WO2022019264A1 - 吸光遮熱膜、吸光遮熱部材、および物品、並びにそれらの製造方法 - Google Patents

吸光遮熱膜、吸光遮熱部材、および物品、並びにそれらの製造方法 Download PDF

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Publication number
WO2022019264A1
WO2022019264A1 PCT/JP2021/026956 JP2021026956W WO2022019264A1 WO 2022019264 A1 WO2022019264 A1 WO 2022019264A1 JP 2021026956 W JP2021026956 W JP 2021026956W WO 2022019264 A1 WO2022019264 A1 WO 2022019264A1
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Prior art keywords
heat
shielding film
metal
metal oxide
uneven shape
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Ceased
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PCT/JP2021/026956
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English (en)
French (fr)
Japanese (ja)
Inventor
佳範 小谷
宏 齋藤
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Canon Inc
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Canon Inc
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Publication date
Application filed by Canon Inc filed Critical Canon Inc
Priority to DE112021003914.8T priority Critical patent/DE112021003914T5/de
Priority to JP2022538000A priority patent/JP7844333B2/ja
Priority to CN202180060439.1A priority patent/CN116134346A/zh
Priority to GB2301399.8A priority patent/GB2612240B/en
Publication of WO2022019264A1 publication Critical patent/WO2022019264A1/ja
Priority to US18/156,942 priority patent/US20230161083A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/003—Light absorbing elements
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general
    • F16L59/08—Means for preventing radiation, e.g. with metal foil
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/204—Filters in which spectral selection is performed by means of a conductive grid or array, e.g. frequency selective surfaces
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present invention relates to an absorbent heat-shielding film, an absorbent heat-shielding member, an article, and a method for manufacturing them.
  • Non-Patent Document 1 an absorbent material plated with black electroless nickel is known (for example, Non-Patent Document 1).
  • Patent Document 1 This is used as an absorbent material by blackening the surface by forming fine irregularities by oxidizing the nickel plating on the surface of the object. Further, a technique for producing a resin having a fine structure on the surface by injection molding using a mold having a fine unevenness on the metal surface is also shown (for example, Patent Document 1).
  • Non-Patent Document 1 has a problem that it emits a large amount of radiation even in the far infrared region and does not show excellent heat shielding properties. Further, the invention described in Patent Document 1 is injection molding of a resin using a mold, and cannot form a metal film having a highly versatile form, and is applied to various products as an absorption heat shield member. Is difficult and has problems in practicality.
  • the heat shield material usually has a problem that the ambient light source is reflected depending on the shooting angle of the thermal image camera, and it is difficult to see the heat shield subject (the reflection (glare) of the light emitted by the light source is large).
  • the present invention has been made in view of the above problems, and absorbs visible light and near-infrared rays that are normally incompatible with each other, and emits far-infrared rays with small characteristics and suppresses reflection of an ambient light source.
  • the purpose is to provide a member.
  • An embodiment according to the present invention is characterized in that a metal layer provided with an uneven shape is provided, and the uneven shape has a second uneven structure formed on the first uneven structure.
  • An embodiment of the present invention is an absorbent heat-shielding film provided with a metal layer, wherein the metal layer includes a base portion and a concave-convex shape portion provided on the base portion, and the concave-convex shape portion includes the concave-convex shape portion. It has a first concavo-convex structure including a plurality of convex portions and a second concavo-convex structure including a plurality of convex portions provided on each of the plurality of convex portions, and the base portion is the first concavo-convex structure.
  • An embodiment according to the present invention is a method for producing an absorbent heat-shielding film, which comprises a step of preparing a mold having an uneven shape and a step of forming a metal layer having the uneven shape transferred onto the mold.
  • the mold has a concavo-convex structure including a plurality of recesses, and the concavo-convex shape includes a plurality of recesses provided on the surface of each of the plurality of recesses included in the concave-convex structure. It is a feature.
  • the method for producing an absorption heat shield film includes a step of preparing a base material having a concavo-convex structure, a first step of forming a concavo-convex shape of a metal oxide on the base material, and the metal oxidation. It is characterized by including a second step of forming a metal layer on the uneven shape of an object.
  • the heat-absorbing heat-shielding film according to the present embodiment includes a fine concavo-convex shape, and the fine concavo-convex shape has a hierarchical structure, and the hierarchical structure has a first concavo-convex structure (first structure) and a second. Concavo-convex structure (second structure) is included. Further, the heat-absorbing heat-shielding film according to the present embodiment includes a metal layer, and the metal layer has a base, a first uneven structure (first structure), and a second uneven structure (second structure). ..
  • first structure a first concavo-convex structure
  • second structure a second concavo-convex structure
  • the fine uneven shape of the heat-absorbing heat-shielding film is a metal layer.
  • the fine concavo-convex shape may be simply referred to as the concavo-convex shape.
  • Highly conductive metals such as aluminum and nickel emit little far infrared rays and have heat shielding properties, but do not show absorbance.
  • the fine uneven shape due to the sub-wavelength structure smaller than the wavelength of visible light has an antireflection effect, and by continuously changing the space occupancy of the structural part, excellent wavelength band characteristics can be obtained. It is known to exhibit incident angle characteristics. Therefore, when the metal surface is made finely uneven, the reflection on the metal surface is suppressed in a wide wavelength region of visible light, the reflectance in the entire visible light region is lowered, the surface looks black, and the absorbance is exhibited.
  • Non-Patent Document 1 has a fine uneven shape obtained by oxidizing the nickel surface on the surface, it emits a large amount of radiation (low reflectance) even in the far infrared region and does not exhibit heat shielding properties. .. Further, in practical use, the heat shield material usually has a problem that the ambient light source is reflected depending on the shooting angle of the thermal image camera, making it difficult to see the heat shield subject (the reflection (glare) of the light emitted by the light source is large). ..
  • the present inventors have formed a hierarchical microstructure in the fine uneven shape of the metal surface in addition to the heat-shielding property of the metal itself forming the absorption heat-shielding film, so that the surrounding light source is reflected.
  • the hierarchical microstructure is composed of at least two types of structures having different structural sizes, for example, a structure having both a first structure having a structure size on the order of micron and a second structure having a structure size on the order of submicron. Means.
  • the first structure has the effect of suppressing the reflection of the surrounding light source, and the second structure has a reduced reflectance in the entire visible light region, looks black, and exhibits absorbance.
  • the above-mentioned absorbance, heat shield, and effect of suppressing the reflection of the light source can be widely controlled by appropriately combining the size of the surface fine structure of the absorption heat shield film and the material used for the film.
  • one embodiment of the absorption heat shield film of the present invention is an absorption heat shield film 10 provided with a metal layer 1 including a fine uneven shape portion 2 (concavo-convex shape portion) on the surface.
  • the absorption heat shield film 10 includes a base portion 11 under the fine uneven shape portion 2, and the base portion 11 is a part of the metal layer 1.
  • a metal having high conductivity is preferable.
  • the fine uneven shape portion 2 provided on the surface of the metal layer 1 is also preferably made of the metal having high conductivity, and more preferably made of the same metal as the base 11 of the metal layer 1.
