EP2791715A1 - Mirror comprising a polymer based add-on film - Google Patents

Mirror comprising a polymer based add-on film

Info

Publication number
EP2791715A1
EP2791715A1 EP12810387.6A EP12810387A EP2791715A1 EP 2791715 A1 EP2791715 A1 EP 2791715A1 EP 12810387 A EP12810387 A EP 12810387A EP 2791715 A1 EP2791715 A1 EP 2791715A1
Authority
EP
European Patent Office
Prior art keywords
film
layer
poly
mirror
reflective layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12810387.6A
Other languages
German (de)
French (fr)
Inventor
Philippe Laval
Vincent Rachet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Glass France SAS
Original Assignee
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saint Gobain Glass France SAS, Compagnie de Saint Gobain SA filed Critical Saint Gobain Glass France SAS
Publication of EP2791715A1 publication Critical patent/EP2791715A1/en
Withdrawn legal-status Critical Current

Links

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
    • C03C17/38—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 at least one coating being a coating of an organic 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
    • B32B17/1022—Metallic coatings
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10743—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing acrylate (co)polymers or salts thereof
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/1077—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyurethane
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10788—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing ethylene vinylacetate
    • 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
    • C03C17/3663—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 specially adapted for use as mirrors
    • G02B1/105—
    • 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
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • G02B5/0816—Multilayer mirrors, i.e. having two or more reflecting layers
    • G02B5/085—Multilayer mirrors, i.e. having two or more reflecting layers at least one of the reflecting layers comprising metal
    • G02B5/0858—Multilayer mirrors, i.e. having two or more reflecting layers at least one of the reflecting layers comprising metal the reflecting layers comprising a single metallic layer with one or more dielectric layers
    • G02B5/0866—Multilayer mirrors, i.e. having two or more reflecting layers at least one of the reflecting layers comprising metal the reflecting layers comprising a single metallic layer with one or more dielectric layers incorporating one or more organic, e.g. polymeric layers
    • 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
    • B32B2327/00—Polyvinylhalogenides
    • 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
    • B32B2333/00—Polymers of unsaturated acids or derivatives thereof
    • B32B2333/04—Polymers of esters
    • 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
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate

