WO2018181424A1 - Heat-shielding and heat-insulating substrate - Google Patents

Heat-shielding and heat-insulating substrate Download PDF

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Publication number
WO2018181424A1
WO2018181424A1 PCT/JP2018/012643 JP2018012643W WO2018181424A1 WO 2018181424 A1 WO2018181424 A1 WO 2018181424A1 JP 2018012643 W JP2018012643 W JP 2018012643W WO 2018181424 A1 WO2018181424 A1 WO 2018181424A1
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Prior art keywords
layer
heat
insulating substrate
heat insulating
insulating
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PCT/JP2018/012643
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French (fr)
Japanese (ja)
Inventor
聖彦 渡邊
雄太 島▲崎▼
浩史 別府
祐輔 山本
友広 紺谷
Original Assignee
日東電工株式会社
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Priority claimed from JP2018059381A external-priority patent/JP7145629B2/en
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Publication of WO2018181424A1 publication Critical patent/WO2018181424A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting filters

Definitions

  • the present invention relates to a heat insulating 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.
  • 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.
  • 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.
  • 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 topcoat layer is 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 Of one or more ingredients.
  • the infrared reflective layer and the topcoat layer are directly laminated.
  • the top coat layer has a thickness of 0.5 nm to 500 nm.
  • 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
  • substrate of this invention It is a schematic sectional drawing which shows one embodiment of the thermal insulation heat 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 topcoat layer on the opposite side of the infrared reflective layer to the transparent substrate layer.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of a heat insulating and heat insulating substrate of the present invention.
  • the heat insulating and heat insulating substrate 100 includes a transparent substrate layer 10, an infrared reflective layer 20, and a topcoat layer 30.
  • the heat-insulating and heat-insulating substrate of the present invention is the opposite side of the transparent substrate layer 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 the infrared reflective layer of the top coat layer.
  • Each of the opposite sides may be provided with any suitable other layers as required.
  • Such other layers may be one layer or two or more layers.
  • 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.
  • the heat insulating and heat insulating substrate 100 includes a transparent substrate layer 10, an undercoat layer 60, an antireflection layer 50, an infrared reflection layer 20, a topcoat layer 30, and a protective film 70.
  • 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.
  • the heat-insulating and heat-insulating substrate of the present invention includes a transparent substrate layer 10, an undercoat layer 60, an antireflection layer 50, an infrared reflection layer 20, a topcoat layer 30, and a protective film. 70 are 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).
  • the transparent substrate layer is preferably a transparent plate member, a transparent film, or a composite thereof.
  • 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, and particularly preferably. Is from 1.5 mm to 18 mm, most preferably from 2 mm to 12 mm.
  • the thickness of the transparent substrate layer is preferably 5 ⁇ m to 500 ⁇ m, more preferably 10 ⁇ m to 300 ⁇ m, still more preferably 20 ⁇ m to 200 ⁇ m, and particularly preferably 30 ⁇ m to 100 ⁇ m. .
  • 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.
  • 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 ⁇ m to 5 ⁇ m, more preferably 0.2 ⁇ m to 5 ⁇ m, still more preferably 0.2 ⁇ m to 3 ⁇ m, and particularly preferably 0.5 ⁇ m to 3 ⁇ m. Most preferably, it is 1 ⁇ m to 2 ⁇ m. 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.
  • 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.
  • Surface modification treatment such as treatment by the above may be performed.
  • Antireflection layer may be provided between the transparent substrate layer and the infrared reflective layer.
  • the antireflection 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
  • 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.
  • 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.
  • a film forming method of the antireflection layer a film forming method by a direct current sputtering method is preferable.
  • Infrared reflective 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.
  • 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.
  • 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.
  • the metal layer is preferably a silver alloy layer mainly composed of silver or a gold alloy layer mainly composed of gold.
  • 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.
  • 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 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.
  • the metal layer 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.
  • 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 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 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 is particularly preferably a composite metal oxide containing zinc oxide.
  • the content of zinc oxide in the 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 the total 100 parts by weight of the metal oxide. Less than parts by weight.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • the impurities may be mixed in the antireflection layer to be formed, or the composition of the layer may be different from the stoichiometric composition, but there is no problem as long as the effect of the present invention is exhibited.
  • an embodiment of a base material layer described in JP-A-2014-30910 can be used.
  • Topcoat layer >> The heat-insulating and heat-insulating substrate of the present invention can exhibit excellent scratch resistance by having a specific topcoat layer, and particularly has high steel wool scratch resistance.
  • the heat-insulating and heat-insulating substrate of the present invention preferably has high transparency by having a specific topcoat layer.
  • the heat-insulating and heat-insulating substrate of the present invention preferably has high cotton scratch resistance 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%.
  • 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.
  • 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.
  • any appropriate method can be adopted as a method for forming the topcoat layer.
  • 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 film formation method for the top coat layer is preferably a film formation method by direct current sputtering.
  • 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.
  • a protective top coat layer may be provided on the side of the top coat layer opposite to the infrared reflective layer.
  • the protective topcoat layer can cause the heat-insulating and heat-insulating substrate of the present invention to exhibit better scratch resistance.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a material for the protective top coat layer a material having high visible light transmittance and excellent mechanical strength and chemical strength is preferable.
  • 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.
  • the organic resin examples 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.
  • the inorganic material examples 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.
  • 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.
  • 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.
  • 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.
  • the adhesiveness of a topcoat layer and a protective topcoat layer improves, the intensity
  • the coordination bond material is preferably a compound having a group having a lone electron pair.
  • 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.
  • 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.
  • 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).
  • phosphoric acid monoester and phosphoric acid diester can also be used together.
  • 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.
  • 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.
  • X represents a hydrogen atom or a methyl group
  • (Y) represents an —OCO (CH 2 ) 5 — group.
  • n is 0 or 1
  • 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.
  • a crosslinked structure be introduced.
  • the mechanical strength and chemical strength of the protective topcoat layer are increased, and the protective function for the infrared reflective layer is increased.
  • 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
  • additives such as an antistatic agent may be contained. As content of these additives, arbitrary appropriate content can be employ
  • any appropriate forming method can be adopted as long as the effects of the present invention are not impaired.
  • a forming method for example, a solution of a material for the protective topcoat layer is applied on the topcoat layer, and after the solvent is dried, it is cured by irradiation with ultraviolet rays or electron beams, or application of thermal energy. A method is mentioned.
  • 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 ⁇ m to 150 ⁇ m, more preferably 25 ⁇ m to 100 ⁇ m, still more preferably 30 ⁇ m to 75 ⁇ m, particularly preferably 35 ⁇ m to 65 ⁇ m, and most preferably 35 ⁇ m to 50 ⁇ m.
  • 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.
  • the adhesive layer those having a high visible light transmittance and a small refractive index difference from the transparent substrate layer are preferable.
  • 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.
  • the adhesive layer 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.
  • the adhesive layer preferably contains an ultraviolet absorber.
  • 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.
  • a separator can prevent contamination due to contact with the outside of the exposed surface of the adhesive layer in a usual handling state.
  • 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.
  • 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.
  • 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.
  • VIS visible light
  • NIR near-infrared light
  • 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
  • FIR far infrared rays
  • 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.
  • 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.
  • 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.
  • a transparent plate member for example, glass, acrylic plate, polycarbonate plate, etc.
  • 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.
  • 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.
  • the film thickness of the top coat layer, metal oxide layer, metal layer, and antireflection layer is measured using a focused ion beam processing and observation device (manufactured by Hitachi, Ltd., product name “FB-2100”).
  • the sample was processed by the above method, and the cross section was obtained by observing with a field emission transmission electron microscope (manufactured by Hitachi, Ltd., product name “HF-2000”).
  • the film thickness of the undercoat layer is obtained by calculation from the interference pattern of the reflectance of visible light when light is incident from the measurement target side using an instantaneous multi-photometry system (manufactured by Otsuka Electronics, product name “MCPD3000”). It was.
  • ⁇ 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 ⁇ m (product name “HJ-9150W” manufactured by Nitto Denko Corporation).
  • an adhesive layer with a thickness of 25 ⁇ m (product name “HJ-9150W” manufactured by Nitto Denko Corporation).
  • ⁇ : Emissivity is 0.20 or more and less than 0.40.
  • ⁇ 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 ⁇ m (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.
  • Double-circle The surface does not have a flaw and peeling does not occur. ⁇ : Some scratches are observed on the surface, but no peeling occurs. X: Many scratches and peelings are observed on the surface.
  • Step 2 ⁇ 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 ⁇ m (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.
  • ⁇ Some scratches are observed on the surface, but no peeling occurs.
  • X Many scratches and peelings are observed on the surface.
  • ⁇ Cross-cut peel test> The adhesion in the heat-insulating and heat-insulating substrate was evaluated by a cross-cut peel test in accordance with JIS K5600-5-6: 1999. More specifically, after the thermal insulation board for measurement is allowed to stand at room temperature for 24 hours, the surface of the top coat layer of the thermal insulation board is cut into 10 vertical and horizontal cuts at 1 mm intervals to form 100 grids. The cellophane pressure-sensitive adhesive tape was completely attached to the film, and one end of the tape was instantaneously separated, and the evaluation was made according to the following classifications 0 to 5 according to the number of grids in which the coating film in the grid was peeled off.
  • the heat insulating and heat insulating films included in the categories 0 to 1 were evaluated as good (indicated by ⁇ ), and the heat insulating and heat insulating films included in the categories 2 to 5 were evaluated as defective (indicated by “ ⁇ ”).
  • the actual measured values of temperature and humidity during the actual test were a temperature of 23 ° C. and a humidity of 50% RH.
  • Classification 0 The edge of the incision is completely smooth, and the coating film in any grid is not peeled off.
  • Classification 1 There is a small peeling of the coating film at the intersection of the cuts. It is clearly not more than 5% that the cut is affected.
  • Classification 2 The coating film is peeled along the edge of the cut and / or at the intersection.
  • Classification 3 The coating film is partially or completely peeled along the edge of the cut, and / or various portions of the grid are partially or completely peeled off. It is clearly over 15% that the cut is affected, but not more than 35%.
  • Classification 4 The coating film is largely or partially peeled along the edge of the cut, and / or some grids are partially or completely peeled off. It is clearly not more than 35% that the cut is affected.
  • Category 5 The case where the degree of peeling exceeds Category 4.
  • Example 1 (Formation of undercoat layer on transparent substrate layer) An acrylic UV curable hard coat layer (JSR, Z7540) is 2 ⁇ m thick on one side of a 50 ⁇ m 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.
  • a 6-nm thick SiC layer and a 30-nm-thick zinc-tin composite oxide (ZTO) are formed on the undercoat layer formed on the transparent substrate layer by direct current magnetron sputtering.
  • Layer, a 15 nm thick Ag—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.
  • a first metal oxide layer, a metal layer, a second metal oxide layer, and a top coat layer were formed in this order on the undercoat layer.
  • a silicon carbide target manufactured by Mitsubishi Materials
  • sputtering was performed at a power density of 2.67 W / cm 2 and a process pressure of 0.4 Pa.
  • the amount of gas introduced into the sputtering film forming chamber was adjusted so that Ar: O 2 was 98: 2 (volume ratio).
  • Ar: O 2 was 98: 2 (volume ratio).
  • 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.
  • 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.
  • the amount of gas introduced into the sputtering film forming chamber was adjusted so that Ar: O 2 was 60:40 (volume ratio).
  • a heat insulating and heat insulating substrate (1) having a configuration of metal oxide layer (thickness 30 nm) / topcoat layer (thickness 10 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.
  • the results are shown in Table 1.
  • 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 ⁇ m 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 ⁇ m 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 ⁇ m 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 ⁇ m 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 ⁇ m 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 ⁇ m 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 ⁇ m 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 ⁇ m 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 ⁇ m 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 topcoat layer to 100 nm, the same procedure as in Example 1 was carried out, and the transparent substrate layer (thickness 50 ⁇ m) / undercoat layer (thickness 2 ⁇ m) / antireflection layer (thickness 6 nm) / first metal oxide
  • Example 20 Except for changing the thickness of the topcoat layer to 400 nm, the same procedure as in Example 1 was carried out, and the transparent substrate layer (thickness 50 ⁇ m) / undercoat layer (thickness 2 ⁇ m) / antireflection layer (thickness 6 nm) / first metal oxide
  • Example 21 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 ⁇ m) / undercoat layer (thickness 2 ⁇ m) / antireflection layer (thickness 6 nm) / first metal oxide
  • Example 1 A heat insulating and heat insulating substrate (C1) 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.
  • Example 2 Except that the SiO 2 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 (C2). The results are shown in Table 2.
  • Example 3 A heat insulating and heat insulating substrate (C3) 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.
  • Example 6 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 (C6). 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.

