Classifications

• • 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
  • C03C17/3657—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 multilayer coating having optical properties
• • 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
  • C03C17/3649—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 made of metals other than 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
  • C03C2217/00—Coatings on glass
  • C03C2217/70—Properties of coatings
  • C03C2217/72—Decorative coatings
• • 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
  • C03C2218/00—Methods for coating glass
  • C03C2218/30—Aspects of methods for coating glass not covered above
  • C03C2218/32—After-treatment
  • C03C2218/328—Partly or completely removing a coating
• • 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
  • C03C2218/00—Methods for coating glass
  • C03C2218/30—Aspects of methods for coating glass not covered above
  • C03C2218/34—Masking

Definitions

• the invention relates to a glazing on which has been deposited by a physical vapor deposition (PVD) process, mainly magnetron-assisted cathodic sputtering, plasma-assisted chemical vapor deposition (PECVD). Plasma Enhanced Chemical Vapor Deposition) or evaporation or a method of liquid deposition, of one or more thin layers having spatial structuring at scales ranging from several cm to less than 10 ⁇ .
• PVD physical vapor deposition
• PECVD plasma-assisted chemical vapor deposition
• the targeted products are decorative: layers modifying the optical properties, the level of reflection in the visible (mirror or anti-reflection %), colored or absorbent layers to modify the transmittance in the visible for aesthetic purposes, electrochromic layers, electroluminescent , anti-iridescence.
• the invention aims at the industrial manufacture of transparency zones in these layers, that is to say zones of ablation of these layers in patterns that may require an extremely fine resolution of the order of a few ⁇ even a few tens of nm in some cases.
• the decorative effect is sought for building glazing applications, interior decoration, street furniture and even transport vehicles (land, air, water).
• the targeted products are in particular the stacks deposited by magnetron sputtering.
• the invention relates in particular to the reflecting layers (mirrors) as described in particular in the document EP 0 962 429 A1.
• thermocontrol function not by a conductive thin layer but not a polyvinyl butyral interlayer (PVB) or other containing nanoparticles of a conductive compound such as indium tin oxide (ITO indium tin oxide) for example.
• ITO indium tin oxide indium tin oxide
• the second solution consists in etching the layer with silver after deposition so as to selectively remove the silver on sufficiently fine strips (100 ⁇ ) to be easily perceived by the eye and separated from each other by a few mm depending on the wavelengths which we wish to promote the transmission.
• Complex patterns can be used for this application in the face. Representatives of this technique are in particular the documents WO9954961 A1 and WO2014033007 A1.
• the heating efficiency of a conductive layer depends on its resistance square R 2 , the voltage between the electrodes but also the distance between the electrodes. For building applications, this dependency is a problem because, at the same power source, an electrical resistance of the glazing is required for each heating zone size.
• One solution may be to burn one more time for example a base layer Ag so as to modulate its resistance by global square to enable it to be compatible with the distance between electrodes and the desired surface heating power.
• a silver-based glazing can be functionalized in the form of an antenna provided the electromagnetic decoupling of the layer with the frame of the car for example. This operation is also ensured by an engraving.
• Alternative selective etching methods are mainly from the microelectronics industry. Some use temporary layers, others consist of direct engraving.
• photolithography uses temporary layers to mask selective acid attacks. The photo lithography allows very fine engravings (45-90 nm today industrially) but remains limited to the size of the masks today limited by the size of the optics.
• the laser etching of the conductive layer is provided by a point-etch laser which will sublimate the thin-film stack by scanning the beam. This operation has a low productivity on large glazings and requires a significant investment compared to the treated surfaces.
• Impact etching of ions or electrons has the same limitations as laser etching in terms of productivity.
• Other engraving methods come from traditional printing.
• inkjet printing techniques are still limited for sizes greater than 10m 2 at print times greater than one minute.
• Screen printing may be preferred over other techniques when a resolution scale smaller than 50 ⁇ is desired: this process provides relatively poor edge qualities at these small scales.
• the invention therefore aims to provide decorative glazing as defined above, having ablation zones - transparency in resolution patterns that can be very thin, a few ⁇ even a few tens of nm.
• the subject of the invention is a process for depositing on a glass substrate a layer or a stack of layers which are essentially mineral (s) decorative (s), characterized in that it comprises the steps of depositing on the substrate an essentially organic coating on a part but not all of its surface, in accordance with a pattern,
