WO2018181424A1 - Substrat de protection thermique et d'isolation thermique - Google Patents

Substrat de protection thermique et d'isolation thermique Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
layer
heat
insulating substrate
heat insulating
insulating
Prior art date
Application number
PCT/JP2018/012643
Other languages
English (en)
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2018059381A external-priority patent/JP7145629B2/ja
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/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un substrat de protection thermique et d'isolation thermique présentant une excellente résistance aux rayures. Le substrat de protection thermique et d'isolation thermique de la présente invention comprend une couche de substrat transparent et une couche réfléchissant les infrarouges, est pourvu d'une couche de revêtement supérieure sur un côté de la couche réfléchissant les infrarouges, ledit côté étant opposé à la couche de substrat transparent, la couche de revêtement supérieure étant formée d'un oxyde, d'un nitrure, d'un oxynitrure ou d'un non oxynitrure ayant, en tant que constituants principaux, un ou plusieurs éléments du groupe XIII ou XIV du tableau périodique des éléments et comprenant un ou plusieurs constituants du groupe III ou IV du tableau périodique des éléments.
PCT/JP2018/012643 2017-03-30 2018-03-28 Substrat de protection thermique et d'isolation thermique WO2018181424A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2017-066617 2017-03-30
JP2017066617 2017-03-30
JP2018-059381 2018-03-27
JP2018059381A JP7145629B2 (ja) 2017-03-30 2018-03-27 遮熱断熱基板

Publications (1)

Publication Number Publication Date
WO2018181424A1 true WO2018181424A1 (fr) 2018-10-04

Family

ID=63677265

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/012643 WO2018181424A1 (fr) 2017-03-30 2018-03-28 Substrat de protection thermique et d'isolation thermique

Country Status (1)

Country Link
WO (1) WO2018181424A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US11299654B2 (en) 2019-08-20 2022-04-12 Roller Bearing Company Of America, Inc. Permanent, self-adhering, self-lubricating, anti-wear composite system

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03223703A (ja) * 1989-03-07 1991-10-02 Asahi Glass Co Ltd 耐久性の優れた光学体の製造方法
JPH0952733A (ja) * 1995-08-17 1997-02-25 Asahi Glass Co Ltd 機能性物品
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 (ja) * 2014-06-05 2015-12-21 セントラル硝子株式会社 車両用窓ガラス
WO2016021532A1 (fr) * 2014-08-05 2016-02-11 日東電工株式会社 Substrat réfléchissant les infrarouges

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03223703A (ja) * 1989-03-07 1991-10-02 Asahi Glass Co Ltd 耐久性の優れた光学体の製造方法
JPH0952733A (ja) * 1995-08-17 1997-02-25 Asahi Glass Co Ltd 機能性物品
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 (ja) * 2014-06-05 2015-12-21 セントラル硝子株式会社 車両用窓ガラス
WO2016021532A1 (fr) * 2014-08-05 2016-02-11 日東電工株式会社 Substrat réfléchissant les infrarouges

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Similar Documents

Publication Publication Date Title
JP6000991B2 (ja) 赤外線反射フィルム
JP6282142B2 (ja) 赤外線反射基板およびその製造方法
EP3179282A1 (fr) Substrat réfléchissant les infrarouges
KR101918425B1 (ko) 적외선 반사 필름
EP2952939A1 (fr) Procédé de fabrication d'un film réfléchissant le rayonnement infrarouge
EP2985145A1 (fr) Film réfléchissant les rayons infrarouges
WO2014119668A1 (fr) Procédé de production d'un film réfléchissant le rayonnement infrarouge
WO2018181424A1 (fr) Substrat de protection thermique et d'isolation thermique
JP6370347B2 (ja) 赤外線反射フィルム
JP7145629B2 (ja) 遮熱断熱基板
WO2018181444A1 (fr) Substrat isolant thermique formant bouclier thermique
JP2018173166A (ja) 遮熱断熱基板
JP6761625B2 (ja) 赤外線反射フィルム
JP2018171914A (ja) 遮熱断熱フィルム
WO2018181446A1 (fr) Film de protection thermique et d'isolation thermique
JP7171211B2 (ja) 遮熱断熱基板
WO2018181433A1 (fr) Substrat thermo-isolant de protection contre la chaleur
JP2016036929A (ja) 赤外線反射基板
KR20240019407A (ko) 열선 반사 투광성 기재 및 열선 반사창

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18778267

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18778267

Country of ref document: EP

Kind code of ref document: A1