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Abstract

Provided is a heat-shielding and heat-insulating substrate having excellent scratch resistance. The heat-shielding and heat-insulating substrate of the present invention comprising a transparent substrate layer and an infrared reflective layer is provided with a top coat layer on a side of the infrared reflective layer, said side being opposite to the transparent substrate layer, wherein the top coat layer is formed of an oxide, a nitride, an oxynitride, or a non-oxynitride having, as main components, one or more of Group XIII or XIV of the Periodic Table and includes one or more components of Group III or IV of the Periodic Table.

Description

遮熱断熱基板Thermal insulation board
　本発明は遮熱断熱基板に関する。 The present invention relates to a heat insulating and heat insulating substrate.
　遮熱断熱基板は、遮熱機能と断熱機能を兼ね備えた基板である。このような遮熱断熱基板は、例えば、窓ガラスに貼着された場合、赤外線反射機能によって、室外から室内への日射熱（近赤外線）の流入、および、室内から室外への暖房熱（遠赤外線）の流出を抑制することができ、年間を通じての室内の快適性の向上と省エネルギー効果の向上を実現することができる。 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.
　このような遮熱断熱基板として、近年、透明基板層と赤外線反射層を含む遮熱断熱基板が提案されている（特許文献１、２）。赤外線反射層は、例えば、金属層の両側に金属酸化物層を備える構成を有し、近赤外線の反射による遮熱性向上と遠赤外線の反射による断熱性向上を両立させることができる。 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.
　遮熱断熱基板自体や、窓ガラスに貼着した遮熱断熱基板は、通常使用時のひっかきや清掃時の拭き作業などによって表面に傷が付きやすい。 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.
特開２０１６－９３８９２号公報JP 2016-93892 A 特開２０１６－９４０１２号公報JP 2016-94012 A
　本発明の課題は、耐擦傷性に優れた遮熱断熱基板を提供することにある。 An object of the present invention is to provide a heat insulating and heat insulating substrate excellent in scratch resistance.
　本発明の遮熱断熱基板は、
　透明基板層と赤外線反射層を含む遮熱断熱基板であって、
　該赤外線反射層の該透明基板層と反対の側にトップコート層を備え、
　該トップコート層が、周期表第１３族または第１４族の１種以上が主成分となる酸化物または窒化物、酸化窒化物、非酸化窒化物であり、周期表第３族または第４族の１種以上の成分を含む。 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 topcoat layer is 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 Of one or more ingredients.
　一つの実施形態においては、上記赤外線反射層と上記トップコート層が直接に積層されてなる。 In one embodiment, the infrared reflective layer and the topcoat layer are directly laminated.
　一つの実施形態においては、上記トップコート層の厚みが０．５ｎｍ～５００ｎｍである。 In one embodiment, the top coat layer has a thickness of 0.5 nm to 500 nm.
　一つの実施形態においては、上記トップコート層が、ＳｉとＺｒを含む酸化物または酸化窒化物、ＳｉとＹを含む酸化物または酸化窒化物、ＳｉとＴｉを含む酸化物または酸化窒化物から選ばれる少なくとも１種を含む。 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
　本発明によれば、耐擦傷性に優れた遮熱断熱基板を提供することができる。 According to the present invention, it is possible to provide a heat insulating and heat insulating substrate excellent in scratch resistance.
本発明の遮熱断熱基板の一つの実施形態を示す概略断面図である。It is a schematic sectional drawing which shows one embodiment of the thermal insulation heat insulation board | substrate of this invention. 本発明の遮熱断熱基板の一つの実施形態を示す概略断面図である。It is a schematic sectional drawing which shows one embodiment of the thermal insulation heat insulation board | substrate of this invention. 本発明の遮熱断熱基板の使用形態の一例を模式的に表す断面図である。It is sectional drawing which represents typically an example of the usage condition of the heat insulation heat insulation board | substrate of this invention.
≪１．遮熱断熱基板の概要≫
　本発明の遮熱断熱基板は、透明基板層と赤外線反射層を含み、該赤外線反射層の該透明基板層と反対の側にトップコート層を備える。 << 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 topcoat layer on the opposite side of the infrared reflective layer to the transparent substrate layer.
　図１は、本発明の遮熱断熱基板の一つの実施形態を示す概略断面図である。図１において、遮熱断熱基板１００は、透明基板層１０と赤外線反射層２０とトップコート層３０とを備える。 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 reflective layer 20, and a topcoat layer 30.
　本発明の遮熱断熱基板は、透明基板層の赤外線反射層と反対の側、透明基板層と赤外線反射層との間、赤外線反射層とトップコート層との間、トップコート層の赤外線反射層と反対の側、のそれぞれに、必要に応じて、任意の適切な他の層を備えていてもよい。このような他の層は１層でもよいし、２層以上でもよい。また、このような他の層は、１種のみであってもよいし、２種以上であってもよい。 The heat-insulating and heat-insulating substrate of the present invention is the opposite side of the transparent substrate layer 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 the infrared reflective layer of the top coat layer. Each of the opposite sides may be provided with any suitable other layers as required. 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.
　図２は、本発明の遮熱断熱基板の一つの実施形態を示す概略断面図である。図２において、遮熱断熱基板１００は、透明基板層１０とアンダーコート層６０と反射防止層５０と赤外線反射層２０とトップコート層３０と保護フィルム７０とを備える。図２において、赤外線反射層２０は、第一金属酸化物層２２ａ、金属層２１、第二金属酸化物層２２ｂの３層からなる。図２に示す一つの実施形態においては、好ましくは、本発明の遮熱断熱基板は、透明基板層１０とアンダーコート層６０と反射防止層５０と赤外線反射層２０とトップコート層３０と保護フィルム７０とがこの順に直接に積層されてなる。 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 antireflection layer 50, an infrared reflection layer 20, a topcoat layer 30, 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 antireflection layer 50, an infrared reflection layer 20, a topcoat layer 30, and a protective film. 70 are directly laminated in this order.
　本発明の遮熱断熱基板は、透明基板層の赤外線反射層と反対の側に、粘着剤層を備えていてもよい。さらに、セパレータフィルムが、このような粘着剤層の表面に備えられていてもよい。 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.
　本発明の遮熱断熱基板の可視光線透過率は、好ましくは３０％以上であり、より好ましくは３０％～８５％であり、さらに好ましくは４５％～８０％であり、特に好ましくは５５％～８０％であり、最も好ましくは５５％～７５％である。なお、可視光線透過率は、ＪＩＳ－Ａ５７５９－２００８（建築窓ガラス用フィルム）に準じて測定される。 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．透明基板層≫
　透明基板層は、好ましくは、透明板状部材、透明フィルム、または、これらの複合体である。透明板状部材としては、例えば、ガラス、アクリル板、ポリカーボネート板などが挙げられる。透明フィルムは、好ましくは可撓性の透明フィルムである。透明基板層の可視光線透過率は、好ましくは１０％以上であり、より好ましくは８０％以上であり、さらに好ましくは８５％以上であり、特に好ましくは８８％以上であり、最も好ましくは９０％以上である。なお、可視光線透過率は、ＪＩＳ－Ａ５７５９－２００８（建築窓ガラス用フィルム）に準じて測定される。 ≪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).
　透明基板層の厚みは、透明基板層が透明板状部材の場合、好ましくは０．２ｍｍ～４０ｍｍであり、より好ましくは０．５ｍｍ～３０ｍｍであり、さらに好ましくは１ｍｍ～２４ｍｍであり、特に好ましくは１．５ｍｍ～１８ｍｍであり、最も好ましくは２ｍｍ～１２ｍｍである。 When the transparent substrate layer is a transparent plate member, 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, and particularly preferably. Is from 1.5 mm to 18 mm, most preferably from 2 mm to 12 mm.
　透明基板層の厚みは、透明基板層がフィルムの場合は、好ましくは５μｍ～５００μｍであり、より好ましくは１０μｍ～３００μｍであり、さらに好ましくは２０μｍ～２００μｍであり、特に好ましくは３０μｍ～１００μｍである。 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. .
　透明基板層がフィルムの場合、透明基板層を構成する材料としては、例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリカーボネート（ＰＣ）などが挙げられ、耐熱性に優れる等の観点から、ポリエチレンテレフタレート（ＰＥＴ）が好ましい。 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．アンダーコート層≫
　透明基板層の赤外線反射層の側の表面上には、アンダーコート層が備えられていてもよい。透明基板層の表面上にアンダーコート層が備えられていることにより、本発明の遮熱断熱基板の機械的強度が高められ得るとともに、本発明の遮熱断熱基板の耐擦傷性が高められ得る。 ≪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. .
　アンダーコート層の厚みは、好ましくは０．０１μｍ～５μｍであり、より好ましくは０．２μｍ～５μｍであり、さらに好ましくは０．２μｍ～３μｍであり、特に好ましくは０．５μｍ～３μｍであり、最も好ましくは１μｍ～２μｍである。アンダーコート層の厚みが上記範囲内にあれば、本発明の遮熱断熱基板の機械的強度が高められ得るとともに、本発明の遮熱断熱基板の耐擦傷性がより高められ得る。 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.
　アンダーコート層は、好ましくは硬化型樹脂の硬化被膜であり、例えば、任意の適切な紫外線硬化型樹脂の硬化被膜を透明基板層上に付設する方式により形成できる。アンダーコート層は、好ましくは、有機樹脂を含む樹脂組成物から形成される樹脂層であり、有機樹脂としては、例えば、紫外線硬化樹脂が挙げられる。有機樹脂としての紫外線硬化樹脂としては、例えば、アクリル系樹脂、シリコーン系樹脂、ポリエステル系樹脂、ウレタン系樹脂、アミド系樹脂、エポキシ系樹脂、オキセタン系樹脂などが挙げられる。 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.
　アンダーコート層の表面（透明基板層と反対の側）には、密着性向上等の目的で、コロナ処理、プラズマ処理、フレーム処理、オゾン処理、プライマー処理、グロー処理、ケン化処理、カップリング剤による処理などの表面改質処理が行われてもよい。 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．反射防止層≫
　透明基板層と赤外線反射層との間には、反射防止層が備えられていてもよい。反射防止層が備えられていることにより、本発明の遮熱断熱基板の透明性が向上し得る。また、反射防止層が備えられていることにより、本発明の遮熱断熱基板の密着性が向上し得る。 << 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.
　反射防止層の厚みは、好ましくは３０ｎｍ以下であり、より好ましくは１ｎｍ～３０ｎｍであり、さらに好ましくは１ｎｍ～２０ｎｍであり、特に好ましくは１ｎｍ～１５ｎｍである。 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.
　反射防止層の製膜方法としては、任意の適切な方法を採用し得る。このような製膜方法としては、例えば、スパッタ法、真空蒸着法、ＣＶＤ法、電子線蒸着法等のドライプロセスによる製膜方法が挙げられる。反射防止層の製膜方法としては、好ましくは、直流スパッタ法による製膜方法である。直流スパッタ法による製膜方法を採用する場合、複数の製膜室を備える巻取り式スパッタ装置を用いれば、これら複数層を１パスで形成することが可能となる。このため、反射防止層の生産性が大幅に向上し得るだけでなく、ひいては、本発明の遮熱断熱基板の生産性が大幅に向上し得る。 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．赤外線反射層≫
　赤外線反射層は、近赤外線の反射による遮熱性向上と遠赤外線の反射による断熱性向上を両立させることができる層であれば、任意の適切な層を採用し得る。 ≪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.
　赤外線反射層の一つの実施形態は、第一金属酸化物層、金属層、第二金属酸化物層をこの順に備え、第一金属酸化物層および第二金属酸化物層は金属層に直接積層されてなる。この実施形態においては、赤外線反射層は、好ましくは、第一金属酸化物層、金属層、第二金属酸化物層の３層からなり、第一金属酸化物層、金属層、第二金属酸化物層をこの順に備える。このような赤外線反射層の一つの実施形態は、例えば、特開２０１６－９３８９２号公報、特開２０１６－９４０１２号公報などに記載の実施形態を援用し得る。 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.