• the product of the combustion of the organic coating is a powder which does not adhere to the substrate, so that it can then be removed with the mineral layer (s) which covers it (s) without exerting a mechanical action of the type brushing, friction or any abrasion likely to deteriorate the substrate and especially the quality of the edges of areas not printed by the organic coating and covered with the mineral layer (s) (sharpness, resolution).
• the method makes it possible to produce on an industrial production line, on a large-area substrate, a substantially organic coating pattern with a surface area of dimensions ranging from 1 m to 10 ⁇ or less.
• the reduced cycle time makes it possible to validate the applicable character industrially.
• the method of the invention may end with the deposition of a layer of paint above the layer or stack of decorative layer (s) when the one (s) is (are) reflective (s), or above another reflective layer covering this (these) mineral layer (s) decorative (s). This measurement is classic in the making of mirrors.
• the method of the invention may also comprise the formation of a metallic discontinuous layer associated with one or more layers dielectric, as described in WO2015177474A1. These layers have the function of modifying the absorption spectrum in the visible of a mirror so as to produce a reflection image whose color is modified.
• the pattern-based deposition of the essentially organic coating is carried out by a liquid, direct or indirect engraved roll method such as offset, flexography, inkjet printing, masking, lithography or screen printing.
• a roll with a width of at least 3210mm can be used, the engraving of which will reproduce the desired pattern. In this case it is a repetitive pattern but it remains compatible for example with the improvement of electromagnetic transmission.
• the essentially organic coating is chosen from a monomer and / or oligomer acrylate, epoxy acrylate, polyester acrylate, polyurethane acrylate, polyvinylpyrrolidone + EDTA composition, polyamide, polyvinyl butyral, positive photosensitive resin diazonaphthoquinone-novolac, any organic material crosslinked under radiation ultraviolet or infrared, alone or in a mixture of several of them.
• the substantially organic coating has a thickness of at most 30, and in order of increasing preference, at most equal to 20 and 10 ⁇ , and particularly preferably of approximately 5 ⁇ . Thicknesses of 1 ⁇ or even a few hundred nm are however not excluded from the invention. Apart from the printed areas of this organic coating corresponding to patterns ranging from 1 m to 10 ⁇ m or less in surface dimensions, it is necessary to have no temporary organic coating so as not to degrade the decorative mineral stack in these supposed areas. have an intact mineral stack after quenching.
• the development of the essentially organic coating comprises a crosslinking by heat treatment and / or under radiation such as ultraviolet (UV ) and / or drying, then the whole is washed.
• the essentially organic coating may be advantageously crosslinked under UV to limit the space required for drying.
• the varnish or resin will be properly dried before going under a conventional washing machine to coater and then the deposition operation of the (mineral) thin layer (s) essentially mineral (s) decorative (s) is performed.
• the layer or stack of essentially mineral (s) decorative layers (s) is formed (e) by a physical vapor deposition (PVD for Physical Vapor Deposition) under vacuum such as cathodic sputtering especially assisted by magnetron, evaporation or plasma enhanced chemical vapor deposition (PECVD for Plasma Enhanced Chemical Vapor Deposition) or liquid.
• PVD Physical Vapor Deposition
• PECVD plasma enhanced chemical vapor deposition
• the layer or the stack of layers essentially mineral decorative (s) consists of Ag, Cr, Ti, Al, Nb, Cu, Au, Ga or similar metal metal oxide such as Ti, Si, Sn, Zn or the like, transparent conductive oxide (TCO) such as tin doped indium oxide (ITO), zinc doped indium oxide (IZO), ZnO: Al, stannate cadmium, compound of Si and N such as Si 3 N 4 undoped or doped with Al or the like, dielectric stack thereon, alone or in combination of several of them.
• TCO transparent conductive oxide
• ITO tin doped indium oxide
• IZO zinc doped indium oxide
• ZnO Al
• stannate cadmium compound of Si and N such as Si 3 N 4 undoped or doped with Al or the like, dielectric stack thereon, alone or in combination of several of them.
• the glass can not be cut once soaked, it can be, in some applications, for example building, stored and cut, started etc. before quenching.
• This glazing can be sold as such, mainly in this case with a layer then removed by quenching at a transformer.
• the heat treatment is part of a thermal tempering of the glass substrate.
• the varnish or the resin disappears by combustion and effectively eliminates the layer or stack of essentially mineral layers (s) decorative (s) at the locations of the grounds, which causes the desired selective etching.
• the heat treatment is part of a bending of the glass substrate, in particular a bending by pressing.