  • a transparent metal oxide may be attached to the surface of the fine uneven shape portion 2.
  • the absorption heat shield film 10 may contain a transparent metal oxide on the surface of the fine uneven shape object (fine uneven shape portion 2) which is the metal layer 1.
  • the metal component of the metal oxide adhering to the surface of the fine uneven shape portion 2 may be different from the metal component of the metal layer 1. That is, for example, if the material of the metal layer 1 is nickel, the metal oxide adhering to the surface of the fine uneven shape portion 2 may be a metal oxide other than nickel. Therefore, the metal oxide adhering to the surface of the fine uneven shape portion 2 is distinguished from the metal oxide having the same metal component as the metal component of the metal layer 1 formed by natural oxidation of the metal layer 1 or the like. sell.
  • the attached metal oxide preferably contains aluminum oxide as a main component, and may be a crystal containing aluminum oxide as a main component.
  • the crystal containing aluminum oxide as a main component is formed by a crystal containing an oxide or hydroxide of aluminum or a hydrate thereof as a main component, and a particularly preferable crystal is boehmite.
  • the crystal containing aluminum oxide as a main component may be a crystal composed of only aluminum oxide, or may be a crystal containing a trace amount of zirconium, silicon, titanium, zinc or the like in the crystal of aluminum oxide.
  • the metal layer 1 includes a base portion 11 and a fine uneven shape portion 2 provided on the base portion 11.
  • the base portion 11 is a portion where the metal layer 1 is continuous in the extending direction (horizontal direction in FIG. 1) of the absorption heat shield film 10, and the fine uneven shape portion 2 is the extension direction of the absorption heat shield film 10.
  • the metal layer 1 is an intermittent portion in (horizontal direction on FIG. 1). In FIG. 1, the boundary 12 between the base portion 11 and the fine uneven shape portion 2 is shown by a broken line.
  • the fine concavo-convex shape portion 2 is a portion having a fine concavo-convex shape provided on one surface of the metal layer 1, and the fine concavo-convex shape portion 2 has a hierarchical structure. That is, the fine concavo-convex shape portion 2 has a first concavo-convex structure 21 and a second concavo-convex structure 22. Since the object having the fine concavo-convex shape portion 2 is the fine concavo-convex shape portion and the fine concavo-convex shape portion 2 is a part or the whole of the fine concavo-convex shape portion 2, the fine concavo-convex shape portion 2 can also be referred to as the fine concavo-convex shape portion. ..
  • the first uneven structure 21 includes a plurality of convex portions (for example, convex portions 211 and convex portions 212). Further, the first concave-convex structure 21 includes a plurality of concave portions (for example, the concave portion 210 between the convex portion 211 and the convex portion 212).
  • the convex portions 221, 212 of the first uneven structure 21 are a part of the metal layer 1, and the concave portions 210 of the first uneven structure 21 do not have the metal layer 1, and a substance other than the metal layer 1 may exist. It is a space.
  • the second uneven structure 22 includes a plurality of convex portions (for example, convex portions 221 and convex portions 222).
  • the second concave-convex structure 22 includes a plurality of concave portions (for example, the concave portion 220 between the convex portion 221 and the convex portion 222).
  • the convex portions 221 and 212 of the second uneven structure 22 are a part of the metal layer 1, and the concave portions 220 of the second concave-convex structure 21 do not have the metal layer 1 and a substance other than the metal layer 1 may exist. It is a space.
  • the second uneven structure 22 is formed on the first uneven structure 21. That is, the second uneven structure 22 is provided on each of the plurality of convex portions (for example, the convex portion 211 and the convex portion 212) included in the first uneven structure 21. It is preferable that the main components of the metal material of the first uneven structure 21 and the second uneven structure 22 are the same.
  • the metal layer 1 which is a concave-convex shape in the absorption heat-shielding film 10 is made of a metal material having the same main component as the first concave-convex structure 21 and the second concave-convex structure 22 under the first concave-convex structure 21. It has a base 11. The base portion 11 extends under a plurality of convex portions (for example, the convex portions 211 and the convex portions 212) included in the first concave-convex structure 21. On the other hand, in the fine uneven shape portion 2, the metal layer 1 is discontinuous due to the concave portion (for example, the concave portion 210) of the first uneven structure 21.
  • the main components of the metal materials of the base 11, the first uneven structure 21, and the second uneven structure 21 are the same.
  • a common metal material that is, a single-layer metal layer 1
  • these are made of different metal materials (that is, a multi-layer metal layer). It is possible to realize excellent absorption and heat shielding characteristics as compared with the case of configuring with.
  • the average roughness Ra1 of the first uneven structure 21 is 0.1 ⁇ m or more and 5 ⁇ m or less, and the average roughness Ra2 of the second uneven structure 22 is 1 nm or more and 50 nm or less.
  • Ra is the average roughness (nm)
  • L is the reference length
  • F (X, Y) is the height at the measurement point (X, Y) where the X coordinate is X and the Y coordinate is Y.
  • the X L ⁇ X R is in the range of X coordinates of the measuring line.
  • the maximum height Rz1 of the first uneven structure 21 on the surface of the metal layer 1 is 1 ⁇ m or more and 10 ⁇ m or less
  • the maximum height Rz2 of the second uneven structure 22 is Is preferably 100 nm or more and 800 nm or less.
  • the maximum height of the fine uneven shape portion 2 or the maximum height of the fine uneven shape portion 2 to which the transparent metal oxide is attached is defined in "Definition and display of surface roughness" of JIS-B-061. Means the maximum height that has been. Only the reference length is extracted from the roughness curve in the direction of the average line, and the distance between the peak line and the valley bottom line of the extracted portion is measured and calculated in the direction of the vertical magnification of the roughness curve. This valley bottom line can correspond to the boundary 12 between the base portion 11 and the fine uneven shape portion 2 shown by the broken line in FIG.
  • the average roughness and the maximum height of the fine uneven shape portion 2 can be obtained by observing the cross section of the absorption heat shield film 10 of the present embodiment with a scanning electron microscope or the like.
  • a transparent fine metal oxide 3 that is in close contact with the fine uneven shape portion 2 may be provided.
  • the fine metal oxide 3 may be simply referred to as a metal oxide.
  • the fine metal oxide 3 is provided between the plurality of convex portions (for example, the convex portions 221 and the convex portions 222) included in the second uneven structure 21. That is, the fine metal oxide 3 fills the concave portion 220 between the convex portion 221 and the convex portion 222.
  • a transparent metal oxide layer 4 covering a surface of the fine metal oxide 3 that is not in contact with the fine uneven shape portion 2 is provided. It may be further prepared.
  • the metal oxide layer 4 covers the fine uneven shape portion 2, and the fine metal oxide 3 is provided between the metal oxide layer 4 and the metal layer 1.
  • close contact means that the metal oxide fills the space (recess) surrounded by the fine uneven shape portion 2 and reaches the metal layer 1.
  • the metal oxide layer 4 may be simply referred to as a metal oxide.
