# US 8,542,424 B2 · Black coating film and production method therefor, black light shading plate, and diaphragm, diaphragm device for light intensity adjustment, shutter using the same, and heat resistant light shading tape > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,542,424 B2 - Document ID: US8542424B2 - Status: Granted - Kind: B2 - Application number: 13/062,435 - Filed: 2009-08-11 - Published: 2011-07-07 - Granted: 2013-09-24 - Earliest claimed: 2008-09-05 - Assignees: Sumitomo Metal Mining Co., Ltd. - Applicants: Yoshiyuki Abe; Katsushi Ono; Yukio Tsukakoshi - Inventors: Yoshiyuki Abe; Katsushi Ono; Yukio Tsukakoshi - Web page: https://patentgrep.com/patent/US8542424B2 ## CPC - G03B 9/02: Diaphragms - C23C 14/0015: {characterized by the colour of the layer} - C23C 14/0036: {Reactive sputtering} - C23C 14/083: {of refractory metals or yttrium} - C23C 14/3414: {Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy} - G02B 5/003: {Light absorbing elements} - G02B 5/005: {Diaphragms (for cameras G03B9/02)} - G02B 5/22: Absorbing filters {(G02B5/201 - G02B5/208 take precedence)} - G03B 9/08: Shutters - Y02T 50/60: Efficient propulsion technologies, e.g. for aircraft - Y10T 428/24355: Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.] - Y10T 428/2848: Three or more layers - G03B: APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR (optical parts of such apparatus G02B; photosensitive materials or processes for photographic purposes G03C; apparatus for processing exposed photographic materials G03D) - C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04) - G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS - Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract A heat resistant black coating film which is capable of making the surface of optical members to be low reflection property and black property, a black light shading plate having a resin film using the same as a base substrate, and a diaphragm, a diaphragm device for light intensity adjustment and a shutter using the same, and heat resistant light shading tape. They are provided by a black coating film (A), where a titanium oxide film containing titanium and oxygen as main components, and having an oxygen content of from 0.7 to 1.4, as atomicity ratio O/Ti, is formed on an opaque or translucent substrate, characterized in that the titanium oxide film takes a constitution of fine columnar crystals assembled, where the longitudinal direction of the crystal extends in a film thickness direction, has protrusions at the film surface, and has a film thickness of equal to or thicker than 50 nm; and a black light shading plate, wherein the metallic light shading film (B), having a film thickness of equal to or thicker than 40 nm, is formed onto at least one surface of the substrate, and still more the black coating film (A) is laminated and formed on the surface of the metallic light shading film (B), or the like. ## Claims ### Claim 1 A black coating film (A), where a titanium oxide film containing titanium and oxygen as main components and having an oxygen content of from 0.7 to 1.4 as atomicity ratio O/Ti, is formed on a substrate, characterized in that said titanium oxide film takes a constitution of fine columnar crystals assembled, where the longitudinal direction of the crystal extends in a film thickness direction, has protrusions at said film surface, and has a film thickness of equal to or thicker than 50 nm. ### Claim 2 (depends on 1) The black coating film according to claim 1, characterized in that the substrate is selected from a thin film of a metal such as stainless steel, SK (carbon steel), Al or Ti, a thin film of ceramic such as alumina, magnesia, silica or zirconia, a glass plate, a resin plate or a resin film. ### Claim 3 (depends on 1) The black coating film according to claim 1, characterized in that the titanium oxide film still more contains carbon, and is a titanium oxy-carbide film having a content of equal to or higher than 0.7 as atomicity ratio C/Ti. ### Claim 4 (depends on 1) The black coating film according to claim 1, characterized in that crystallite size of the fine columnar crystal, which constitutes the titanium oxide film or the titanium oxy-carbide film, is from 10 to 40 nm as diameter (width). ### Claim 5 (depends on 1) The black coating film according to claim 1, characterized in that the film thickness is from 50 to 250 nm. ### Claim 6 (depends on 1) The black coating film according to claim 1, characterized in that an arithmetic average height (Ra) in a region of 1 μm×1 μm, measured with an atomic force microscope, is equal to or higher than 1.8 nm. ### Claim 7 (depends on 6) The black coating film according to claim 6, characterized in that an arithmetic average height (Ra) in a region of 1 μm×1 μm, measured with an atomic force microscope, is equal to or higher than 2.4 nm. ### Claim 8 (depends on 1) The black coating film according to, claim 1, characterized in that a parallel light