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
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3613—Coatings of type glass/inorganic compound/metal/inorganic compound/metal/other
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3626—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3639—Multilayers containing at least two functional metal layers
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3647—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer in combination with other metals, silver being more than 50%
• • 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
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/28—Interference filters
  • G02B5/281—Interference filters designed for the infrared light
  • G02B5/282—Interference filters designed for the infrared light reflecting for infrared and transparent for visible light, e.g. heat reflectors, laser protection
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
  • Y10T428/24917—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including metal layer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
  • Y10T428/24926—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including ceramic, glass, porcelain or quartz layer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31507—Of polycarbonate
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31605—Next to free metal
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31609—Particulate metal or metal compound-containing

Definitions

• the invention relates to a stack of thin, interference layers, reflecting at least partially in the infrared, in particular emitted by solar radiation, and which comprises at least one "functional" layer and coatings of dielectric material arranged on each side of it.
• “Functional layer (s)” is understood to mean, within the meaning of the invention, the layer or layers which have the desired thermal reflection properties in the stack, and which are metallic, more particularly based on noble metal of the type Ag.
• Dielectric material coatings is understood to mean, within the meaning of the invention, a layer or a superposition of layers of dielectric material of the metal oxide, metal nitride or silicon nitride type, having in particular a function for adjusting the optical appearance of the stack, in particular for lowering the light reflection, and optionally a protective function with respect to the "functional" layer or layers.
• the invention is concerned with stacking layers on a rigid substrate of the glass or rigid polymer type such as polycarbonates PC or polymethyl methacrylate PMMA.
• Substrates can be used in glazing, alone or mounted in insulating or laminated glazing.
• the invention is however more particularly interested in flexible substrates based on polymer, in particular in PU polyurethane or in polyethylene terephthalate.
• Studies have already been carried out on stacks with silver layers interspersed with dielectrics made of AIN and / or metal oxide and deposited on PET substrates.
• nitride-based dielectrics are particularly chemically stable, and can thus effectively fulfill the role of "barrier layer” with respect to the silver layer or layers. It is therefore advantageous to arrange them at least in “sublayer”, directly on the substrate and / or in "overlayer”, as the last layer of the stack.
• the object of the invention is therefore to remedy the aforementioned drawbacks, in particular to improve the quality of the stacks of thin layers comprising both silver-based layers and nitride-based layers, without causing difficulties or complications. in their manufacturing mode on an industrial scale.
• the invention firstly relates to a transparent, flexible or rigid substrate, provided with a stack of thin layers comprising at least one functional layer predominantly based on silver Ag disposed between two coatings of dielectric material, at least one coatings comprising a layer mainly based on aluminum nitride AIN.
• the (or at least one of) the functional layer (s) is chemically modified by incorporating at least one minority metal M other than Ag.
• the (or at least one of) layer (s) based on AIN is also chemically modified by incorporation of at least one minority metal M ′ other than aluminum Al.
• the incorporation of the metal M and of the metal M ′ can be carried out using (as for all the other layers of the stack, moreover), the known vacuum deposition technique which is sputtering, preferably assisted by magnetic field: a silver target alloyed with the metal M in question can then be provided respectively (deposition in an inert atmosphere, possibly containing nitrogen) and an aluminum target alloyed with the metal M 'in question (deposition of the nitride in a reactive nitriding atmosphere, containing nitrogen).
• the known vacuum deposition technique which is sputtering, preferably assisted by magnetic field: a silver target alloyed with the metal M in question can then be provided respectively (deposition in an inert atmosphere, possibly containing nitrogen) and an aluminum target alloyed with the metal M 'in question (deposition of the nitride in a reactive nitriding atmosphere, containing nitrogen).
• the term "metal" includes silicon.
• the alloy can be made in a known manner by sintering a mixture of powders of the metals in question. It is also possible to partially cover the Al target with the metal in question.
• the substrates as recalled in the preamble of this text, can be rigid or flexible.