  • the material of the fine metal oxide 3 is not particularly limited, but it is preferable that it contains aluminum oxide as a main component, and it is more preferable that it contains a plate-shaped crystal (hereinafter referred to as a plate-shaped crystal) containing aluminum oxide as a main component.
  • the plate-like crystals containing aluminum oxide as a main component are formed of crystals containing an oxide or hydroxide of aluminum or a hydrate thereof as a main component, and a particularly preferable crystal is boehmite.
  • the plate-shaped crystal containing aluminum oxide as a main component may be a plate-shaped crystal composed of only aluminum oxide, or a plate-shaped crystal containing a trace amount of zirconium, silicon, titanium, zinc, etc. in the plate-shaped crystal of aluminum oxide. It may be a crystal.
  • the fine uneven shape portion 2 can be protected.
  • the fine metal oxide 3 has a plate-like structure of plate-like crystals containing aluminum oxide as a main component, the plate-like crystals containing aluminum oxide as a main component are perpendicular to the plane direction of the metal layer 1. It is preferably arranged and its spatial occupancy is continuously changing.
  • the material of the metal oxide layer 4 is not particularly limited, but it is preferable to include an amorphous gel of aluminum oxide.
  • the metal oxide layer 4 increases the hardness of the surface of the heat-absorbing heat-shielding film 10 of the present embodiment, while lowering the absorbance. Therefore, the thickness of the metal oxide layer 4 may be appropriately determined so as to satisfy the required hardness and absorbance.
  • the aluminum element, silicon element, etc. in the fine uneven shape portion 2, the fine metal oxide 3, and the metal oxide layer 4 are detected by surface measurement with a scanning electron microscope (SEM) or a transmission electron microscope (TEM). can do. It can also be detected by energy dispersive X-ray analysis (EDX) or X-ray electron spectroscopy (XPS) measurement during cross-sectional observation.
  • metal elements such as silver, copper, gold, aluminum, magnesium, tungsten, cobalt, zinc, nickel, and chromium in the metal layer 1 are also surfaced by a scanning electron microscope (SEM) or a transmission electron microscope (TEM). It can be detected by measurement of.
  • the fine uneven shape portion 2 the fine metal oxide 3, or the metal oxide layer 4 is provided, the surface (metal oxide layer 4) to the inside (metal) is provided in the direction perpendicular to the surface direction of the metal layer 1.
  • the proportion of metal oxides such as elemental aluminum decreases relatively toward layer 1).
  • the proportion of the metal element constituting the metal layer 1 and the fine uneven shape portion 2 increases relatively from the surface (metal oxide layer 4) toward the inside (metal layer 1), and finally only the metal element. Is detected.
  • the base material 5 is provided on the surface of the metal layer 1 of the heat-absorbing heat-shielding film 10 of the present invention on the side opposite to the fine uneven shape portion 2.
  • the absorption heat shield member 100 includes a base material 5 and an absorption heat shield film 10 provided on the base material 5.
  • the shape of the base material 5 may be any shape as long as it can be made into a shape according to the purpose of use, and may be, for example, a molded product, a flat plate shape, a film shape, a sheet shape, or the like, but is limited thereto. Not done.
  • Examples of the material of the base material 5 include, but are not limited to, metal, glass, ceramics, wood, paper, and resin.
  • Examples of the resin include thermoplastic resins such as polyester, triacetyl cellulose, cellulose acetate, polyethylene terephthalate, polypropylene, polystyrene, polycarbonate and polymethylmethacrylate.
  • ABS resin, polyphenylene oxide, polyurethane, polyethylene, polyvinyl chloride and the like can also be mentioned as thermoplastic resins.
  • thermosetting resins such as unsaturated polyester resin, phenol resin, crosslinked polyurethane, crosslinked acrylic resin, and crosslinked saturated polyester resin can be mentioned.
  • the absorption heat shield film 10 and the base material 5 may be adhered by an adhesive layer 6.
  • the adhesive layer 6 included in the heat-absorbing heat-shielding member 100 may be any layer as long as the heat-absorbing heat-shielding film and the base material 5 can be adhered to each other. Examples include layers and double-sided tape.
  • FIGS. 2A and 2B show the absorption heat shield member 100 provided with the absorption heat shield film 10 shown in FIG. 1C, it is shown in FIG. 1A or FIG. 1B instead of the absorption heat shield film 10 shown in FIG. 1C.
  • the absorption heat shield member 100 provided with the absorption heat shield film 10 may be used.
  • the manufacturing method of the present embodiment includes a step of preparing a mold 9 having a fine uneven shape 92. Since the fine concavo-convex shape 92 is included in the concavo-convex shape 90, the step can be said to be a step of preparing the mold 9 having the concavo-convex shape 90.
  • the mold 9 has an uneven structure 91.
  • the uneven shape formed by the uneven structure 91 is included in the uneven shape 90.
  • the concave-convex structure 91 includes a plurality of recesses (for example, recesses 911 and 912).
  • a plurality of convex portions are provided between the plurality of concave portions (for example, concave portions 911 and 912) of the concave-convex structure 91.
  • the fine uneven shape 92 includes a plurality of recesses (for example, recesses 921 and 922).
  • a plurality of convex portions (for example, convex portions 920) are provided between the plurality of concave portions (for example, concave portions 921 and 922) of the fine uneven shape 92.
  • the plurality of recesses (for example, recesses 921, 922) included in the fine uneven shape 92 are provided on the surface of each of the plurality of recesses (for example, recesses 911, 912) included in the concave-convex structure 91.
  • the mold 9 may include a substrate 8 and a metal oxide provided on the substrate 8.
  • the metal oxide provided on the substrate 8 may include the fine metal oxide 3 and the metal oxide layer 4 between the fine metal oxide 3 and the substrate 8.
  • the fine metal oxide 3 forms a fine uneven shape 92. That is, each of the plurality of convex portions (for example, the convex portion 920) of the fine concavo-convex shape 92 is each of the plurality of fine metal oxides 3.
  • the space between the plurality of fine metal oxides 3 is a plurality of recesses (for example, recesses 921 and 922) of the fine uneven shape 92.
  • the mold 9 has a fine uneven shape of the metal oxide.
  • the fine uneven shape of the metal oxide when paying attention to the metal oxide, it means the fine metal oxide 3, and when paying attention to the fine uneven shape, it means the fine uneven shape 92.
  • the manufacturing method of the present embodiment includes a step of forming a metal layer 1 to which the fine uneven shape 92 is transferred on a mold 9 having the fine uneven shape 92.
  • the metal layer 1 has a second concavo-convex structure 22 that reflects the fine concavo-convex shape 92 of the mold 9.
  • the metal layer 1 also has a first concavo-convex structure 21 that reflects the concavo-convex shape of the concavo-convex structure 91 of the mold 9.
  • the plurality of concave portions (for example, concave portions 911 and 912) of the concave-convex structure 91 of the mold 9 are reflected in the plurality of convex portions (for example, convex portions 211 and 212) of the first concave-convex structure 21 shown in FIG. To. Further, the plurality of concave portions (for example, concave portions 921 and 922) of the fine uneven shape 92 of the mold 9 are reflected in the plurality of convex portions (for example, convex portions 221 and 222) of the second uneven structure 22 shown in FIG. ..