　金属層は、赤外線反射の中心的な役割を有する。積層数を増加させることなく可視光線透過率と近赤外線反射率を高める観点から、金属層は、好ましくは、銀を主成分とする銀合金層または金を主成分とする金合金層である。例えば、銀は高い自由電子密度を有するため、近赤外線・遠赤外線の高い反射率を実現することができる。したがって、赤外線反射層を構成する層の積層数が少ない場合でも、近赤外線の反射による遮熱性向上と遠赤外線の反射による断熱性向上を両立させることができる。 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.
　金属層が銀を主成分とする銀合金層である場合、金属層中の銀の含有割合は、好ましくは８５重量％～９９．９重量％であり、より好ましくは９０重量％～９９．８重量％であり、さらに好ましくは９５重量％～９９．７重量％であり、特に好ましくは９７重量％～９９．６重量％である。金属層中の銀の含有割合が高いほど、透過率および反射率の波長選択性を高め、可視光線透過率を高めることができる。一方、銀は、水分、酸素、塩素等が存在する環境下に暴露された場合や、紫外光や可視光が照射された場合に、酸化や腐食等の劣化を生じる場合がある。このため、金属層は、耐久性を高める目的で、銀以外の金属を含有する銀合金層であることが好ましく、具体的には、上記のように、金属層中の銀の含有割合が９９．９重量％以下であることが好ましい。 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.
　金属層が銀を主成分とする銀合金層である場合、金属層は、上記のように、耐久性を高める目的から、銀以外の金属を含有することが好ましい。金属層中の銀以外の金属の含有割合は、好ましくは０．１重量％～１５重量％であり、より好ましくは０．２重量％～１０重量％であり、さらに好ましくは０．３重量％～５重量％であり、特に好ましくは０．４重量％～３重量％である。銀以外の金属としては、例えば、パラジウム（Ｐｄ）、金（Ａｕ）、銅（Ｃｕ）、ビスマス（Ｂｉ）、ゲルマニウム（Ｇｅ）、ガリウム（Ｇａ）などが挙げられ、高い耐久性を付与できる観点から、パラジウム（Ｐｄ）が好ましい。 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.
　金属酸化物層（第一金属酸化物層および第二金属酸化物層）は、金属層との界面における可視光線の反射量を制御して、高い可視光線透過率と高い赤外線反射率とを両立させる等の目的で設けられる。金属酸化物層は、金属層の劣化を防止するための保護層としても機能し得る。赤外線反射層における反射および透過の波長選択性を高める観点から、金属酸化物層の可視光に対する屈折率は、好ましくは１．５以上であり、より好ましくは１．６以上であり、さらに好ましくは１．７以上である。 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.
　金属酸化物層（第一金属酸化物層および第二金属酸化物層）は、好ましくは、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｚｎ、Ａｌ、Ｇａ、Ｉｎ、Ｔｌ、Ｓｎ等の金属の酸化物、あるいはこれらの金属の複合酸化物を含む。金属酸化物層は、より好ましくは、酸化亜鉛を含有する複合金属酸化物を含む。金属酸化物層は、好ましくは非晶質である。金属酸化物層が酸化亜鉛を含有する非晶質層である場合、金属酸化物層自体の耐久性が高められるとともに、金属層に対する保護層としての作用が増大するため、金属層の劣化が抑制され得る。 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.
　金属酸化物層（第一金属酸化物層および第二金属酸化物層）は、特に好ましくは、酸化亜鉛を含有する複合金属酸化物である。この場合、金属酸化物層中（第一金属酸化物層および第二金属酸化物層のそれぞれ中）の酸化亜鉛の含有割合は、金属酸化物の合計１００重量部に対して、好ましくは３重量部以上であり、より好ましくは５重量部以上であり、さらに好ましくは７重量部以上である。酸化亜鉛の含有割合が上記範囲内にあれば、金属酸化物層が非晶質層となりやすく、耐久性が高められる傾向がある。一方、酸化亜鉛の含有割合が過度に大きいと、耐久性が低下したり、可視光線透過率が低下したりするおそれがある。そのため、金属酸化物層中の酸化亜鉛の含有割合は、金属酸化物の合計１００重量部に対して、好ましくは６０重量部以下であり、より好ましくは５０重量部以下であり、さらに好ましくは４０重量部以下である。 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 the total 100 parts by weight of the metal oxide. Less than parts by weight.
　酸化亜鉛を含有する複合金属酸化物としては、可視光線透過率、屈折率、耐久性の全てを満足し得る観点から、インジウム－亜鉛複合酸化物（ＩＺＯ）、亜鉛－錫複合酸化物（ＺＴＯ）、インジウム－錫－亜鉛複合酸化物（ＩＴＺＯ）が好ましい。これらの複合酸化物は、さらに、ＡｌやＧａ等の金属や、これらの金属の酸化物を含有していてもよい。 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.
　金属層および金属酸化物層（第一金属酸化物層および第二金属酸化物層）の厚みは、赤外線反射層が、可視光線を透過し近赤外線を選択的に反射するように、材料の屈折率等を勘案して適宜に設定され得る。金属層の厚みは、好ましくは５ｎｍ～５０ｎｍであり、より好ましくは５ｎｍ～２５ｎｍであり、さらに好ましくは１０ｎｍ～１８ｎｍである。金属酸化物層の厚み（第一金属酸化物層および第二金属酸化物層のそれぞれの厚み）は、好ましくは１ｎｍ～８０ｎｍであり、より好ましくは１ｎｍ～５０ｎｍであり、さらに好ましくは１ｎｍ～４０ｎｍであり、特に好ましくは２ｎｍ～３０ｎｍである。本発明の遮熱断熱基板は、好ましくは機械的強度が高められ得るので、金属酸化物層の厚み（第一金属酸化物層および第二金属酸化物層のそれぞれの厚み）を従来品レベルよりも薄くすることが可能となる。 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.
　金属層および金属酸化物層の製膜方法としては、任意の適切な方法を採用し得る。このような製膜方法としては、例えば、スパッタ法、真空蒸着法、ＣＶＤ法、電子線蒸着法等のドライプロセスによる製膜方法が挙げられる。金属層および金属酸化物層の製膜方法としては、好ましくは、直流スパッタ法による製膜方法である。直流スパッタ法による製膜方法を採用する場合、複数の製膜室を備える巻取り式スパッタ装置を用いれば、これら複数層を１パスで形成することが可能となる。このため、赤外線反射層の生産性が大幅に向上し得るだけでなく、ひいては、本発明の遮熱断熱基板の生産性が大幅に向上し得る。また、直流スパッタするターゲットは、導電性を付与するために導電性の不純物を添加されていてもよく、一部を還元性としてもよい。そのため、製膜される反射防止層にも該不純物が混入したり、層の組成が化学量論組成と異なったりする場合があるが、本発明の効果を奏する限りは問題とならない。 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. For this reason, the impurities may be mixed in the antireflection layer to be formed, or the composition of the layer may be different from the stoichiometric composition, but there is no problem as long as the effect of the present invention is exhibited.
　赤外線反射層の別の一つの実施形態としては、例えば、特開２０１４－３０９１０号公報に記載の基材層の実施形態を援用し得る。 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．トップコート層≫
　本発明の遮熱断熱基板は、特定のトップコート層を有することにより、優れた耐擦傷性を発現でき、特に、スチールウール耐擦傷性が高い。 ≪6. Topcoat layer >>
The heat-insulating and heat-insulating substrate of the present invention can exhibit excellent scratch resistance by having a specific topcoat layer, and particularly has high steel wool scratch resistance.
　本発明の遮熱断熱基板は、特定のトップコート層を有することにより、好ましくは、透明性が高い。本発明の遮熱断熱基板は、特定のトップコート層を有することにより、好ましくは、コットン耐擦傷性が高い。 The heat-insulating and heat-insulating substrate of the present invention preferably has high transparency by having a specific topcoat layer. The heat-insulating and heat-insulating substrate of the present invention preferably has high cotton scratch resistance by having a specific topcoat layer.
　トップコート層は、好ましくは、周期表第１３族または第１４族の１種以上が主成分となる酸化物または窒化物、酸化窒化物、非酸化窒化物であり、周期表第３族または第４族の１種以上の成分を含む。トップコート層は、より好ましくは、第１４族の１種以上が主成分となる酸化物または窒化物、酸化窒化物、非窒化物または非酸化物であり、周期表第３族または第４族の１種以上の成分を含む。トップコート層は、さらに好ましくは、ＳｉとＺｒを含む酸化物または酸化窒化物、ＳｉとＹを含む酸化物または酸化窒化物、ＳｉとＴｉを含む酸化物または酸化窒化物から選ばれる少なくとも１種を含む。トップコート層は、特に好ましくは、ＳｉとＺｒを含む酸化物、ＳｉとＹを含む酸化物、ＳｉとＴｉを含む酸化物から選ばれる少なくとも１種を含む。 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.
　第１４族の元素は最外殻電子が４つのためイオンになりにくい。第１３族の元素は最外殻電子が３つのため陰イオンになりにくい。そのため、窒化物、酸化窒化物、非窒化物または非酸化物の硬度が高くなると考察される。 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.
　周期表第３族または第４族の元素の添加は、主成分元素の結晶緻密化、分子構造の最密化などによって、強度の増加や耐腐食性、耐熱性を向上させる。 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.
　周期表第３族または第４族の元素の添加量は、本発明の効果をより発現させ得る点で、好ましくは０．０１ａｔｍ％～４９．９ａｔｍ％であり、より好ましくは０．０５ａｔｍ％～４０．０ａｔｍ％であり、さらに好ましくは０．１ａｔｍ％～４０．０ａｔｍ％であり、特に好ましくは０．５ａｔｍ％～３５．０ａｔｍ％である。周期表第３族または第４族の元素の添加量が少ない場合は、マトリックス全体に均一に元素が挿入されないために、本発明の効果が発現できないおそれがある。一方、周期表第３族または第４族の元素の添加量が多すぎる場合は、主成分との相溶性が悪くなり、本発明の効果が発現できないおそれがある。相溶性は相図によって確認することができる。 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.
　トップコート層の厚みは、好ましくは０．５ｎｍ～３０ｎｍであり、より好ましくは１ｎｍ～２５ｎｍであり、さらに好ましくは２ｎｍ～２０ｎｍであり、特に好ましくは３ｎｍ～１５ｎｍである。トップコート層の厚みが上記範囲内にあれば、本発明の遮熱断熱基板は、より優れた耐擦傷性を発現できる。 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.
　トップコート層の製膜方法としては、任意の適切な方法を採用し得る。このような製膜方法としては、例えば、スパッタ法、真空蒸着法、ＣＶＤ法、電子線蒸着法等のドライプロセスによる製膜方法が挙げられる。トップコート層の製膜方法としては、好ましくは、直流スパッタ法による製膜方法である。直流スパッタ法による製膜方法を採用する場合、複数の製膜室を備える巻取り式スパッタ装置を用いれば、これら複数層を１パスで形成することが可能となる。このため、トップコート層の生産性が大幅に向上し得るだけでなく、ひいては、本発明の遮熱断熱基板の生産性が大幅に向上し得る。 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 by a dry process such as a sputtering method, a vacuum evaporation method, a CVD method, and an electron beam evaporation method. The film formation method for the top coat layer is preferably a film formation method by direct current sputtering. 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.
≪７．保護トップコート層≫
　トップコート層の赤外線反射層と反対の側には、保護トップコート層が備えられていてもよい。保護トップコート層は、本発明の遮熱断熱基板に、より優れた耐擦傷性を発現させ得る。 ≪7. Protective topcoat layer >>
A protective top coat layer may be provided on the side of the top coat layer opposite to the infrared reflective layer. The protective topcoat layer can cause the heat-insulating and heat-insulating substrate of the present invention to exhibit better scratch resistance.
　保護トップコート層は、高い可視光線の透過率を有することが好ましい。 The protective topcoat layer preferably has a high visible light transmittance.
　保護トップコート層は、遠赤外線の吸収が小さいことが好ましい。保護トップコート層において遠赤外線の吸収が小さいと、室内の遠赤外線が赤外線反射層によって室内に反射されるため、断熱効果が高められ得る。保護トップコート層による遠赤外線吸収量を小さくする方法としては、保護トップコート層の材料として遠赤外線の吸収率が小さいものを用いる方法、保護トップコート層の厚みを小さくする方法などが挙げられる。一方、保護トップコート層において遠赤外線の吸収が大きいと、室内の遠赤外線が保護トップコート層で吸収され、赤外線反射層によって反射されることなく、熱伝導により外部に放熱されるため、断熱性が低下するおそれがある。 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.
　保護トップコート層の材料として遠赤外線の吸収率が小さいものを用いれば、保護トップコート層の厚みが大きい場合でも、遠赤外線吸収量を小さく保つことができ、赤外線反射層に対する保護効果を高めることができる。遠赤外線の吸収が小さい保護トップコート層の材料としては、Ｃ＝Ｃ結合、Ｃ＝Ｏ結合、Ｃ－Ｏ結合、芳香族環などの含有量が小さい化合物が好適に用いられる。このような化合物としては、例えば、ポリエチレン、ポリプロピレン等のポリオレフィンや、シクロオレフィン系ポリマー等の脂環式ポリマー、ゴム系ポリマーなどが挙げられる。 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.
　保護トップコート層は、遠赤外線吸収量を小さくする観点から、その厚みは、好ましくは５００ｎｍ以下であり、より好ましくは３００ｎｍ以下であり、さらに好ましくは２００ｎｍ以下であり、さらに好ましくは１５０ｎｍ以下であり、特に好ましくは１２０ｎｍ以下であり、最も好ましくは１００ｎｍ以下である。保護トップコート層の光学膜厚（屈折率と物理的な膜厚の積）が可視光の波長範囲と重複すると、界面での多重反射干渉によって、本発明の遮熱断熱基板の表面が虹模様に見える「虹彩現象」を生じる場合がある。一般的な樹脂の屈折率は１．５程度であるため、虹彩現象を抑制する観点からも保護トップコート層の厚みは２００ｎｍ以下であることがさらに好ましい。 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.
　保護トップコート層は、それに機械的強度および化学的強度を付与するとともに、本発明の遮熱断熱基板の耐久性を高める観点から、その厚みは、好ましくは５ｎｍ以上であり、より好ましくは１５ｎｍ以上であり、さらに好ましくは３０ｎｍ以上であり、特に好ましくは５０ｎｍ以上である。 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.
　保護トップコート層の厚みが上記範囲内にあれば、保護トップコート層の表面側での反射光と赤外線反射層側界面での反射光との多重反射干渉により、可視光線の反射率を低下させることができる。そのため、赤外線反射層の光吸収による反射率低下効果に加えて、保護トップコート層による反射防止効果が得られ、本発明の遮熱断熱基板の視認性がさらに高められ得る。 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.