transmittance of the film itself, in a wavelength of from 380 to 780 nm, is from 13 to 35%, as an average value. ### Claim 9 (depends on 1) A method for producing the black coating film according to claim 1, characterized in that a titanium oxide film or a titanium oxy-carbide film is formed on a substrate by sputtering under a film-formation gas pressure of equal to or higher than 1.5 Pa, by using any of sintered body target selected from titanium oxide, titanium oxide and titanium carbide, or titanium oxy-carbide. ### Claim 10 (depends on 9) The method for producing the black coating film according to claim 9, characterized in that the film-formation gas is inert gas comprising mainly argon or helium, and a content of oxygen gas is equal to or lower than 0.8% by volume. ### Claim 11 (depends on 1) A laminated body of a black light shading thin film having sequential lamination, on the black coating film (A) selected from the titanium oxide film or the titanium oxy-carbide film according to claim 1, of a metallic light shading film (B) and the black coating film (A) similar to the above. ### Claim 12 (depends on 11) The laminated body of a black light shading thin film according to claim 11, characterized in that the metallic light shading film (B) is a metal material containing one or more kinds of elements selected from titanium, tantalum, tungsten, cobalt, nickel, niobium, iron, zinc, copper, aluminum, or silicon, as main components. ### Claim 13 (depends on 11) The laminated body of a black light shading thin film according to claim 11, characterized in that the metallic light shading film (B) is a titanium carbide film or a titanium oxy-carbide film, and a carbon content in said film is equal to or higher than 0.6 as atomicity ratio C/Ti, and an oxygen content in the film is equal to or lower than 0.4 as atomicity ratio O/Ti. ### Claim 14 (depends on 11) A black light shading plate, where the laminated body of a black light shading thin film according to claim 11 is formed at one surface side of a translucent substrate, characterized in that the metallic light shading film (B) has a film thickness of equal to or thicker than 100 nm, an average optical density in a wavelength of from 380 to 780 nm is equal to or higher than 4.0, and an average value of direct optical reflectance at the surface of the laminated body and at the substrate surface not formed with the film in a wavelength of from 380 to 780 nm is equal to or lower than 18%. ### Claim 15 (depends on 14) The black light shading plate according to claim 14, characterized in that the translucent substrate is a resin film, a resin plate, a glass plate, a ceramic plate or a single crystal plate of an inorganic compound. ### Claim 16 (depends on 15) The black light shading plate according to claim 15, characterized in that the translucent substrate is a polyimide film. ### Claim 17 (depends on 14) The black light shading plate according to claim 14, characterized in that the translucent substrate has surface irregular property. ### Claim 18 (depends on 14) The black light shading plate according to claim 14, characterized in that surface roughness at the translucent substrate side is from 0.0001 to 0.7 μm (arithmetic average height), and an average value of direct optical reflectance at the surface of the laminated body of a black light shading thin film in a wavelength of from 380 to 780 nm is equal to or lower than 0.8%. ### Claim 19 (depends on 14) The black light shading plate according to claim 14, characterized in that the lightness (L*) of the film surface side of the black light shading plate formed with the laminated body of a black light shading thin film, is from 25 to 45. ### Claim 20 (depends on 14) The black light shading plate according to claim 14, characterized in that the lightness (L*) of the translucent substrate surface side of the black light shading plate formed with the laminated body of a black light shading thin film, is from 25 to 45. ### Claim 21 (depends on 11) A black light shading plate, characterized in that a surface roughness of the black coating film (A) formed at the surface of the metallic light shading film (B), in the laminated body of a black light shading thin film according to claim 11 is from 0.05 to 0.7 μm (arithmetic average height), and an average value of direct optical reflectance at the surface of the black coating film (A) in a wavelength of from 380 to 780 nm is equal to or lower than 0.8%. ### Claim 22 (depends on 1) A black light shading plate, wherein by using a resin film, a resin plate, a metal thin plate or a ceramic thin plate, as a substrate, the metallic light shading film (B) having a film thickness of equal to or thicker than 40nm, is formed onto at least one surface thereof, and still more the black coating film (A) according to claim 1 is laminated and formed onto the surface of the metallic light shading film (B), characterized in that an average optical density in a wavelength of