  • the manufacturing method of the present embodiment further comprises a step of adhering the base material 5 to the surface of the metal layer 1 of the heat-absorbing heat-shielding film 10 opposite to the surface on which the fine concavo-convex shape 92 is transferred.
  • a step of adhering the base material 5 to the surface of the metal layer 1 of the heat-absorbing heat-shielding film 10 opposite to the surface on which the fine concavo-convex shape 92 is transferred include.
  • the manufacturing method of the present embodiment includes a step of removing at least a part of the mold 9 from the top of the metal layer 1.
  • the substrate 8 of the mold 9 is removed.
  • the metal oxide layer 4 in the mold 9 is removed.
  • the fine metal oxide 3 in the mold 9 is removed.
  • the entire mold 9 is removed.
  • the substrate 8 of the mold 9 is a translucent material such as glass
  • the metal layer 1 can be used as the heat-absorbing heat-shielding film without removing the substrate 8. That is, it can also be used as the absorption heat shield member 100 having the morphology shown in FIGS. 3D and 3E.
  • Each step shown in FIGS. 3A to 3H may be a part of the method for manufacturing the heat-absorbing heat-shielding film 10 or may be a part of the method for manufacturing the heat-absorbing heat-shielding member 100.
  • the first step of forming the fine uneven shape of the metal oxide on the substrate 8 and the metal layer 1 are formed on the fine uneven shape of the metal oxide.
  • the method for manufacturing the heat-absorbing heat-shielding member of the present embodiment further includes a step of adhering the base material 5 to the surface of the metal layer 1 of the heat-absorbing heat-shielding film 10 opposite to the surface in contact with the fine uneven shape of the metal oxide. ..
  • the first structure (first uneven structure 21) of the hierarchical fine structure in the absorption heat shield film 10 reflects the roughness structure size of the base base material used for the mold 9, and the second structure (second uneven structure 21). Reflects the size of the fine uneven shape 92 of the metal oxide.
  • First step A step of producing a fine uneven shape of a metal oxide
  • a fine uneven shape of the metal oxide to be the mold 9 is formed.
  • the base base material (base material) is referred to as a base material 8 in order to distinguish it from the base material 5, but the base material 8 is synonymous with the base base material or the base material.
  • the substrate 8 to be used may be any as long as it has a micro-order concavo-convex structure 81 on the surface of the substrate 8, and examples thereof include a substrate 8 processed with an abrasive, ground glass roughened with an etching solution such as acid or alkali, or an electron beam. However, it is not limited to these.
  • a micro-order structure may be formed on the film applied to the surface to serve as the substrate 8.
  • the concave-convex structure 81 of the substrate 8 has a plurality of concave portions (for example, concave portions 811 and 812) and a plurality of convex portions (for example, concave portions 811 and 812) between the plurality of concave portions (for example, concave portions 811 and 812). It has a convex portion 810) between them.
  • a film 7 containing aluminum is formed on a substrate 8 having a micro-order concavo-convex structure 81. Since the film 7 is formed along the concave-convex structure 81 of the substrate 8, it has a concave-convex structure 71 that reflects the concave-convex structure 81 of the substrate 8.
  • the concave-convex structure 71 of the film 7 has a plurality of concave portions (for example, concave portions 711 and 712) and a plurality of convex portions between a plurality of concave portions (for example, concave portions 711 and 712) (for example, convex portions 710 between the concave portions 711 and 712). And have.
  • the plurality of recesses of the film 7 reflect the plurality of recesses of the substrate 8 (eg, recesses 811, 812), and the plurality of protrusions of the film 7 (eg, protrusions 710).
  • the fine metal oxide 3 forming the fine uneven shape 92 is formed on the substrate 8.
  • the fine metal oxide 3 forming the fine uneven shape 92 is formed by deteriorating the film 7. Therefore, they are arranged along a plurality of concave portions (for example, concave portions 711 and 712) of the film 7 and a plurality of convex portions (for example, convex portions 710) of the film 7. Therefore, the fine metal oxide 3 forming the fine concavo-convex shape 92 also constitutes the concavo-convex structure 91 in the concavo-convex shape 90.
  • the metal oxide layer 4 derived from the film 7 can be formed between the substrate 8 and the fine metal oxide 3 forming the fine uneven shape 92.
  • the material of the metal oxide having a fine uneven shape is not particularly limited, but it is preferable that aluminum oxide is the main component.
  • the fine uneven shape can be formed by a known vapor phase method such as chemical vapor deposition (CVD) or physical vapor deposition (PVD), or a sol-gel liquid phase method. From these methods, it is possible to provide a fine concavo-convex shape of a metal oxide containing a plate-like crystal containing aluminum oxide as a main component. Above all, a method of treating a film containing aluminum with warm water to grow aluminum oxide plate-like crystals is preferable.
  • the film 7 containing aluminum examples include an aluminum oxide gel film formed by applying a sol-gel coating liquid containing an aluminum compound, and a film containing metallic aluminum formed by dry film formation such as vacuum deposition or a sputtering method. Be done. It is preferable to form the fine uneven shape of the metal oxide by using the aluminum oxide gel film because the reactivity and the height of the fine uneven shape of the metal oxide can be easily adjusted.
  • an aluminum compound such as an aluminum alkoxide, an aluminum halide, or an aluminum salt can be used. From the viewpoint of film forming property, it is preferable to use aluminum alkoxide.
  • the aluminum compound examples include aluminum alkoxides such as aluminum ethoxyde, aluminum isopropoxide, aluminum-n-butoxide, aluminum-sec-butoxide, and aluminum-tert-butoxide. Further, these oligomers, halides of aluminum such as aluminum chloride, aluminum acetylacetonate of aluminum salts such as aluminum nitrate, aluminum acetate, aluminum phosphate and aluminum sulfate, aluminum acetylacetonate, aluminum hydroxide and the like can be mentioned.
  • aluminum alkoxides such as aluminum ethoxyde, aluminum isopropoxide, aluminum-n-butoxide, aluminum-sec-butoxide, and aluminum-tert-butoxide.
  • these oligomers halides of aluminum such as aluminum chloride, aluminum acetylacetonate of aluminum salts such as aluminum nitrate, aluminum acetate, aluminum phosphate and aluminum sulfate, aluminum acetylacetonate, aluminum hydroxide and the like
  • the aluminum oxide gel film may contain other compounds.
  • Other compounds include, for example, zirconium, silicon, titanium, zinc alkoxides, halides, salts and combinations thereof.
  • the height of the fine uneven shape of the metal oxide to be formed can be increased as compared with the case where these are not contained.
  • the aluminum oxide gel film is formed on the substrate 8 by applying a sol-gel coating liquid containing an aluminum compound.
  • the sol-gel coating solution is prepared by dissolving an aluminum compound in an organic solvent.
  • the amount of the organic solvent with respect to the aluminum compound is preferably about 20 times the molar ratio.