　保護トップコート層の材料としては、可視光線透過率が高く、機械的強度および化学的強度に優れるものが好ましい。保護トップコート層の材料としては、例えば、有機樹脂、無機材料、有機成分と無機成分が化学結合した有機無機ハイブリッド材料などが挙げられる。有機樹脂は、１種のみであってもよいし、２種以上であってもよい。無機材料は、１種のみであってもよいし、２種以上であってもよい。有機無機ハイブリッド材料は、１種のみであってもよいし、２種以上であってもよい。 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.
　有機樹脂としては、例えば、活性光線硬化型あるいは熱硬化型の有機樹脂が挙げられ、具体的には、例えば、フッ素系樹脂、アクリル系樹脂、ウレタン系樹脂、エステル系樹脂、エポキシ系樹脂、シリコーン系樹脂などが挙げられる。本発明の効果をより発現させ得る点で、有機樹脂としては、好ましくは、アクリル系樹脂である。 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.
　無機材料としては、例えば、酸化シリコン、窒化シリコン、酸化窒化シリコン、酸化アルミニウム、酸化チタン、酸化ジルコニウム、サイアロン（ＳｉＡｌＯＮ）などが挙げられる。 Examples of the inorganic material include silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, titanium oxide, zirconium oxide, and sialon (SiAlON).
　保護トップコート層としては、好ましくは、有機樹脂を含む樹脂組成物から形成される樹脂層、有機無機ハイブリッド材料を含む組成物から形成される樹脂層が挙げられ、より好ましくは、有機樹脂を含む樹脂組成物から形成される樹脂層が挙げられる。 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.
　保護トップコート層は、好ましくは、配位結合型材料を含む。配位結合型材料としては、他の化合物と配位結合を形成し得る材料であれば、本発明の効果を損なわない範囲で、任意の適切な配位結合型材料を採用し得る。配位結合型材料は、１種のみであってもよいし、２種以上であってもよい。保護トップコート層が配位結合型材料を含むことにより、例えば、トップコート層が該保護トップコート層と直接に積層されている場合に、これらの２層の間に配位結合性の結合力が発現して密着性が向上し得る。特に、トップコート層が金属酸化物を含有する場合、保護トップコート層中の酸性基がトップコート層中の金属酸化物と配位結合性の高い親和力を発現し得る。また、トップコート層と保護トップコート層との密着性が向上することにより、表面保護層の強度が向上し得るため、赤外線反射層の耐久性を高め得る。 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.
　配位結合型材料としては、好ましくは、孤立電子対を持つ基を有する化合物であり、該孤立電子対を持つ基としては、例えば、リン原子、硫黄原子、酸素原子、窒素原子などの配位原子を有する基が挙げられ、具体的には、例えば、リン酸基、硫酸基、チオール基、カルボキシル基、アミノ基などが挙げられる。 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.
　配位結合型材料は、好ましくは、金属イオンとの作用によって密着力を高め得る。配位結合型材料は、他の樹脂材料等との密着力を高めるために、反応性基を有していてもよい。 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.
　配位結合型材料としては、好ましくは、酸性基と重合性官能基とを同一分子中に有するエステル化合物が挙げられる。 Preferred examples of the coordinate bond material include ester compounds having an acidic group and a polymerizable functional group in the same molecule.
　酸性基と重合性官能基とを同一分子中に有するエステル化合物としては、リン酸、硫酸、シュウ酸、コハク酸、フタル酸、フマル酸、マレイン酸等の多価の酸と、エチレン性不飽和基、シラノール基、エポキシ基等の重合性官能基と水酸基とを分子中に有する化合物とのエステルが挙げられる。なお、このようなエステル化合物は、ジエステルやトリエステル等の多価エステルでもよいが、多価の酸の少なくとも１つの酸性基がエステル化されていないことが好ましい。 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.
　保護トップコート層の機械的強度および化学的強度を高める観点から、酸性基と重合性官能基とを同一分子中に有するエステル化合物は、重合性官能基として（メタ）アクリロイル基を含有することが好ましい。酸性基と重合性官能基とを同一分子中に有するエステル化合物は、分子中に複数の重合性官能基を有していてもよい。酸性基と重合性官能基とを同一分子中に有するエステル化合物としては、好ましくは、一般式（Ａ）で表される、リン酸モノエステル化合物またはリン酸ジエステル化合物が挙げられる。なお、リン酸モノエステルとリン酸ジエステルとを併用することもできる。酸性基と重合性官能基とを同一分子中に有するエステル化合物として、一般式（Ａ）で表される、リン酸モノエステル化合物またはリン酸ジエステル化合物を採用すると、リン酸ヒドロキシ基は金属酸化物との親和性に優れるため、トップコート層が保護トップコート層と直接に積層されている場合であって該トップコート層が金属酸化物を含有する場合、これらの２層の間の密着性がより向上し得る。 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.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　一般式（Ａ）中、Ｘは水素原子またはメチル基を表し、（Ｙ）は－ＯＣＯ（ＣＨ２）５－基を表す。ｎは０または１であり、ｐは１または２である。 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.
　保護トップコート層中の配位結合型材料の含有割合は、好ましくは１重量％～２０重量％であり、より好ましくは１．５重量％～１７．５重量％であり、さらに好ましくは２重量％～１５重量％であり、特に好ましくは２．５重量％～１２．５重量％である。保護トップコート層中の配位結合型材料の含有割合が過度に小さいと、強度や密着性の向上効果が十分に得られないおそれがある。保護トップコート層中の配位結合型材料の含有割合が過度に大きいと、保護トップコート層形成時の硬化速度が小さくなって硬度が低下したりするおそれや、保護トップコート層表面の滑り性が低下して耐擦傷性が低下したりするおそれがある。 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.
　保護トップコート層の材料として有機樹脂あるいは有機・無機ハイブリッド材料が用いられる場合、架橋構造が導入されることが好ましい。架橋構造が形成されることによって、保護トップコート層の機械的強度および化学的強度が高められ、赤外線反射層に対する保護機能が増大する。このような架橋構造の中でも、酸性基と重合性官能基とを同一分子中に有するエステル化合物に由来する架橋構造が導入されることが好ましい。 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.
　保護トップコート層の材料には、シランカップリング剤、チタンカップリング剤等のカップリング剤、レベリング剤、紫外線吸収剤、酸化防止剤、熱安定剤、滑剤、可塑剤、着色防止剤、難燃剤、帯電防止剤等の添加剤が含まれていてもよい。これらの添加剤の含有量としては、本発明の効果を損なわない範囲で任意の適切な含有量を採用し得る。 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.
　保護トップコート層の形成方法としては、本発明の効果を損なわない範囲で任意の適切な形成方法を採用し得る。このような形成方法としては、例えば、保護トップコート層の材料の溶液をトップコート層上に塗布し、溶媒を乾燥させた後、紫外線や電子線等の照射や熱エネルギーの付与によって、硬化させる方法が挙げられる。 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 solution of a material for the protective topcoat layer is applied on the topcoat layer, and after the solvent is dried, it is cured by irradiation with ultraviolet rays or electron beams, or application of thermal energy. A method is mentioned.
≪８．保護フィルム≫
　保護トップコート層のトップコート層と反対の側には、保護フィルムが備えられていてもよい。 ≪8. Protective film >>
A protective film may be provided on the side of the protective topcoat layer opposite to the topcoat layer.
　保護フィルムの厚みは、好ましくは１０μｍ～１５０μｍであり、より好ましくは２５μｍ～１００μｍであり、さらに好ましくは３０μｍ～７５μｍであり、特に好ましくは３５μｍ～６５μｍであり、最も好ましくは３５μｍ～５０μｍである。 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．その他の構成部材≫
　透明基板層の赤外線反射層と反対の側には、接着剤層が備えられていてもよい。接着剤層は、例えば、窓ガラス等との貼り合せに用いられ得る。 ≪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.
　接着剤層としては、可視光線透過率が高く、透明基板層との屈折率差が小さいものが好ましい。接着剤層の材料としては、本発明の効果を損なわない範囲で任意の適切な材料を採用し得る。このような材料としては、例えば、アクリル系粘着剤（アクリル系感圧接着剤）が挙げられる。アクリル系粘着剤（アクリル系感圧接着剤）は、光学的透明性に優れ、適度な濡れ性と凝集性と接着性を示し、耐候性や耐熱性等に優れることから、接着剤層の材料として好適である。 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.
　接着剤層としては、可視光線の透過率が高く、かつ、紫外線透過率が小さいものが好ましい。接着剤層の紫外線透過率を小さくすることにより、太陽光等の紫外線に起因する赤外線反射層の劣化を抑制し得る。接着剤層の紫外線透過率を小さくする観点から、接着剤層は紫外線吸収剤を含有することが好ましい。なお、紫外線吸収剤を含有する透明基板層等を用いることによっても、屋外からの紫外線に起因する赤外線反射層の劣化を抑制し得る。 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.
　接着剤層の露出面は、本発明の遮熱断熱基板が実用に供されるまでの間、露出面の汚染防止等を目的として、セパレータが仮着されてカバーされていることが好ましい。このようなセパレータにより、通例の取扱状態で、接着剤層の露出面の外部との接触による汚染を防止し得る。 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．遮熱断熱基板の用途≫
　本発明の遮熱断熱基板は、建物や乗り物等の窓、植物等を入れる透明ケース、冷凍もしくは冷蔵のショーケース等に用いることができ、冷暖房効果の向上や急激な温度変化を防ぐ作用を有し得る。 << 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.
　図３は、本発明の遮熱断熱基板の使用形態の一例を模式的に表す断面図である。この使用形態において、本発明の遮熱断熱基板１００は、透明基板層１０側が、任意の適切な接着剤層８０を介して、建物や自動車の窓１０００の室内側に貼り合せて配置される。図３に模式的に示すように、本発明の遮熱断熱基板１００は、屋外からの可視光（ＶＩＳ）を透過して室内に導入するとともに、屋外からの近赤外線（ＮＩＲ）を赤外線反射層２０で反射する。近赤外線反射により、太陽光等に起因する室外からの熱の室内への流入が抑制される（遮熱効果が発揮される）ため、例えば、夏場の冷房効率を高めることができる。さらに、赤外線反射層２０は、暖房器具９０から放射される室内の遠赤外線（ＦＩＲ）を反射するため、断熱効果が発揮され、冬場の暖房効率を高めることができる。また、本発明の遮熱断熱基板１００は、赤外線反射層２０を備えることにより可視光の反射率が低減されるため、ショーケースやショーウィンドウ等に用いた場合に、商品等の視認性を低下させることなく、遮熱性と断熱性を付与することができる。 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.
　本発明の遮熱断熱基板は、例えば、特開２０１３－６１３７０号公報に開示されているように、枠体等に嵌め込んで用いることもできる。このような形態では、接着剤層を設ける必要がないため、接着剤層による遠赤外線の吸収が生じない。このため、透明基板層として、例えば、Ｃ＝Ｃ結合、Ｃ＝Ｏ結合、Ｃ－Ｏ結合、芳香族環等の官能基の含有量が少ない材料（例えば、環状ポリオレフィン）を用いることにより、透明基板層側からの遠赤外線を赤外線反射層で反射させることができ、本発明の遮熱断熱基板の両面側に断熱性を付与できる。このような構成は、例えば、冷蔵ショーケースや冷凍ショーケース等で特に有用である。 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.
　本発明の遮熱断熱基板は、透明基板層が、例えば、透明板状部材（例えば、ガラス、アクリル板、ポリカーボネート板など）や、該透明板状部材と透明フィルムの複合体である場合には、例えば、そのまま、建物や自動車の窓などに適用できる。 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.
　以下、実施例により本発明を具体的に説明するが、本発明はこれら実施例になんら限定されるものではない。なお、実施例等における、試験および評価方法は以下のとおりである。なお、「部」と記載されている場合は、特記事項がない限り「重量部」を意味し、「％」と記載されている場合は、特記事項がない限り「重量％」を意味する。 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.
＜各層の膜厚＞
　トップコート層、金属酸化物層、金属層、反射防止層の膜厚は、集束イオンビーム加工観察装置（日立製作所製、製品名「ＦＢ－２１００」）を用いて、集束イオンビーム（ＦＩＢ）法により試料を加工し、その断面を、電界放出形透過電子顕微鏡（日立製作所製、製品名「ＨＦ－２０００」）により観察して求めた。
　アンダーコート層の膜厚は、瞬間マルチ測光システム（大塚電子製、製品名「ＭＣＰＤ３０００」）を用い、測定対象側から光を入射させた際の可視光の反射率の干渉パターンから、計算により求めた。 <Thickness of each layer>
The film thickness of the top coat layer, metal oxide layer, metal layer, and antireflection layer is measured using a focused ion beam processing and observation device (manufactured by Hitachi, Ltd., product name “FB-2100”). The sample was processed by the above method, and the cross section was obtained by observing with a field emission transmission electron microscope (manufactured by Hitachi, Ltd., product name “HF-2000”).
The film thickness of the undercoat layer is obtained by calculation from the interference pattern of the reflectance of visible light when light is incident from the measurement target side using an instantaneous multi-photometry system (manufactured by Otsuka Electronics, product name “MCPD3000”). It was.
＜放射率＞
　測定用の遮熱断熱基板を室温に２４時間放置し、その遮熱断熱基板の透明基板層側の面を、厚み２５μｍの粘着剤層（日東電工社製、製品名「ＨＪ－９１５０Ｗ」）を介して厚み３ｍｍのフロート板ガラス（松浪硝子製）に貼り合せたものを試料として用い、放射率計（Ｄｅｖｉｃｅｓ　ａｎｄ　Ｓｅｒｖｉｃｅｓ社製、Ｍｏｄｅｌ　ＡＥ１）を用いて赤外線反射層の透明基板層と反対の側を測定した。なお、実際の試験の際の温度、湿度の実測値は、温度２３℃、湿度５０％ＲＨであった。
〇：放射率が０．２０以下。
△：放射率が０．２０以上０．４０未満。
×：放射率が０．４０以上。 <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.
＜コットン耐擦傷性試験＞
　測定用の遮熱断熱基板を室温に２４時間放置し、その遮熱断熱基板の透明基板層側の面を、厚み２５μｍの粘着剤層（日東電工社製、製品名「ＨＪ－９１５０Ｗ」）を介してアルミ板に貼り合せたものを試料として用いた。学振摩耗試験機を用いて、試験用綿布（金巾３号）で５００ｇの荷重を加えながら、アルミ板上の遮熱断熱基板の、赤外線反射層の透明基板層と反対の側の最表面を、１０００往復擦った。試験後の試料への傷、剥離の有無を目視で評価し、以下の評価基準に従い、評価した。なお、実際の試験の際の温度、湿度の実測値は、温度２３℃、湿度５０％ＲＨであった。