• the metal M that can be incorporated in the layer based on silver is aluminum, copper or gold. Preferably, between 0.1 and 10%, especially between 0.5 and 2% by weight, of metal M is added to the silver layer.
• the metal M ′ which can be incorporated into the layer based on AIN is chosen from at least one of the following metals: Zn, Ti, Sn, Mn, Mg, Ag. preferably adding about 0.1 to 10%, especially 0.5 to 2% by weight, of the metal M 'relative to the aluminum of the layer.
• the first preferred embodiment of the invention consists in that the stack comprises at least one functional layer based on silver modified according to the invention which is contiguous with at least one layer based on AlN, standard (or also modified according to the invention): here it is rather a question of adapting the layer of Ag to the layer of AIN.
• the second preferred embodiment according to the invention alternative or cumulative with the first embodiment, consists in that the stack comprises at least one layer based on modified AIN according to the invention which is contiguous with a functional layer based on standard silver (or also modified according to the invention).
• the opposite approach is here adapted, where we seek rather to make the AIN more " compatible " with money.
• a possible variant of the invention consists in that the functional layer (at least one of them or each of them if the stack comprises more than one) is in contact on one of its faces with a AlN layer (one of the two or both being modified in accordance with the invention), the other side of the functional layer being in contact with a layer of metal oxide or mixed metal oxides such as ZnO, TiO 2 , SnO 2 , Nb 2 Os, Ta 2 O 5 .
• metal oxide or mixed metal oxides such as ZnO, TiO 2 , SnO 2 , Nb 2 Os, Ta 2 O 5 .
• This oxide layer may be the last of a superposition of layers of oxides and / or nitride such as AIN or Si 3 N 4 .
• Another variant (cumulative with the previous one) is that the layer of AIN modified according to the invention is in direct contact with the silver layer and has a higher metal concentration M 'near its interface with this silver layer. In other words, one can have a concentration gradient of the metal AIN layer M ', with an increasing concentration towards the AIN / Ag interface.
• the simplest embodiment industrially consists in fact of dividing the AIN layer into several " strata": the one closest to silver being the richest in metal M '(obtained from a target Al- M ') and the rest of the layer being poor in metal M 'or even completely devoid of metal M' (target Al).
• AIN M '/ AIN or AIN / AIN: M'
• metal oxide is understood a layer of metal oxide or several different oxides, or a layer of nitride AIN or Si N 4 "framed” by layers of oxide (or thin layers of Ti or NiCr type metal).
• TiO 2 is particularly preferred.
• one of the functional layers of Ag does not follow the teaching of the invention unlike the other, and is for example in contact with a layer of AIN or If 3 N 4 through a thin layer intended to increase their mutual adhesion, for example made of titanium.
• the subject of the invention is also any glazing incorporating the layer substrate described above. It is in particular a laminated glazing which uses a flexible substrate of the PET type coated with the layers according to the invention, laminated by means of two thermoplastic adhesive sheets of the polyvinyl butyral (PVB) or ethylene vinyl acetate (EVA) type with two substrates rigid, glass type.
• PVB polyvinyl butyral
• EVA ethylene vinyl acetate
• the glazing of the invention whether monolithic, laminated, mounted in insulating double glazing, can be used in the building or to equip vehicles, in particular as windshield or laminated side glasses.
• PET / TiO 2 / Ag / TiO 2 / Ag / AlN Ti
• Ti contains 1.5% Ti by weight relative to Al, as in Examples 2 and 3. This content can be varied in a range preferably from 0.5 to 2.5%.
• PET / AIN / Ag / TiO 2 / Ag / AlN Ti 30nm 10nm 56nm 10nm 40nm
• Example 1 and 2 it is optionally possible to interpose between the layers of TiO 2 and the layers of Ag metallic layers, in particular of Ti of very small thickness. It is more particularly preferred above the first layer of silver as a "blocker" layer to avoid the possible degradation of the silver during deposition under a reactive oxidizing atmosphere of the layer of Ti0 2 . It is thus possible to provide, above the first layer of Ag, between 1 and 2 nm of Ti.

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• Chemical & Material Sciences (AREA)
• Materials Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Life Sciences & Earth Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Toxicology (AREA)
• Health & Medical Sciences (AREA)
• Laminated Bodies (AREA)
• Surface Treatment Of Optical Elements (AREA)

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• 1999
  • 1999-09-16 FR FR9911571A patent/FR2798738B1/fr not_active Expired - Fee Related
• 2000
  • 2000-09-15 JP JP2001523901A patent/JP2003509716A/ja active Pending
  • 2000-09-15 WO PCT/FR2000/002582 patent/WO2001020375A1/fr not_active Application Discontinuation
  • 2000-09-15 KR KR1020027003270A patent/KR20020031183A/ko not_active Application Discontinuation
  • 2000-09-15 EP EP00964311A patent/EP1212643A1/fr not_active Withdrawn
• 2002
  • 2002-02-28 US US10/084,060 patent/US6680134B2/en not_active Expired - Fee Related

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