  • alcohol carboxylic acid, aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, ester, ketone, ether, or a mixed solvent thereof
  • examples of the alcohol include methanol, ethanol, 2-propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol and the like.
  • 1-propanol, 4-methyl-2-pentanol, 2-ethylbutanol, 3-methoxy-3-methylbutanol, ethylene glycol, diethylene glycol, glycerin and the like can be mentioned.
  • Examples of the carboxylic acid include n-butyric acid, ⁇ -methylbutyric acid, iso-valeric acid, 2-ethylbutyric acid, 2,2-dimethylbutyric acid, 3,3-dimethylbutyric acid, 2,3-dimethylbutyric acid, and 3-methyl.
  • Examples thereof include pentanoic acid and 4-methylpentanoic acid.
  • 2-ethylpentanoic acid, 3-ethylpentanoic acid, 2,2-dimethylpentanoic acid, 3,3-dimethylpentanoic acid, 2,3-dimethylpentanoic acid, 2-ethylhexanoic acid, 3-ethylhexanoic acid, etc. Can be mentioned.
  • Examples of the aliphatic hydrocarbon or the alicyclic hydrocarbon include n-hexane, n-octane, cyclohexane, cyclopentane, cyclooctane and the like.
  • Examples of aromatic hydrocarbons include toluene, xylene, ethylbenzene and the like.
  • Examples of the esters include ethyl formate, ethyl acetate, n-butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate and the like.
  • ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like.
  • ethers include dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether and the like. Above all, it is preferable to use alcohol from the viewpoint of the stability of the sol-gel coating liquid.
  • aluminum alkoxide When aluminum alkoxide is used as the aluminum compound, it is highly reactive with water, so the aluminum alkoxide may be rapidly hydrolyzed by the addition of moisture or water in the air, resulting in cloudiness and precipitation of the sol-gel coating liquid. In order to prevent these, it is preferable to add a stabilizer to the sol-gel coating liquid to stabilize it.
  • a stabilizer As the stabilizer, ⁇ -diketone compounds, ⁇ -ketoester compounds, alkanolamines and the like can be used.
  • Examples of ⁇ -diketone compounds include acetylacetone, trifluoroacetylacetone, hexafluoroacetylacetone, benzoylacetone, 3-methyl-2,4-pentandione, 3-ethyl-2,4-pentandione and the like.
  • Examples of ⁇ -ketoester compounds include methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate, hexyl acetoacetic acid, allyl acetoacetic acid, benzyl acetoacetic acid, and -iso-propyl acetoacetic acid.
  • acetoacetic acid-2-methoxyethyl acetoacetic acid-sec-butyl
  • acetoacetic acid-tert-butyl acetoacetic acid-iso-butyl, and the like
  • alkanolamines include monoethanolamine, diethanolamine, triethanolamine and the like.
  • the amount of the stabilizer with respect to the aluminum alkoxide is preferably about 1 time in molar ratio.
  • a catalyst may be used to promote the hydrolysis reaction of aluminum alkoxide.
  • the catalyst include nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, ammonia and the like.
  • a water-soluble organic polymer compound can be added to the aluminum oxide gel film as needed.
  • the water-soluble organic polymer compound is easily eluted from the aluminum oxide gel film by immersion in warm water, which increases the reaction surface area between the aluminum compound and hot water and forms fine uneven shapes at low temperature and in a short time. enable. Further, by changing the type and molecular weight of the organic polymer to be added, it is possible to control the height of the formed fine uneven shape.
  • the organic polymer polyether glycols such as polyethylene glycol and polypropylene glycol are preferable because they are easily eluted from the aluminum oxide gel film by immersion in warm water.
  • the amount of polyether glycols with respect to the weight of the aluminum compound in the aluminum oxide gel film is preferably in the range of 0.1 to 10 times by weight.
  • an aluminum compound and, if necessary, other compounds, a stabilizer, and a water-soluble organic polymer compound are dissolved or suspended in an organic solvent to prepare a sol-gel coating liquid.
  • This sol-gel coating liquid is applied onto the substrate 8 and dried to form an aluminum oxide gel film as a film 7 containing aluminum.
  • a film containing metallic aluminum as the film 7 containing aluminum is formed on the substrate 8 by dry film formation such as vacuum deposition or sputtering.
  • the material of the substrate 8 is not particularly limited, and various materials such as glass, plastic, and metal can be used.
  • the atmosphere for coating is an inert gas atmosphere such as dry air or dry nitrogen.
  • the relative humidity in the dry atmosphere is preferably 30% or less.
  • known coating means such as a dipping method, a spin coating method, a spraying method, a printing method, a flow coating method, and a combination thereof can be appropriately adopted.
  • the film thickness can be controlled by changing the pulling speed in the dipping method, the substrate rotation speed in the spin coating method, and the like, and by changing the concentration of the sol-gel coating liquid. Drying may be performed at room temperature for about 30 minutes.
  • the suitable film thickness of the film 7 containing aluminum is 100 nm or more and 600 nm or less, preferably 100 nm or more and 300 nm or less, and more preferably 100 nm or more and 200 nm or less.
  • the film 7 containing aluminum is immersed in warm water to form aluminum oxide having a fine uneven shape.
  • the surface layer of the aluminum oxide gel film undergoes a gluing action or the like.
  • plate-like crystals containing aluminum oxide as a main component are deposited, grown and formed on the surface layer of the aluminum oxide gel film due to the difference in the solubility of various hydroxides in warm water. ..
  • a metal oxide layer 4 containing an amorphous gel of aluminum oxide which is the above-mentioned metal oxide layer 4 (see FIG. 1), is formed on the substrate 8.
  • the fine uneven shape 92 of the metal oxide layer 4 and the fine metal oxide 3 is formed as described above (see FIG. 1).
  • a film containing metallic aluminum is used instead of the aluminum oxide gel film, aluminum reacts with warm water and is oxidized to aluminum oxide. After that, the fine uneven shape 92 of the fine metal oxide 3 is formed on the surface of the film containing metallic aluminum as in the case of using the aluminum oxide gel film. Therefore, when the material of the substrate 8 mainly contains aluminum or aluminum oxide, it is possible to omit the film formation of the film 7 containing aluminum on the substrate 8.
  • the temperature of the hot water is preferably 40 ° C. or higher and lower than 100 ° C.
  • the immersion treatment time is preferably about 5 minutes to 24 hours.
  • the plate-like crystals of aluminum oxide are crystallized by using the difference in the solubility of each component in warm water. Therefore, unlike the dipping treatment of the aluminum oxide gel film containing a single component of aluminum oxide, the size of the plate-like crystal can be controlled over a wide range by changing the composition of the inorganic component. By adjusting the film thickness of the film 7 containing aluminum, the height of the fine uneven shape 92 of the metal oxide layer 4 and the fine metal oxide 3 can also be adjusted.
  • the average height of the fine uneven shape 92 of the fine metal oxide 3 is preferably 100 nm or more and 1000 nm or less, and more preferably 100 nm or more and 500 nm or less. As a result, it becomes possible to control the fine irregularities formed by the plate-like crystals over the above-mentioned wide range.