◎：表面に傷が認められず剥離が生じていないもの。
〇：表面に若干の傷が認められるが剥離は生じていないもの。
×：表面に多数の傷や剥離が認められるもの。 <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.
(Double-circle): The surface does not have a flaw and peeling does not occur.
○: Some scratches are observed on the surface, but no peeling occurs.
X: Many scratches and peelings are observed on the surface.
＜スチールウール（ＳＷ）耐擦傷性試験＞
　測定用の遮熱断熱基板を室温に２４時間放置した後、その透明基板層側の面を、厚み２５μｍの粘着剤層（日東電工社製、製品名「ＨＪ－９１５０Ｗ」）を介して厚み１．３ｍｍのガラス板に貼り合せたものを試料として用いた。１０連式ペン試験機を用いて、スチールウール（ボンスター製、＃００００）で１０００ｇの荷重を加えながら、ガラス板上の遮熱断熱基板の、赤外線反射層の透明基板層と反対の側の最表面を、１０往復擦った。試験後の試料への傷、剥離の有無を目視で評価し、以下の評価基準に従い、評価した。なお、実際の試験の際の温度、湿度の実測値は、温度２３℃、湿度５０％ＲＨであった。
〇：表面に傷が認められず剥離が生じていないもの。
△：表面に若干の傷が認められるが剥離は生じていないもの。
×：表面に多数の傷や剥離が認められるもの。 <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.
＜結露サイクル１８０回後のスチールウール（ＳＷ）耐擦傷性試験＞
　測定用の遮熱断熱基板を室温に２４時間放置した後、その透明基板層側の面を、厚み２５μｍの粘着剤層（日東電工社製、製品名「ＨＪ－９１５０Ｗ」）を介して厚み１．３ｍｍのガラス板に貼り合せたものを試料として用いた。結露サイクル試験機を用いて、試料を結露環境で保存した後、１０連式ペン試験機を用いて、スチールウール（ボンスター製、＃００００）で１０００ｇの荷重を加えながら、ガラス板上の遮熱断熱基板の、赤外線反射層の透明基板層と反対の側の最表面を、１０往復擦った。結露試験は、－１０℃で１０分間保存、５０℃９０％ＲＨで１０分間保存、常温（温度２３℃、湿度５０％ＲＨ）で１０分間保存を１サイクルとした。上記１サイクルを１８０回繰り返した。試験後の試料への傷、剥離の有無を目視で評価し、以下の評価基準に従い、評価した。
〇：表面に傷が認められず剥離が生じていないもの。
△：表面に若干の傷が認められるが剥離は生じていないもの。
×：表面に多数の傷や剥離が認められるもの。 <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.
＜碁盤目剥離試験＞
　遮熱断熱基板における密着性については、ＪＩＳ　Ｋ５６００‐５‐６：１９９９に準じて、碁盤目剥離試験によって評価した。より具体的には、測定用の遮熱断熱基板を室温に２４時間放置した後、その遮熱断熱基板のトップコート層表面に１ｍｍ間隔で縦横１０本ずつの切込みを入れて１００個の碁盤目を作成し、この上にセロハン粘着テープを完全に付着させ、テープの一端を瞬間的に引き離し、碁盤目内の塗膜が剥がれた碁盤目の個数により、以下の分類０～５に従って評価した。すなわち、分類０～１に含まれる遮熱断熱フィルムを良好と評価し（○と表示）、分類２～５に含まれる遮熱断熱フィルムを不良と評価した（「×」と表示）。なお、実際の試験の際の温度、湿度の実測値は、温度２３℃、湿度５０％ＲＨであった。
　分類０：切込みの縁が完全に滑らかで、どの碁盤目内の塗膜にも剥がれがない。
　分類１：切込みの交差点における塗膜の小さな剥がれがある。切れ込み部分で影響を受けるのは、明確に５％を上回ることはない。
　分類２：塗膜が切れ込みの縁に沿って、及び／又は交差点において剥がれている。切れ込み部分で影響を受けるのは、明確に５％を超えるが、１５％を上回ることはない。
　分類３：塗膜が切れ込みの縁に沿って、部分的又は全面的に大剥がれを生じており、及び／又は碁盤目の色々な部分が、部分的又は全面的に剥がれている。切れ込み部分で影響を受けるのは、明確に１５％を超えるが、３５％を上回ることはない。
　分類４：塗膜が切れ込みの縁に沿って、部分的又は全面的に大剥がれを生じており、及び／又は数箇所の碁盤目が、部分的又は全面的に剥がれている。切れ込み部分で影響を受けるのは、明確に３５％を上回ることはない。
　分類５：剥がれの程度が分類４を超える場合である。 <Cross-cut peel test>
The adhesion in the heat-insulating and heat-insulating substrate was evaluated by a cross-cut peel test in accordance with JIS K5600-5-6: 1999. More specifically, after the thermal insulation board for measurement is allowed to stand at room temperature for 24 hours, the surface of the top coat layer of the thermal insulation board is cut into 10 vertical and horizontal cuts at 1 mm intervals to form 100 grids. The cellophane pressure-sensitive adhesive tape was completely attached to the film, and one end of the tape was instantaneously separated, and the evaluation was made according to the following classifications 0 to 5 according to the number of grids in which the coating film in the grid was peeled off. That is, the heat insulating and heat insulating films included in the categories 0 to 1 were evaluated as good (indicated by ◯), and the heat insulating and heat insulating films included in the categories 2 to 5 were evaluated as defective (indicated by “×”). The actual measured values of temperature and humidity during the actual test were a temperature of 23 ° C. and a humidity of 50% RH.
Classification 0: The edge of the incision is completely smooth, and the coating film in any grid is not peeled off.
Classification 1: There is a small peeling of the coating film at the intersection of the cuts. It is clearly not more than 5% that the cut is affected.
Classification 2: The coating film is peeled along the edge of the cut and / or at the intersection. It is clearly over 5% but not more than 15% that is affected by the cut.
Classification 3: The coating film is partially or completely peeled along the edge of the cut, and / or various portions of the grid are partially or completely peeled off. It is clearly over 15% that the cut is affected, but not more than 35%.
Classification 4: The coating film is largely or partially peeled along the edge of the cut, and / or some grids are partially or completely peeled off. It is clearly not more than 35% that the cut is affected.
Category 5: The case where the degree of peeling exceeds Category 4.
〔実施例１〕
（透明基板層上へのアンダーコート層の形成）
　厚み５０μｍのポリエチレンテレフタレートフィルム基材（東レ製、商品名「ルミラーＵ４８」、可視光透過率９３％）の一方の面に、アクリル系紫外線硬化型ハードコート層（ＪＳＲ製、Ｚ７５４０）を２μｍの厚みで形成した。詳しくは、グラビアコーターにより、上記ハードコート層の溶液を塗布し、８０℃で乾燥後、超高圧水銀ランプにより積算光量３００ｍＪ／ｃｍ２の紫外線を照射し、硬化を行い、透明基板層上へアンダーコート層を形成した。
（反射防止層、第一金属酸化物層、金属層、第二金属酸化物層、トップコート層の形成）
　巻取式スパッタ装置を用いて、上記透明基板層上に形成されたアンダーコート層上に、直流マグネトロンスパッタ法により、膜厚６ｎｍのＳｉＣ層、膜厚３０ｎｍの亜鉛－錫複合酸化物（ＺＴＯ）層、膜厚１５ｎｍのＡｇ－Ｐｄ合金層、膜厚３０ｎｍの亜鉛－錫複合酸化物（ＺＴＯ）層、および、膜厚１０ｎｍのＳｉＺｒＯｘ層（Ｓｉ：６６ａｔｍ％、Ｚｒ：３４ａｔｍ％）を順次形成し、上記アンダーコート層上に、第一金属酸化物層、金属層、第二金属酸化物層、トップコート層をこの順に形成した。
　ＳｉＣ層の形成には、炭化ケイ素ターゲット（三菱マテリアル製）を用い、電力密度：２．６７Ｗ／ｃｍ２、プロセス圧力：０．４Ｐａでスパッタを行った。
　ＺＴＯ層の形成には、酸化亜鉛と酸化錫と金属亜鉛粉末とを、８．５：８３：８．５の重量比で焼結させたターゲットを用い、電力密度：２．６７Ｗ／ｃｍ２、プロセス圧力：０．４Ｐａの条件でスパッタを行った。この際、スパッタ製膜室へのガス導入量を、Ａｒ：Ｏ２が９８：２（体積比）となるように調整した。
　Ａｇ－Ｐｄ合金層の形成には、銀：パラジウムを９６．４：３．６の重量比で含有する金属ターゲットを用い、電力密度：１．３３Ｗ／ｃｍ２、プロセス圧力：０．４Ｐａの条件でスパッタを行った。
　ＳｉＺｒＯｘ層の形成にはＳｉ：Ｚｒを６７：３３の原子量比で焼結させたターゲットを用い、電力密度：２．６７Ｗ／ｃｍ２、プロセス圧力：０．４Ｐａの条件でスパッタを行った。この際、スパッタ製膜室へのガス導入量を、Ａｒ：Ｏ２が６０：４０（体積比）となるように調整した。
（遮熱断熱基板）
　以上のようにして、透明基板層（厚み５０μｍ）／アンダーコート層（厚み２μｍ）／反射防止層（厚み６ｎｍ）／第一金属酸化物層（厚み３０ｎｍ）／金属層（厚み１５ｎｍ）／第二金属酸化物層（厚み３０ｎｍ）／トップコート層（厚み１０ｎｍ）の構成を有する遮熱断熱基板（１）を得た。
　結果を表１に示した。 [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 antireflection layer, first metal oxide layer, metal layer, second metal oxide layer, topcoat layer)
Using a winding-type sputtering apparatus, a 6-nm thick SiC layer and a 30-nm-thick zinc-tin composite oxide (ZTO) are formed on the undercoat layer formed on the transparent substrate layer by direct current magnetron sputtering. Layer, a 15 nm thick Ag—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. Then, a first metal oxide layer, a metal layer, a second metal oxide layer, and a top coat layer were formed in this order on the undercoat layer.
For the formation of the SiC layer, a silicon carbide target (manufactured by Mitsubishi Materials) was used, and sputtering was performed at a power density of 2.67 W / cm 2 and a process pressure of 0.4 Pa.
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).
(Thermal insulation board)
As described above, the transparent substrate layer (thickness 50 μm) / undercoat layer (thickness 2 μm) / antireflection layer (thickness 6 nm) / first metal oxide layer (thickness 30 nm) / metal layer (thickness 15 nm) / second A heat insulating and heat insulating substrate (1) having a configuration of metal oxide layer (thickness 30 nm) / topcoat layer (thickness 10 nm) was obtained.
The results are shown in Table 1.
〔実施例２〕
　ＳｉＺｒＯｘ層の形成にＳｉ：Ｚｒを９７：３の原子量比で焼結させたターゲットを用いた以外は、実施例１と同様に行い、遮熱断熱基板（２）を得た。
　結果を表１に示した。 [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.
〔実施例３〕
　ＳｉＺｒＯｘ層に代えてＳｉＹＯｘ層の形成にＳｉ：Ｙを９４：６の原子量比で焼結させたターゲットを用いた以外は、実施例１と同様に行い、遮熱断熱基板（３）を得た。
　結果を表１に示した。 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.
The results are shown in Table 1.
〔実施例４〕
　ＳｉＹＯｘ層の形成にＳｉ：Ｙを９７：３の原子量比で焼結させたターゲットを用いた以外は、実施例３と同様に行い、遮熱断熱基板（４）を得た。
　結果を表１に示した。 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.
〔実施例５〕
　ＳｉＺｒＯｘ層に代えてＳｉＴｉＯｘ層の形成にＳｉ：Ｔｉを９９：１の原子量比で焼結させたターゲットを用いた以外は、実施例１と同様に行い、遮熱断熱基板（５）を得た。
　結果を表１に示した。 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.
〔実施例６〕
　ＳｉＺｒＯｘ層に代えてＳｉＡｌＺｒＯｘ層の形成にＳｉ：Ａｌ：Ｚｒを６０：３０：１０の原子量比で焼結させたターゲットを用いた以外は、実施例１と同様に行い、遮熱断熱基板（６）を得た。
　結果を表１に示した。 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.
〔実施例７〕
　ＳｉＺｒＯｘ層に代えてＳｉＡｌＹＯｘ層の形成にＳｉ：Ａｌ：Ｙを６０：３７：３の原子量比で焼結させたターゲットを用いた以外は、実施例１と同様に行い、遮熱断熱基板（７）を得た。
　結果を表１に示した。 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.
〔実施例８〕
　ＳｉＺｒＯｘ層に代えてＳｉＡｌＺｒＮｘＯＹ層の形成にＳｉ：Ａｌ：Ｚｒを６０：３０：１０の原子量比で焼結させたターゲットを用いた以外は、実施例１と同様に行い、遮熱断熱基板（８）を得た。
　結果を表１に示した。 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.
〔実施例９〕
　ＳｉＺｒＯｘ層に代えてＳｉＡｌＹＮｘＯＹ層の形成にＳｉ：Ａｌ：Ｙを６０：３９：１の原子量比で焼結させたターゲットを用いた以外は、実施例１と同様に行い、遮熱断熱基板（９）を得た。
　結果を表１に示した。 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.
〔実施例１０〕
　透明基板層として、厚み５０μｍのポリエチレンテレフタレートフィルム基材（東レ製、商品名「ルミラーＵ４８」、可視光透過率９３％）に代えて、厚み３ｍｍのフロート板ガラス（松浪硝子製、可視光透過率９１％）を用いた以外は、実施例１と同様に行い、遮熱断熱基板（１０）を得た。
