 μm) / first metal oxide layer (thickness 30 nm) / metal layer A heat insulating and heat insulating substrate (22) having a structure of (thickness 15 nm) / second metal oxide layer (thickness 30 nm) / topcoat layer (thickness 100 nm) / protective topcoat layer (thickness 60 nm) was obtained.
The results are shown in Table 1.

Example 23
Except for changing the thickness of the topcoat layer to 400 nm, the same procedure as in Example 1 was performed, and the transparent substrate layer (thickness 50 μm) / undercoat layer (thickness 2 μm) / first metal oxide layer (thickness 30 nm) / metal layer A heat insulating and heat insulating substrate (23) having a configuration of (thickness 15 nm) / second metal oxide layer (thickness 30 nm) / top coat layer (thickness 400 nm) / protective top coat layer (thickness 60 nm) was obtained.
The results are shown in Table 1.

Example 24
Except for changing the thickness of the topcoat layer to 800 nm, the same procedure as in Example 1 was performed, and the transparent substrate layer (thickness 50 μm) / undercoat layer (thickness 2 μm) / first metal oxide layer (thickness 30 nm) / metal layer A heat insulating and heat insulating substrate (24) having a structure of (thickness 15 nm) / second metal oxide layer (thickness 30 nm) / top coat layer (thickness 800 nm) / protective top coat layer (thickness 60 nm) was obtained.
The results are shown in Table 1.

Example 25
As a coordination bond material contained in the protective topcoat layer, dipentaerythritol pentaacrylate-succinic acid modified product (Kyoeisha Chemical Co., Ltd.) instead of the phosphate ester compound (product name “KAYAMER PM-21” manufactured by Nippon Kayaku Co., Ltd.) The product was manufactured in the same manner as in Example 1 except that the product name “Light Acrylate DPE-6A-MS” was used to obtain a heat-insulating and heat-insulating substrate (25).
The results are shown in Table 1.

Example 26
Except having changed the formation of a protection topcoat layer as follows, it carried out similarly to Example 1 and obtained the heat-shielding heat insulation board | substrate (26).
The results are shown in Table 1.
Moreover, the measurement result of the softening temperature of the obtained protective topcoat layer was shown in FIG. The softening temperature was 95 ° C.
(Formation of protective topcoat layer)
On the topcoat layer, a protective topcoat layer made of an acrylic ultraviolet curable resin having a coordinate bond material was formed to a thickness of 60 nm. Specifically, silica particles (trade name “PGM-AC-2140Y”, manufactured by Nissan Chemical Co., Ltd.) are added to 100 parts by weight of the solid content of the acrylic hard coat resin solution (trade name “Z-773”, manufactured by Aika Industry). 50 parts by weight, 5 parts by weight of a phosphoric acid ester compound (product name “KAYAMER PM-21”, manufactured by Nippon Kayaku Co., Ltd.) and 10 fluorine-based additives (product name “OPTOOL DAC-HP”, manufactured by Daikin Industries) The solution added with parts by weight was applied using a spin coater, dried at 100 ° C. for 1 minute, and then cured by irradiating with an ultra-high pressure mercury lamp with an ultra-high pressure mercury lamp with an integrated light amount of 400 mJ / cm ² . The phosphoric acid ester compound is a phosphoric acid monoester compound having one acryloyl group in the molecule (in the above general formula (1), X is a methyl group, n = 0, p = 1) And a phosphoric acid diester compound having two acryloyl groups in the molecule (in the above general formula (1), X is a methyl group, n = 0, p = 2).

Example 27
The heat shielding and heat insulating substrate (27) was prepared in the same manner as in Example 26 except that the ultraviolet light irradiation amount used for curing the protective topcoat layer was changed to an integrated light amount of 100 mJ / cm ² instead of the integrated light amount of 400 mJ / cm ^2. Obtained.
The results are shown in Table 1.
Moreover, the softening temperature of the obtained protective topcoat layer was 70 degreeC.

[Comparative Example 1]
Except that the protective topcoat layer was not formed, the same procedure as in Example 1 was performed to obtain a heat insulating and heat insulating substrate (C1).
The results are shown in Table 2.

[Comparative Example 2]
Except that the protective topcoat layer was not formed, the same procedure as in Example 2 was performed to obtain a heat insulating and heat insulating substrate (C2).
The results are shown in Table 2.

[Comparative Example 3]
Except that the protective topcoat layer was not formed, the same procedure as in Example 3 was performed to obtain a heat insulating and heat insulating substrate (C3).
The results are shown in Table 2.

[Comparative Example 4]
Except not having formed the protective topcoat layer, it carried out similarly to Example 4 and obtained the heat-shielding heat insulation board | substrate (C4).
The results are shown in Table 2.

[Comparative Example 5]
Except that the protective topcoat layer was not formed, the same procedure as in Example 5 was performed to obtain a heat insulating and heat insulating substrate (C5).
The results are shown in Table 2.

[Comparative Example 6]
Except not having formed the protective topcoat layer, it carried out similarly to Example 6 and obtained the heat-shielding heat insulation board | substrate (C6).
The results are shown in Table 2.

[Comparative Example 7]
Except not having formed the protective topcoat layer, it carried out similarly to Example 7 and obtained the heat-shielding heat insulation board | substrate (C7).
The results are shown in Table 2.