  • step 1 step of forming the metal layer 1
  • the metal layer 1 having the fine uneven shape portion 2 to which the fine uneven shape 92 of the mold 9 is transferred is formed.
  • FIG. 3C a step of forming the metal layer 1 on the fine uneven shape 92 of the metal oxide will be described below.
  • a metal plating treatment is preferable, and an electroless plating treatment is further preferable.
  • an aqueous solution in which a palladium compound such as palladium chloride, a gold compound such as gold chloride, a silver compound such as silver chloride, and a tin compound such as tin chloride is dissolved is applied to the fine uneven shape 92 of the metal oxide.
  • activation is performed.
  • the activation may be carried out by immersing the fine uneven shape 92 of the metal oxide together with the substrate 8 in an aqueous solution in which the palladium compound is dissolved. Then, the metal layer 1 is deposited on the fine uneven shape 92 of the metal oxide using the electroless plating solution.
  • the metal ions in the electroless plating solution correspond to the metal layer of the absorption heat shield film of the present embodiment, and an electroless plating solution containing nickel ions, chromium ions, and zinc ions is preferable, and nickel plating containing nickel ions is preferable. Liquids are particularly preferred.
  • the nickel plating solution may contain a phosphorus component and a boron component in addition to the nickel component. Examples of commercially available nickel plating solutions include the Top Nicolon series of Okuno Pharmaceutical Industry Co., Ltd.
  • the temperature of the plating solution in the electroless plating treatment is preferably 30 ° C. or higher and 98 ° C. or lower, more preferably 50 ° C. or higher and 90 ° C. or lower.
  • the time for performing the electroless plating treatment can be adjusted according to the thickness of the metal layer to be formed, and is usually 30 seconds to 1 hour.
  • the metal layer 1 is formed so as to fill the gaps of the fine concavo-convex shape, and the metal layer 1 including the fine concavo-convex shape portion 2 to which the fine concavo-convex shape 92 of the metal oxide is transferred is formed.
  • the portion located above the apex of the convex portion (for example, the convex portion 910) of the concave-convex structure 91 becomes the base portion 11, and the convex portion of the concave-convex structure 91 (for example, the convex portion 910).
  • the portion located below the apex (on the side of the mold 9) is the fine uneven shape portion 2. That is, the metal layer 1 having the base portion 11, the first uneven structure 21 (first structure), and the second uneven structure 22 (second structure) is formed.
  • the metal layer 1 provided with the base 11, the first uneven structure 21 (first structure), and the second uneven structure 22 (second structure) is preferably a plated layer.
  • the main components of the metal material of the metal layer 1 provided with the base 11, the first uneven structure 21, and the second uneven structure 22 are the same.
  • the thickness of the metal layer 1 including the fine uneven shape portion 2 is 200 nm or more and 15,000 nm or less. Since the metal layer 1 is formed so as to cover the apex of the convex portion (for example, the convex portion 910) of the concave-convex structure 91 and the portion becomes the base portion 11, the thickness of the base portion 11 can be 200 nm or more and 15000 nm or less. .. Further, the average height of the second uneven structure 22 in the fine uneven shape portion 2 corresponds to the average height of the fine uneven shape 92 of the metal oxide, and is 100 nm or more and 1000 nm or less. When the thickness of the metal layer 1 including the fine uneven shape portion 2 is 200 nm or more, the heat-absorbing heat-shielding film of the present embodiment exhibits excellent heat-absorbing heat-shielding characteristics.
  • electroplating may be performed on the surface of the metal layer 1 opposite to the surface provided with the fine uneven shape portion 2. ..
  • a known electroplating solution can be used for the electroplating treatment, and for example, an electroplating solution containing nickel ions, iron ions, copper ions and the like can be used as the metal ions.
  • the electroplating treatment is performed using the same metal as the metal of the metal layer 1, the thickness of the metal layer can be increased by the electroplating treatment.
  • an electroplating treatment is performed on the metal layer 1 using a metal different from the metal of the metal layer 1, the metal layer provided by the electroplating treatment becomes the base material 5.
  • the electroplating solution contains a conductive salt, a salt for adjusting counterions, and a carboxylic acid-based additive for improving the homogeneity of the plating film, if necessary.
  • a brightener or the like may be added.
  • the thickness of the metal layer 1 can be made a desired thickness by adjusting the liquid temperature, the current density, and the plating time of the electroplating liquid.
  • an aqueous solution containing an acid or the like may be used to activate a surface opposite to the surface on which the fine uneven shape portion 2 of the metal layer 1 is provided.
  • a step of removing foreign matters in the electroplating solution may be provided.
  • the base material 5 is adhered to the surface opposite to the surface of the metal layer 1 obtained above where the fine uneven shape portion 2 is provided. ..
  • the shape and material of the base material 5 those described above can be used.
  • the metal to be the base material 5 may be further laminated on the surface opposite to the surface of the metal layer 1 on which the fine uneven shape portion 2 is provided.
  • the metal may be laminated by the above-mentioned electroplating treatment, or may be laminated by physical vapor deposition such as sputtering.
  • the base material is provided by depositing the resin to be the base material 5 on the surface opposite to the fine uneven shape 92 of the metal oxide of the metal layer 1 and then curing the base material 5. May be good.
  • the base material 5 may be adhered to the metal layer 1 by the adhesive layer 6.
  • the adhesive material used for the adhesive layer 6 is not particularly limited, and may be any material as long as the base material 5 and the metal layer 1 are firmly adhered to each other.
  • FIGS. 3E to 3H the etching step will be described in detail using the absorption heat shield member provided with the base material 5 and the adhesive layer 6 as an example. The same applies to the heat-absorbing heat-shielding film that does not include the heat member, the base material 5, and the adhesive layer 6. Note that FIG. 3E is an upside-down view of the heat-absorbing heat-shielding member shown in FIG. 3D.
  • the substrate 8 is removed as shown in FIG. 3F.
  • the heat-absorbing and heat-shielding member after removal of the substrate 8 includes a film 7 containing metallic aluminum or a metal oxide layer 4 on the surface thereof.
  • a film containing metallic aluminum visible light is reflected by the metallic aluminum, so that it is necessary to further remove the film containing metallic aluminum by etching as shown in FIG. 3G.
  • the metal oxide layer 4 layer containing the amorphous gel of aluminum oxide
  • the layer containing the amorphous gel of aluminum oxide is the metal oxide layer 4 of the absorption heat shield member.
  • the layer containing the amorphous gel of aluminum oxide may be removed by etching so as to satisfy the required surface hardness and absorbance.
  • etching method wet etching in which a film containing metallic aluminum or a metal oxide layer 4 is dissolved using an acid or alkaline solution is preferable.
  • the acid include hydrochloric acid, nitric acid, sulfuric acid and the like.
  • the alkali include sodium hydroxide, potassium hydroxide and the like. From the viewpoint of work efficiency, an etching method using an alkaline solution is more preferable.
  • the etching concentration is preferably in the range of several% to several tens of percent, and the etching time is preferably in the range of several hours to several days.