　結果を表１に示した。 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.
〔実施例１１〕
　透明基板層として、厚み５０μｍのポリエチレンテレフタレートフィルム基材（東レ製、商品名「ルミラーＵ４８」、可視光透過率９３％）に代えて、厚み３ｍｍのフロート板ガラス（松浪硝子製、可視光透過率９１％）を用いた以外は、実施例２と同様に行い、遮熱断熱基板（１１）を得た。
　結果を表１に示した。 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.
〔実施例１２〕
　透明基板層として、厚み５０μｍのポリエチレンテレフタレートフィルム基材（東レ製、商品名「ルミラーＵ４８」、可視光透過率９３％）に代えて、厚み３ｍｍのフロート板ガラス（松浪硝子製、可視光透過率９１％）を用いた以外は、実施例３と同様に行い、遮熱断熱基板（１２）を得た。
　結果を表１に示した。 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.
〔実施例１３〕
　透明基板層として、厚み５０μｍのポリエチレンテレフタレートフィルム基材（東レ製、商品名「ルミラーＵ４８」、可視光透過率９３％）に代えて、厚み３ｍｍのフロート板ガラス（松浪硝子製、可視光透過率９１％）を用いた以外は、実施例４と同様に行い、遮熱断熱基板（１３）を得た。
　結果を表１に示した。 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.
〔実施例１４〕
　透明基板層として、厚み５０μｍのポリエチレンテレフタレートフィルム基材（東レ製、商品名「ルミラーＵ４８」、可視光透過率９３％）に代えて、厚み３ｍｍのフロート板ガラス（松浪硝子製、可視光透過率９１％）を用いた以外は、実施例５と同様に行い、遮熱断熱基板（１４）を得た。
　結果を表１に示した。 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.
〔実施例１５〕
　透明基板層として、厚み５０μｍのポリエチレンテレフタレートフィルム基材（東レ製、商品名「ルミラーＵ４８」、可視光透過率９３％）に代えて、厚み３ｍｍのフロート板ガラス（松浪硝子製、可視光透過率９１％）を用いた以外は、実施例６と同様に行い、遮熱断熱基板（１５）を得た。
　結果を表１に示した。 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.
〔実施例１６〕
　透明基板層として、厚み５０μｍのポリエチレンテレフタレートフィルム基材（東レ製、商品名「ルミラーＵ４８」、可視光透過率９３％）に代えて、厚み３ｍｍのフロート板ガラス（松浪硝子製、可視光透過率９１％）を用いた以外は、実施例７と同様に行い、遮熱断熱基板（１６）を得た。
　結果を表１に示した。 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.
〔実施例１７〕
　透明基板層として、厚み５０μｍのポリエチレンテレフタレートフィルム基材（東レ製、商品名「ルミラーＵ４８」、可視光透過率９３％）に代えて、厚み３ｍｍのフロート板ガラス（松浪硝子製、可視光透過率９１％）を用いた以外は、実施例８と同様に行い、遮熱断熱基板（１７）を得た。
　結果を表１に示した。 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.
〔実施例１８〕
　透明基板層として、厚み５０μｍのポリエチレンテレフタレートフィルム基材（東レ製、商品名「ルミラーＵ４８」、可視光透過率９３％）に代えて、厚み３ｍｍのフロート板ガラス（松浪硝子製、可視光透過率９１％）を用いた以外は、実施例９と同様に行い、遮熱断熱基板（１８）を得た。
　結果を表１に示した。 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.
〔実施例１９〕
　トップコート層の厚みを１００ｎｍに変更した以外は、実施例１と同様に行い、透明基板層（厚み５０μｍ）／アンダーコート層（厚み２μｍ）／反射防止層（厚み６ｎｍ）／第一金属酸化物層（厚み３０ｎｍ）／金属層（厚み１５ｎｍ）／第二金属酸化物層（厚み３０ｎｍ）／トップコート層（厚み１００ｎｍ）の構成を有する遮熱断熱基板（１９）を得た。
　結果を表１に示した。 Example 19
Except for changing the thickness of the topcoat layer to 100 nm, the same procedure as in Example 1 was carried out, and the transparent substrate layer (thickness 50 μm) / undercoat layer (thickness 2 μm) / antireflection layer (thickness 6 nm) / first metal oxide A heat insulating and heat insulating substrate (19) having a structure of layer (thickness 30 nm) / metal layer (thickness 15 nm) / second metal oxide layer (thickness 30 nm) / topcoat layer (thickness 100 nm) was obtained.
The results are shown in Table 1.
〔実施例２０〕
　トップコート層の厚みを４００ｎｍに変更した以外は、実施例１と同様に行い、透明基板層（厚み５０μｍ）／アンダーコート層（厚み２μｍ）／反射防止層（厚み６ｎｍ）／第一金属酸化物層（厚み３０ｎｍ）／金属層（厚み１５ｎｍ）／第二金属酸化物層（厚み３０ｎｍ）／トップコート層（厚み４００ｎｍ）の構成を有する遮熱断熱基板（２０）を得た。
　結果を表１に示した。 Example 20
Except for changing the thickness of the topcoat layer to 400 nm, the same procedure as in Example 1 was carried out, and the transparent substrate layer (thickness 50 μm) / undercoat layer (thickness 2 μm) / antireflection layer (thickness 6 nm) / first metal oxide A heat insulating and heat insulating substrate (20) having a structure of layer (thickness 30 nm) / metal layer (thickness 15 nm) / second metal oxide layer (thickness 30 nm) / topcoat layer (thickness 400 nm) was obtained.
The results are shown in Table 1.
〔実施例２１〕
　トップコート層の厚みを８００ｎｍに変更した以外は、実施例１と同様に行い、透明基板層（厚み５０μｍ）／アンダーコート層（厚み２μｍ）／反射防止層（厚み６ｎｍ）／第一金属酸化物層（厚み３０ｎｍ）／金属層（厚み１５ｎｍ）／第二金属酸化物層（厚み３０ｎｍ）／トップコート層（厚み８００ｎｍ）の構成を有する遮熱断熱基板（２１）を得た。
　結果を表１に示した。 Example 21
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) / antireflection layer (thickness 6 nm) / first metal oxide A heat insulating and heat insulating substrate (21) having a structure of layer (thickness 30 nm) / metal layer (thickness 15 nm) / second metal oxide layer (thickness 30 nm) / topcoat layer (thickness 800 nm) was obtained.
The results are shown in Table 1.
〔比較例１〕
　ＳｉＺｒＯｘ層に代えてＺｒＯ２層を形成した以外は、実施例１と同様に行い、遮熱断熱基板（Ｃ１）を得た。
　結果を表２に示した。 [Comparative Example 1]
A heat insulating and heat insulating substrate (C1) 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.
〔比較例２〕
　ＳｉＺｒＯｘ層に代えてＳｉＯ２層を形成した以外は、実施例１と同様に行い、遮熱断熱基板（Ｃ２）を得た。
　結果を表２に示した。 [Comparative Example 2]
Except that the SiO 2 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 (C2).
The results are shown in Table 2.
〔比較例３〕
　ＳｉＺｒＯｘ層に代えてＡｌ２Ｏ３層を形成した以外は、実施例１と同様に行い、遮熱断熱基板（Ｃ３）を得た。
　結果を表２に示した。 [Comparative Example 3]
A heat insulating and heat insulating substrate (C3) 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.
〔比較例４〕
　ＳｉＺｒＯｘ層に代えてＳｉＳｎＯｘ層の形成にＳｉ：Ｓｎを５０：５０の原子量比で焼結させたターゲットを用いた以外は、実施例１と同様に行い、遮熱断熱基板（Ｃ４）を得た。
　結果を表２に示した。 [Comparative Example 4]
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 (C4) Obtained.
The results are shown in Table 2.
〔比較例５〕
　ＳｉＺｒＯｘ層に代えてＳｉ層を形成した以外は、実施例１と同様に行い、遮熱断熱基板（Ｃ５）を得た。
　結果を表２に示した。 [Comparative Example 5]
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 (C5).
The results are shown in Table 2.
〔比較例６〕
　ＳｉＺｒＯｘ層を形成しなかった以外は、実施例１と同様に行い、遮熱断熱基板（Ｃ６）を得た。
　結果を表２に示した。 [Comparative Example 6]
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 (C6).
The results are shown in Table 2.
〔比較例７〕
　ＳｉＣを形成しなかった以外は、実施例１と同様に行い、遮熱断熱基板（Ｃ７）を得た。
　結果を表２に示した。 [Comparative Example 7]
Except not forming SiC, it carried out similarly to Example 1 and obtained the heat-shielding heat insulation board | substrate (C7).
The results are shown in Table 2.
〔比較例８〕
　透明基板層として、厚み５０μｍのポリエチレンテレフタレートフィルム基材（東レ製、商品名「ルミラーＵ４８」、可視光透過率９３％）に代えて、厚み３ｍｍのフロート板ガラス（松浪硝子製、可視光透過率９１％）を用いた以外は、比較例１と同様に行い、遮熱断熱基板（Ｃ８）を得た。
　結果を表２に示した。 [Comparative Example 8]
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 1 to obtain a heat insulating and heat insulating substrate (C8).
The results are shown in Table 2.
〔比較例９〕
　透明基板層として、厚み５０μｍのポリエチレンテレフタレートフィルム基材（東レ製、商品名「ルミラーＵ４８」、可視光透過率９３％）に代えて、厚み３ｍｍのフロート板ガラス（松浪硝子製、可視光透過率９１％）を用いた以外は、比較例２と同様に行い、遮熱断熱基板（Ｃ９）を得た。
　結果を表２に示した。 [Comparative Example 9]
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 2 to obtain a heat insulating and heat insulating substrate (C9).
The results are shown in Table 2.
〔比較例１０〕
　透明基板層として、厚み５０μｍのポリエチレンテレフタレートフィルム基材（東レ製、商品名「ルミラーＵ４８」、可視光透過率９３％）に代えて、厚み３ｍｍのフロート板ガラス（松浪硝子製、可視光透過率９１％）を用いた以外は、比較例３と同様に行い、遮熱断熱基板（Ｃ１０）を得た。
　結果を表２に示した。 [Comparative 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 Comparative Example 3 to obtain a heat insulating and heat insulating substrate (C10).
The results are shown in Table 2.
〔比較例１１〕
　透明基板層として、厚み５０μｍのポリエチレンテレフタレートフィルム基材（東レ製、商品名「ルミラーＵ４８」、可視光透過率９３％）に代えて、厚み３ｍｍのフロート板ガラス（松浪硝子製、可視光透過率９１％）を用いた以外は、比較例４と同様に行い、遮熱断熱基板（Ｃ１１）を得た。
　結果を表２に示した。 [Comparative 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 Comparative Example 4 to obtain a heat insulating and heat insulating substrate (C11).
The results are shown in Table 2.
〔比較例１２〕
　透明基板層として、厚み５０μｍのポリエチレンテレフタレートフィルム基材（東レ製、商品名「ルミラーＵ４８」、可視光透過率９３％）に代えて、厚み３ｍｍのフロート板ガラス（松浪硝子製、可視光透過率９１％）を用いた以外は、比較例５と同様に行い、遮熱断熱基板（Ｃ１２）を得た。
　結果を表２に示した。 [Comparative 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 Comparative Example 5 to obtain a heat insulating and heat insulating substrate (C12).
The results are shown in Table 2.
〔比較例１３〕
　透明基板層として、厚み５０μｍのポリエチレンテレフタレートフィルム基材（東レ製、商品名「ルミラーＵ４８」、可視光透過率９３％）に代えて、厚み３ｍｍのフロート板ガラス（松浪硝子製、可視光透過率９１％）を用いた以外は、比較例６と同様に行い、遮熱断熱基板（Ｃ１３）を得た。
　結果を表２に示した。 [Comparative 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 Comparative Example 6 to obtain a heat insulating and heat insulating substrate (C13).
The results are shown in Table 2.
〔比較例１４〕
　透明基板層として、厚み５０μｍのポリエチレンテレフタレートフィルム基材（東レ製、商品名「ルミラーＵ４８」、可視光透過率９３％）に代えて、厚み３ｍｍのフロート板ガラス（松浪硝子製、可視光透過率９１％）を用いた以外は、比較例７と同様に行い、遮熱断熱基板（Ｃ１４）を得た。
　結果を表２に示した。 [Comparative 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 Comparative Example 7 to obtain a heat insulating and heat insulating substrate (C14).
The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　本発明の遮熱断熱基板は、例えば、建物や乗り物等の窓、植物等を入れる透明ケース、冷凍もしくは冷蔵のショーケース等に利用することができる。 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.
１０　　　透明基板層
２０　　　赤外線反射層
２１　　　金属層
２２ａ　　第一金属酸化物層
２２ｂ　　第二金属酸化物層
３０　　　トップコート層
５０　　　反射防止層
６０　　　アンダーコート層
７０　　　保護フィルム
８０　　　接着剤層
９０　　　暖房器具
１００　　遮熱断熱基板
１０００　窓 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 50 Antireflection layer 60 Undercoat layer 70 Protective film 80 Adhesive layer 90 Heating appliance 100 Heat insulation Insulation board 1000 window