[Comparative Example 8]
Except not having formed the protective topcoat layer, it carried out similarly to Example 8 and obtained the heat-insulation board | substrate (C8).
The results are shown in Table 2.

[Comparative Example 9]
Except not having formed the protective topcoat layer, it carried out similarly to Example 9 and obtained the heat-insulation board | substrate (C9).
The results are shown in Table 2.

[Comparative Example 10]
A heat insulating and heat insulating substrate (C10) was obtained in the same manner as in Example 1 except that a ZrO ₂ layer was formed instead of the SiZrO _x layer.
The results are shown in Table 2.

[Comparative Example 11]
A heat insulating and heat insulating substrate (C11) was obtained in the same manner as in Example 1 except that a SiO ₂ layer was formed instead of the SiZrO _x layer.
The results are shown in Table 2.

[Comparative Example 12]
A heat insulating and heat insulating substrate (C12) was obtained in the same manner as in Example 1 except that an Al ₂ O ₃ layer was formed instead of the SiZrO _x layer.
The results are shown in Table 2.

[Comparative Example 13]
Instead of SiZrO _x layer for the formation of SiSnO _x layer Si: except that using a target obtained by sintering in atomic weight ratio of 50:50 Sn were performed in the same manner as in Example 1, the thermal barrier insulation substrate (C13) Obtained.
The results are shown in Table 2.

[Comparative Example 14]
Except that the Si layer was formed in place of the SiZrO _x layer, the same procedure as in Example 1 was performed to obtain a heat insulating and heat insulating substrate (C14).
The results are shown in Table 2.

[Comparative Example 15]
Except that the SiZrO _x layer was not formed, the same procedure as in Example 1 was performed to obtain a heat insulating and heat insulating substrate (C15).
The results are shown in Table 2.

[Comparative Example 16]
A protective top coat layer was formed in the same manner as in Example 1 except that the coordination bond type material was not used to obtain a heat insulating and heat insulating substrate (C16).
The results are shown in Table 2.

[Comparative Example 17]
Instead of a 50 μm thick polyethylene terephthalate film substrate (trade name “Lumirror U48”, visible light transmittance 93%) as a transparent substrate layer, a 3 mm thick float plate glass (manufactured by Matsunami Glass, visible light transmittance 91) %) Was performed in the same manner as in Comparative Example 1 to obtain a heat insulating and heat insulating substrate (C17).
The results are shown in Table 2.

[Comparative Example 18]
Instead of a 50 μm thick polyethylene terephthalate film substrate (trade name “Lumirror U48”, visible light transmittance 93%) as a transparent substrate layer, a 3 mm thick float plate glass (manufactured by Matsunami Glass, visible light transmittance 91) %) Was carried out in the same manner as in Comparative Example 10 to obtain a heat insulating and heat insulating substrate (C18).
The results are shown in Table 2.

[Comparative Example 19]
Instead of a 50 μm thick polyethylene terephthalate film substrate (trade name “Lumirror U48”, visible light transmittance 93%) as a transparent substrate layer, a 3 mm thick float plate glass (manufactured by Matsunami Glass, visible light transmittance 91) %) Was carried out in the same manner as in Comparative Example 11 to obtain a heat insulating and heat insulating substrate (C19).
The results are shown in Table 2.

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

DESCRIPTION OF SYMBOLS 10 Transparent substrate layer 20 Infrared reflective layer 21 Metal layer 22a First metal oxide layer 22b Second metal oxide layer 30 Topcoat layer 40 Protective topcoat layer 60 Undercoat layer 70 Protective film 80 Adhesive layer 90 Heating appliance 100 Insulation Thermal insulation board 1000 window

Claims (8)

1. A heat insulating and heat insulating substrate including a transparent substrate layer and an infrared reflective layer,
   A top coat layer and a protective top coat layer are provided on the opposite side of the infrared reflective layer to the transparent substrate layer,
   The topcoat layer is an oxide or nitride, oxynitride, or non-oxynitride mainly composed of one or more of Group 13 or Group 14 of the Periodic Table, Group 3 or Group 4 of the Periodic Table Including one or more ingredients of
   The protective topcoat layer comprises a coordination bond material;
   Thermal insulation board.
2. The heat-insulating and heat-insulating substrate according to claim 1, wherein the protective topcoat layer does not have a softening temperature within a range of 30 ° C to 75 ° C.
3. The heat insulating and heat insulating substrate according to claim 1 or 2, wherein the top coat layer is disposed between the infrared reflective layer and the protective top coat layer.
4. The heat-insulating and heat-insulating substrate according to claim 3, wherein the infrared reflective layer, the top coat layer, and the protective top coat layer are directly laminated in this order.
5. The heat-insulating and heat-insulating substrate according to any one of claims 1 to 4, wherein the thickness of the top coat layer is 0.5 nm to 500 nm.
6. The heat-insulating and heat-insulating substrate according to any one of claims 1 to 5, wherein the protective topcoat layer has a thickness of 5 nm to 500 nm.
7. The topcoat layer includes at least one selected from an oxide or oxynitride containing Si and Zr, an oxide or oxynitride containing Si and Y, an oxide or oxynitride containing Si and Ti, The heat insulation heat insulation board | substrate in any one of Claim 1-6.
8. The heat-insulating and heat-insulating substrate according to any one of claims 1 to 7, wherein the topcoat layer is a layer formed by a dry process, and the protective topcoat layer is a layer formed by coating.
   
   

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