  • the fine metal oxide 3 having a fine uneven shape 92 may also be removed by etching.
  • the metal layer 1 in which the metal oxide adheres to the fine uneven shape portion 2 in other words, the absorption heat shield film 10 containing the metal oxide adhered to the fine uneven shape portion 2.
  • the absorption heat shield member in which the metal layer 1 including the fine uneven shape portion 2 on the outermost surface is adhered to the base material 5 via the adhesive layer 6 realizes particularly excellent absorption.
  • the metal layer 1 in which the metal oxide is attached to the fine uneven shape portion 2 also has extremely excellent absorbance, and the strength of the fine uneven shape portion 2 can be improved, so that the durability and environmental resistance are improved. Is also excellent.
  • the residual metal oxide such as aluminum oxide after etching can be detected by measuring EDX or XPS when observing the surface or cross section by SEM or TEM. ..
  • the degree of etching treatment may be adjusted according to the balance between the absorption performance and the surface hardness of the desired absorption heat shield member or absorption heat shield film. Further, the etching step of this step may be performed before the bonding step of the base material 5 which is the third step, and then the base material 5 may be bonded.
  • the light-absorbing heat-shielding member and the light-absorbing heat-shielding film of the present embodiment thus obtained include the metal layer 1 including the fine uneven shape portion 2, the reflectance in the visible light region is low and far away because it absorbs visible light. Infrared radiation is small. Therefore, the reflectance in the far-infrared region becomes high, and excellent heat-absorbing and heat-shielding characteristics can be realized.
  • the absorption heat shield film 10 of the present embodiment is preferably used for a heating element as a member or an article.
  • a heating element examples include a battery, an engine, a motor, a vehicle, and the like.
  • Engines include reciprocating engines, rotary engines, diesel engines, gas turbine engines, jet engines, rocket engines, etc.
  • Motors include DC motors, AC motors, PM motors, brush motors, stepping motors, induction motors, servo motors, ultrasonic motors, in-wheel motors, linear motors, and the like.
  • the transport device including at least one of the engine and the motor may be provided with the absorption heat shield film 10.
  • Transportation equipment including at least one of an engine and a motor is not limited to various vehicles such as automobiles and trains, but also ships, aircraft such as drones, and various robots such as AGVs.
  • the transportation equipment is not limited to passenger transportation, but may be freight transportation, or may be unmanned operation by remote control or autonomous guidance.
  • a hybrid vehicle is a vehicle equipped with a battery, an engine, and a motor.
  • the heat-absorbing heat-shielding film 10 and the heat-absorbing heat-shielding member 100 of the present embodiment can be used as a stray light prevention and heat-shielding member inside an optical device, or as an interior / exterior member of a space-related device such as an artificial satellite, and are for exterior use. It can also be used as a film, solar collector, etc. In addition, the heat-absorbing heat-shielding film of the present embodiment can also be used for clothes and the like. Further, the absorbent heat-shielding film of the present embodiment may be used as a heat-shielding decorative film.
  • the absorbent heat-shielding film of the present embodiment can be provided as a heat-shielding decorative film on the surface of a vehicle interior, mobile device, home electric appliance, parasol, or tent article.
  • Various adhesives can be used when the heat-absorbing heat-shielding film of the present embodiment is provided on the surface of a member or an article. Therefore, the heat-absorbing heat-shielding film of the present embodiment can be provided on the surface of the member and the article depending on the purpose of use, and the surface of the member and the article is not limited to a smooth one, and has a two-dimensional or three-dimensional curved surface. It may have.
  • the member or article provided with the light-absorbing heat-shielding film on the outermost surface of the present embodiment has a difference in the detection temperature as compared with the member or article not provided with the light-absorbing heat-shielding film, the light-absorbing heat-shielding film of the present embodiment is provided. It is possible to clearly identify a member or an article by using.
  • the detection temperature on the surface opposite to the surface of the light-absorbing heat-shielding film in contact with the member or the article is provided by the light-absorbing heat-shielding film of the member or the article. It suffices if it is 3 ° C. or more lower than the detected temperature in the unmarked portion. At this time, if the member or the article is a heating element, it can be more clearly identified.
  • a lens reflectance measuring device (trade name: USPM-RU III, manufactured by Olympus Co., Ltd.) was used for the reflectance spectrum measurement in the visible light region of the example.
  • a Fourier transform infrared spectrophotometer (FT / IR-6600, manufactured by Nippon Spectroscopy Co., Ltd.) was used to measure the reflectance spectrum in the infrared region of the examples.
  • Example 1 Manufacturing of absorption heat shield member
  • Aluminum-sec-butoxide hereinafter, also referred to as “Al (O-sec-Bu) 3
  • EtOAc Ac ethyl acetoacetate
  • IPA 2-propanol
  • the mixture was stirred at room temperature for about 3 hours to prepare an aluminum oxide sol solution.
  • a 0.01 M dilute hydrochloric acid aqueous solution was added to the aluminum oxide sol solution so that the hydrochloric acid additive was doubled in terms of molar ratio with respect to Al (O-sec-Bu) 3, and the mixture was refluxed for about 6 hours to allow the sol-.
  • a gel coating solution was prepared.
  • the sol-gel coating liquid was applied by a spin coating method onto a quartz glass substrate (# 1200) having a surface as a base material in a threaded state to form a coating film. Then, the coating film was heat-treated at 100 ° C. for 1 hour to obtain a transparent aluminum oxide gel film. Next, the aluminum oxide gel film was immersed in warm water at 80 ° C. for 30 minutes and then dried at 100 ° C. for 10 minutes to form an aluminum oxide layer having a fine uneven shape.
  • a palladium chloride aqueous solution was applied on an aluminum oxide layer having a fine uneven shape by a spin coating method, and then dried at 100 ° C. Then, it was immersed in a nickel-phosphorus plating solution (phosphorus content of about 1 to 2 wt%) set at 80 ° C. for 20 minutes to form a nickel layer as a metal layer having a fine uneven shape portion and a base portion under the fine uneven shape portion. .. Then, the heat-absorbing heat-shielding film was peeled off from the quartz glass substrate and etched with a 3M sodium hydroxide aqueous solution at room temperature for 50 hours as an etching step to produce the heat-absorbing heat-shielding film. The total film thickness of the obtained absorbent heat-shielding film was about 10 ⁇ m.
  • the obtained heat-absorbing heat-shielding film is formed of two different hierarchical structures, a large structure derived from the base substrate (first structure) and a small structure derived from the fine uneven shape of aluminum oxide (second structure).
  • first structure a large structure derived from the base substrate
  • second structure a small structure derived from the fine uneven shape of aluminum oxide
  • Table 1 shows the surface roughness of the obtained heat-absorbing heat-shielding film.
  • the surface roughness was calculated from image analysis.
  • the method of image analysis is as follows. Image analysis software ImageJ (available from NIH Image, https: //imagej.nih.gov/ij/) was used for image processing.