Claims (4)

  1. 　透明基板層と赤外線反射層を含む遮熱断熱基板であって、
    　該赤外線反射層の該透明基板層と反対の側にトップコート層を備え、
    　該トップコート層が、周期表第１３族または第１４族の１種以上が主成分となる酸化物または窒化物、酸化窒化物、非酸化窒化物であり、周期表第３族または第４族の１種以上の成分を含む、
    　遮熱断熱基板。     A heat insulating and heat insulating substrate including a transparent substrate layer and an infrared reflective layer,
    A topcoat layer is 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
    Thermal insulation board.
  2. 　前記赤外線反射層と前記トップコート層が直接に積層されてなる、請求項１に記載の遮熱断熱基板。 The heat-insulating and heat-insulating substrate according to claim 1, wherein the infrared reflective layer and the topcoat layer are directly laminated.
  3. 　前記トップコート層の厚みが０．５ｎｍ～５００ｎｍである、請求項１または２に記載の遮熱断熱基板。 The heat-insulating and heat-insulating substrate according to claim 1 or 2, wherein the top coat layer has a thickness of 0.5 nm to 500 nm.
  4. 　前記トップコート層が、ＳｉとＺｒを含む酸化物または酸化窒化物、ＳｉとＹを含む酸化物または酸化窒化物、ＳｉとＴｉを含む酸化物または酸化窒化物から選ばれる少なくとも１種を含む、請求項１から３までのいずれかに記載の遮熱断熱基板。
     