• a preliminary heat treatment causes the disappearance of the varnish or the resin. If pressing tools are used to bend, it will be ensured that the combustion of the essentially organic coating takes place before this pressing phase.
• the deposition of the layer or the stack of essentially mineral (s) decorative layers (s) is deposited again at least one essentially organic coating sequence - layer or stack of essentially mineral layers (s) decorative (s).
• This deposition is preferably carried out before the heat treatment for the combustion of the essentially organic coating closest to the substrate, and a subsequent heat treatment will produce the combustion of several superimposed organic overlays as well as the subsequent removal of several layers or layers of layers. essentially mineral decorative covering them.
• essentially organic coating sequences - layer or stack of essentially mineral (s) decorative layers (s), from the second sequence, after the combustion heat treatment of the first substantially organic coating and wiping or gaseous blast removal of its organic residues and mineral residues covering them is also part of the invention. It is thus possible to combine different patterns of areas of transparency of a mirror, or such areas of transparency with differently colored areas.
• the glass substrate obtained by the process of the invention is also capable of being integrated in a laminated glazing unit or other laminated composite product, and / or in a multiple glazing unit.
• Other objects of the invention consist in
• a glazing obtained by a method as described previously as a decorative mirror having zones of transparency in accordance with a pattern; it may be a layer glazing modifying the optical properties, the level of reflection in the visible (mirror or anti-reflection ...), colored or absorbent layers to modify the transmittance in the visible for aesthetic purposes, electrochromic, electroluminescent, anti-iridescent layers, for building, interior decoration, street furniture and even transport vehicles (land, air, water).
• Example 1 Referring to Figure 1, the method of the invention can be represented in four views corresponding to three successive main steps, from left to right in the Figure.
• a UV crosslinkable acrylate lacquer having the following formulation is used, in which the proportions are by weight: 57% of aliphatic urethane hexaacrylate oligomer (CN9276 manufactured by Sartomer), 38% of monomers and more exactly 19% of tricyclodecanedimethanol diacrylate (TCDDMDA or SR833S from Sartomer) as well as 19% trimethylolpropane thacrylate (TMPTA or SR351 from Sartomer) and finally 5% of ketone-type photoinitiator is more precisely a mixture of benzophenone and methanone (Speedcure 500 or Irgacure 500 from BASF).
• This varnish is prepared by mechanically mixing all these compounds (resins and photoinitiator) using a blade. After several hours of agitation, the varnish can be stored for several months if it is protected from light and strong temperature variations.
• step 1 of Figure 1 a certain amount of this varnish is applied to the clean glass and sharpened by the method of indirect gravure roller as shown in step 1 of Figure 1. After rolling, the substrate + varnish deposited is exposed to UV (mercury type lamp). The thickness of the lacquer pattern coating is 5 ⁇ .
• a stack of thin layers is deposited in a conformal manner by sputtering in step 2 on the glass + acrylate varnish system.
• This stack of thin layers has the following constitution (starting from the glass substrate), in which the thicknesses are in nm: SiO 2 20 / Cr 27 / Si 3 N: Al 1 1, 7 / TiO x 2.3. This stack reflecting the visible light is soakable.
• a quenching step (in FIG. 1), generally in a convection oven at 730 ° C. for 35 seconds per mm of glass (140 seconds for a 4 mm thick glass), the organic layer is degraded. which leads to the detachment of the magnetron layers in the areas where it is present.
• the final system consists of the stack of thin layers described above, structured in a pattern corresponding to the negative of that made with the resin.
• Example 2 This example differs from the previous one by the essentially organic coating.
• This is an ink jet deposit of an ink marketed by the Marabu Company in the Ultra-Jet DUV A range, especially in cyan or magenta color. A thickness of a few hundred nm to a few ⁇ is obtained.
• the ink (patterns) is cross-linked under ultraviolet light.
• the resolution provided by the process of the invention depends solely on the method of printing the organic coating. It is not or little modified during quenching. Printed lines having a fineness of 25 ⁇ gave a pattern width in transparency of 25 ⁇ (line of ablation of the reflective stack in the visible).

Applications Claiming Priority (2)

Publications (1)

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• 2016
  • 2016-02-26 FR FR1651630A patent/FR3048245B1/fr not_active Expired - Fee Related
• 2017
  • 2017-02-23 CN CN201780013216.3A patent/CN108698920A/zh active Pending
  • 2017-02-23 KR KR1020187024209A patent/KR20180101585A/ko not_active Application Discontinuation
  • 2017-02-23 EP EP17710353.8A patent/EP3419945A1/de not_active Withdrawn
  • 2017-02-23 WO PCT/FR2017/050406 patent/WO2017144824A1/fr active Application Filing
  • 2017-02-23 MX MX2018010200A patent/MX2018010200A/es unknown

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