  • the average roughness Ra of the acquired cross-sectional SEM image was calculated as follows. First, the grayscale image was binarized, and the roughness curve of the uneven surface was quantified by Line Graph. The average line was obtained from the quantified roughness curve at low and high magnifications as follows. At low magnification, the linear equation was fitted to the quantified roughness curve by the method of least squares to obtain the average line. At high magnification, the quantified roughness curve was smoothed with a Savitzky-Goray filter to obtain an average line. From the quantified roughness curve, the difference between the average lines was set to Y, the average line direction was set to X, and the average roughness Ra was calculated according to the equation (1).
  • the average roughness Ra of the first structure of the heat-absorbing heat-shielding film obtained in Example 1 was 0.2 ⁇ m, and the maximum height Rz was 1.3 ⁇ m.
  • the average roughness Ra of the second structure was 36 nm, and the maximum height Rz was 165 nm.
  • Table 1 shows the reflectances in the visible light and infrared regions obtained by measuring the reflectance spectra in the visible light region and the infrared region of the heat-absorbing heat shield member. Further, in Table 1, the one having low reflectance in the visible light region and excellent absorbance is designated as A, and in the mid-infrared and far-infrared regions, the reflectance is high toward the long wavelength side and the heat shielding property is excellent. The one that is present is designated as A.
  • the heat-absorbing heat-shielding member of this embodiment has excellent absorbance because the reflectance in the visible light region is low.
  • the heat-absorbing heat-shielding member of this embodiment has excellent heat-shielding properties because the reflectance increases toward the long wavelength side in the mid-infrared and far-infrared regions.
  • Table 1 shows the results of photographing the heat-absorbing heat-shielding member by a thermal image camera (infrared camera) by 45 ° from eight directions with different shooting angles.
  • A is the one in which the reflection of the ambient light source is not seen from any angle and the glare due to the reflection from the surrounding light source is small.
  • B the reflection from the ambient light source
  • Example 2 An absorption heat-shielding film was produced in the same manner as in Example 1 except that the base substrate was changed to # 600 ground glass.
  • Example 3 An absorption heat-shielding film was produced in the same manner as in Example 1 except that the base substrate was changed to # 400 ground glass.
  • Example 4 An absorption heat-shielding film was produced in the same manner as in Example 1 except that the base substrate was changed to # 240 ground glass.
  • Example 5 An absorption heat-shielding film was produced in the same manner as in Example 1 except that the base substrate was changed to # 120 ground glass.
  • Table 1 shows the surface roughness of the heat-absorbing heat-shielding film produced in Examples 1 to 5, and the reflectances in the visible light region and the infrared region obtained by the reflection spectrum measurement in the visible light region and the infrared region.
  • Example 6 An article in which the absorbent heat-shielding film produced in Example 1 was attached to the surface of a plate-shaped stainless steel (SUS) (hereinafter, referred to as "an article having an absorbent heat-shielding film") was produced.
  • the same article as the article having the absorption heat shield film on the surface hereinafter referred to as “the article without the absorption heat shield film” except that the article having the absorption heat shield film and the article not having the absorption heat shield film are on the heater.
  • the article with the absorption heat shield film and the absorption heat shield film are used with an infrared thermography device (model: H2640, manufactured by Nippon Avionics Co., Ltd.).
  • the surface temperature of the article not provided with was measured.
  • the surface temperature measurement environment was room temperature, and the distance between the article and the measuring device was about 40 cm.
  • the surface temperature of the article provided with the heat-absorbing heat-shielding film was about 30 ° C., which was about 10 ° C. lower than the surface temperature of the article without the heat-absorbing heat-shielding film.
  • the surface temperature of the article without the heat-absorbing heat-shielding film was about 60 ° C.
  • the surface temperature of the article with the heat-absorbing heat-shielding film was about 36 ° C., which was about 24 ° C. lower. From the above, it was found that the absorbent heat-shielding film of this example has excellent heat-shielding properties. A clear temperature difference was observed in the detected temperature of the article compared to the actual temperature, and it was found that the article can be identified by the infrared thermal image camera.
  • the same evaluation was performed on the heat-absorbing heat-shielding membranes obtained in Examples 2 to 5.
  • the detection temperature on the surface of the member or the article opposite to the surface in contact with the member or the article is 3 ° C. or higher than the detection temperature in the portion of the member or the article not provided with the absorption heat shield, and the heat shield is excellent.
  • the reflection of the surrounding light source was also suppressed as in the article of Example 1.
  • the article of the present embodiment is excellent in both absorbance and heat shielding property while suppressing the reflection of the surrounding light source.
  • the present embodiment provides an absorbent heat shield film and an absorbent heat shield member that absorb visible light and near infrared rays (low reflectance) and emit small far infrared rays (high reflectance), which are usually incompatible with each other. be able to.

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  • Physics & Mathematics (AREA)
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  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
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  • General Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Laminated Bodies (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Thermal Insulation (AREA)
PCT/JP2021/026956 2020-07-22 2021-07-19 吸光遮熱膜、吸光遮熱部材、および物品、並びにそれらの製造方法 Ceased WO2022019264A1 (ja)

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DE112021003914.8T DE112021003914T5 (de) 2020-07-22 2021-07-19 Lichtabsorbierender wärmeabschirmender film, lichtabsorbierendes wärmeabschirmendes element, gegenstand und verfahren zu ihrer herstellung
JP2022538000A JP7844333B2 (ja) 2020-07-22 2021-07-19 吸光遮熱膜、吸光遮熱部材、および物品、並びにそれらの製造方法
CN202180060439.1A CN116134346A (zh) 2020-07-22 2021-07-19 吸光性隔热膜、吸光性隔热构件、制品及其制造方法
GB2301399.8A GB2612240B (en) 2020-07-22 2021-07-19 Light absorptive heat shielding film, light absorptive heat shielding member, article, and methods for manufacturing same
US18/156,942 US20230161083A1 (en) 2020-07-22 2023-01-19 Light-absorbing heat-shielding film, light-absorbing heat-shielding member, article, and method for producing them

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JP2020125161 2020-07-22

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WO2024147293A1 (ja) 2023-01-06 2024-07-11 キヤノン株式会社 吸光遮熱膜、吸光遮熱部材、物品、吸光遮熱膜の製造方法、及び吸光遮熱部材の製造方法

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WO2024147293A1 (ja) 2023-01-06 2024-07-11 キヤノン株式会社 吸光遮熱膜、吸光遮熱部材、物品、吸光遮熱膜の製造方法、及び吸光遮熱部材の製造方法
EP4644956A1 (en) 2023-01-06 2025-11-05 Canon Kabushiki Kaisha Light-absorbing/heat-insulating film, light-absorbing/heat-insulating member, article, method for manufacturing light-absorbing/heat-insulating film, and method for manufacturing light-absorbing/heat-insulating member

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JPWO2022019264A1 (https=) 2022-01-27
US20230161083A1 (en) 2023-05-25
GB202301399D0 (en) 2023-03-15
CN116134346A (zh) 2023-05-16
JP7844333B2 (ja) 2026-04-13
DE112021003914T5 (de) 2023-05-11
GB2612240A (en) 2023-04-26

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