          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-insulating and heat-insulating substrate according to any one of claims 1 to 3.

PCT/JP2018/012643 2017-03-30 2018-03-28 Heat-shielding and heat-insulating substrate WO2018181424A1 (en)

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JP2017066617 2017-03-30
JP2017-066617 2017-03-30
JP2018-059381 2018-03-27
JP2018059381A JP7145629B2 (en) 2017-03-30 2018-03-27 Thermal insulation board

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US11299654B2 (en) 2019-08-20 2022-04-12 Roller Bearing Company Of America, Inc. Permanent, self-adhering, self-lubricating, anti-wear composite system

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JPH0952733A (en) * 1995-08-17 1997-02-25 Asahi Glass Co Ltd Functional article
US20090324967A1 (en) * 2008-06-25 2009-12-31 C.R.V.C. Coated article with low-E coating including zirconium oxide and/or zirconium silicon oxynitride and methods of making same
JP2015229614A (en) * 2014-06-05 2015-12-21 セントラル硝子株式会社 Window glass for vehicle
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JPH03223703A (en) * 1989-03-07 1991-10-02 Asahi Glass Co Ltd Optical body having excellent durability
JPH0952733A (en) * 1995-08-17 1997-02-25 Asahi Glass Co Ltd Functional article
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JP2015229614A (en) * 2014-06-05 2015-12-21 セントラル硝子株式会社 Window glass for vehicle
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US10550191B2 (en) 2017-03-29 2020-02-04 Shionogi & Co., Ltd. Method of treating cancer with an anti-CCR8 having antibody-dependent cell-mediated cytotoxicity (ADCC) activity against cells expressing CCR8
US11932696B2 (en) 2017-03-29 2024-03-19 Shionogi & Co., Ltd. Method of treating cancer with an anti-CCR8 that binds tumor infiltrating cells
US11299654B2 (en) 2019-08-20 2022-04-12 Roller Bearing Company Of America, Inc. Permanent, self-adhering, self-lubricating, anti-wear composite system

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