from 380 to 780 nm is equal to or higher than 4.0, and an average value of direct optical reflectance at the surface of the black coating film in a wavelength of from 380 to 780 nm is equal to or lower than 18%. ### Claim 23 (depends on 22) The black light shading plate according to claim 22, characterized in that the resin film, the resin plate, the metal thin plate or the ceramic thin plate has surface irregular property. ### Claim 24 (depends on 22) The black light shading plate according to claim 22, characterized in that the resin film is a polyimide film. ### Claim 25 (depends on 22) The black light shading plate according to claim 22, characterized in that the metallic light shading film (B) is a metal material containing one or more kinds of elements selected from titanium, tantalum, tungsten, cobalt, nickel, niobium, iron, zinc, copper, aluminum, or silicon, as main components. ### Claim 26 (depends on 22) The black light shading plate according to claim 22, characterized in that the metallic light shading film (B) is a titanium carbide film or a titanium oxy-carbide film, and a carbon content in said film is equal to or higher than 0.6, as atomicity ratio C/Ti, and an oxygen content in the film is equal to or lower than 0.4, as atomicity ratio O/Ti. ### Claim 27 (depends on 22) The black light shading plate according to claim 22, characterized in that the metallic light shading film (B) having substantially the same film thickness and the same composition is formed at both surfaces of the substrate of the resin film, the resin plate, the metal thin plate or the ceramic thin plate, and still more the black coating film (A) having substantially the same film thickness and the same composition is laminated and formed at the surface of the metallic light shading film (B), and they have a symmetric structure to the substrate. ### Claim 28 (depends on 22) The black light shading plate according to claim 22, characterized in that a surface roughness of the black coating film (A) formed at the surface of the metallic light shading film (B) is from 0.05 to 0.7 μm (arithmetic average height), and an average value of direct optical reflectance at the surface of the black coating film (A) in a wavelength of from 380 to 780 nm is equal to or lower than 0.8%. ### Claim 29 (depends on 22) The black light shading plate according to claim 22, characterized in that a lightness (L*) of the black light shading plate, where the black coating film (A) is formed on the surface of the metallic light shading film (B), is from 25to 45. ### Claim 30 (depends on 22) A diaphragm obtained by fabrication of the black light shading plate according to claim 22. ### Claim 31 (depends on 22) A diaphragm device for light intensity adjustment using blade materials obtained by fabrication of the black light shading plate according to claim 22. ### Claim 32 (depends on 22) A shutter using the blade materials obtained by fabrication of the black light shading plate according to claim 22. ### Claim 33 (depends on 22) A heat resistant light shading tape comprising an adhesive layer placed at one surface or both surfaces of the black light shading plate according to claim 22. ### Claim 34 (depends on 1) A black light shading plate, wherein by using a colored resin film as a substrate, the black coating film (A) according to claim 1 is formed on at least one surface thereof, characterized in that film thickness of the black coating film (A) is equal to or thicker than 20 nm, and an average value of direct optical reflectance at the surface of the black light shading plate, in a wavelength of from 380 to 780 nm, is equal to or lower than 1%. ### Claim 35 (depends on 34) The black light shading plate according to claim 34, characterized in that the colored resin film has surface irregular property. ### Claim 36 (depends on 34) The black light shading plate according to claim 34, characterized in that the film thickness of the black coating film (A) is from 20 to 150 nm. ### Claim 37 (depends on 34) The black light shading plate according to claim 34, characterized in that the lightness (L*) of the black light shading plate obtained by formation of the black coating film (A) on the colored resin film, is from 25 to 45. ### Claim 38 A method for producing a black coating film, characterized in that oxygen contained in a sintered body and/or oxygen in residual gas in a film-formation room is incorporated into the film by sputtering film-formation by using any of a sintered body target selected from titanium oxide, titanium oxide and titanium carbide, or titanium oxy-carbide, without introducing oxygen gas and introducing inert gas comprising mainly argon or helium, as the film-formation gas, during film-formation. ### Claim 39 (depends on 38) The method for producing the black coating film according to claim 38, characterized in that film-formation is performed under a film-formation gas pressure of equal to or higher than 1.5 Pa, in sputtering.