Definitions

  • the invention relates to a mirror comprising a protective coating against chemical and mechanical attack consisting of a polymer-based film and its method of manufacture.
  • a mirror usually comprises a transparent and rigid substrate on which a reflective layer has been deposited.
  • the reflective layer often made of metal such as silver or aluminum tends to corrode in the ambient air due to the presence of pollutants in the atmosphere such as sulphides and chlorides and is therefore necessary to protect it to increase its life.
  • one or more layers of paint are deposited on the silvering mirrors to protect them against chemical and / or external mechanical aggression.
  • These paints are generally of the acrylic, alkyd, epoxy or polyurethane type. They most often contain significant amounts of inorganic or organic pigments and are usually fired in the factory at high temperatures, often above 170 ° C. In order to obtain a satisfactory quality for the desired applications, it is often necessary to also play on the cooking time.
  • patent application FR 2 936 240 describes a mirror comprising a protective coating combining two types of paint that do not contain lead, one being of alkyd type and the other of polyurethane type.
  • US application 2009/0220685 proposes to apply a layer of epoxy paint on the silver substrate.
  • the paints are generally solvent-based, which is not without problems at the sanitary and environmental level because of emissions of volatile organic compounds or VOCs, as well as at the level of safety (risk of fires) and costs (treatment and disposal of solvents). Important problems are also encountered regarding the durability of the products during their external exposure. The reduction in the level of lead currently imposed in paints is such that their durability is strongly impacted.
  • Another method of protecting the silvering layer is to laminate the mirror with a counter-glass or a metal foil, for example aluminum.
  • a tie layer is generally used to facilitate the adhesion of both parties.
  • EP 0882997 discloses the use of a polyether-based polyether material as a tie layer.
  • a counter-glass or a metal sheet weighs the final product, makes it difficult to manipulate and transformable.
  • a PVB encapsulant film with a thickness of the order of several hundred ⁇ , must be used to erase the surface asperities, which poses corrosion problems at the level of edges of the mirrors.
  • the invention paves the above-mentioned problems by proposing to cover the reflective layer with an attached film comprising at least one polymer-based layer protecting against corrosion and mechanical aggression such as scratches and to retain a light and easily cuttable product.
  • the mirror according to the present invention comprising a glass sheet and at least one reflecting layer, preferably metal, applied to the glass comprises an outer protective coating of the reflective layer against corrosion and mechanical aggression, consisting of an attached film , whose thickness is between 5 and 500 ⁇ , said film comprising at least one layer based on polymer.
  • the reflective layer of the mirror is coated with a coating against corrosion and mechanical aggression, said coating being an added film whose thickness is between 5 and 500 ⁇ , and comprising at least one polymer-based layer.
  • the added film forming the protective coating is manufactured independently of the mirror and is ready for use. The film is therefore self-supporting.
  • the protective coating is called “external” since it constitutes the outer face of the mirror, in contact with the ambient air. No layer or other coating is deposited on the outer protective coating.
  • the thickness of the film is that measured once the protective film is applied to the mirror.
  • the reflective layer may be a layer of silver, aluminum, tin, chromium, copper or their alloys.
  • the mirror may include at least one inorganic water and gas barrier layer between the reflective layer and the attached film.
  • the film comprises at least one layer based on a polymer chosen from:
  • polyesters such as poly (ethyleneterephthalate) or PET, poly (ethylenenaphthalate) or PEN, polyglycolic acid or PGA, polylactic acid or PLA, poly (caprolactone) or PCL, poly (ethylene adipate) or PEA, poly (butylene terephthalate) or PBT, poly (trimethylene terephthalate) or PTT, poly (hydroxyalkanoate) or PHA,
  • halogenated polymers such as polyvinyl chloride or PVC, polyvinyl fluoride or PVF, polyvinylidene fluoride or PVDF, polytetrafluoroethylene or PTFE, poly (chlorotrifluoroethylene or PCTFE), perfluoroalkoxy or PFA, ethylene tetrafluoroethylene or ETFE, fluorinated ethylene propylene or FEP, poly (ethylenechlorotrifluoroethylene) or ECTFE, perfluoropolyether or PFPE, polyvinylidene chloride or PVDC, polychloroprene
  • vinyl polymers such as polyvinyl acetate or PVAC, polystyrene or PS, ethylene vinyl acetate or EVA acrylic polymers such as poly (methyl methacrylate) or PMMA, ethylene-ethyl acrylate or EEA, ethylene-methyl acrylate or EMA,
  • polyolefins such as polypropylene or PP, polyethylene or PE, poly (methylpentene) or PMP, polyisobutylene or PIB,
  • cellulose-based polymers such as hydrates or cellulose nitrates or
  • the corrosion agents are in particular water, gases such as oxygen or SO 2 and small molecules such as sulphides or chlorides. It is necessary that the protective film acts as a barrier layer to the corrosion agents. Depending on the polymer chosen from the above-mentioned list, the barrier effect on water, gases and / or small molecules will be more or less important.
  • the material constituting the film may especially be characterized by a permeability to water vapor of less than 200 g / mm 2 / day, at a temperature of 25 ° C. and with a relative humidity of 95%, and a permeability to oxygen less than 100 g.mm/m 2 / day / atm, at a temperature of 23 ° C and with a relative humidity of 85%.
  • the water and oxygen flow measurements are respectively performed according to ASTM F1249 and ASTM D3985.
  • the variation of the permeability of the film as a function of the humidity is low.
  • the adhesion of the attached film on its support can be done either by the deposition of an adhesion primer before the application of said film, either directly via the attached film.
  • the attached film is directly placed on the reflecting layer or on the inorganic barrier layer when it is present, the adhesion of said film being formed by an adhesion primer covering all or part of the reflective layer or layer inorganic barrier.
  • the adhesion primer used may be of silane type, coating, hot wax, resin, for example epoxy, paraffin, glue or any other type of material conventionally used to allow the adhesion of a polymer-based film to a substrate. substrate.
  • the attached film is a multilayer film and further comprises at least one adhesion layer.
  • the adhesion layer is the outer layer of the attached film which is in direct contact with the mirror, that is to say with the metal layer or with the inorganic barrier layer if present, and which allows the adhesion of the protective film on the mirror.
  • the presence of an adhesion primer is optional.
  • the adhesion layer makes it possible to fix the attached film on the mirror. It may especially consist of polymer and be for example polyvinyl butyral or PVB, copolymer of ethylene and vinyl acetate or EVA, polyurethane or PU, poly (methyl methacrylate) or PMMA, polyethylene or PE .
  • the attached film When the attached film is of the multilayer type, it may comprise, in addition to the adhesion layer, one or more inorganic layers, to improve the barrier properties against the corrosion agents.
  • the inorganic layers may be metal layers, for example aluminum, or oxide layers such as silicon oxynitrides and / or silicon oxycarbides, and also silicon nitride layers.
  • the protective film may optionally consist of only one layer, and the latter may act both as a bonding layer and a barrier layer.
  • the attached film may for example be a polyethylene film.
  • the thickness of the film is advantageously between 10 and 200 ⁇ .
  • multilayer polymeric films in which at least one layer is optically active.
  • optically active it is understood that the layer modifies the nature of the transmitted light.
  • the layer may for example be colored and / or opaque.
  • the added film protects the reflective layer of the mirrors, without the use of solvent. As a result, fire risks and volatile organic compound (VOC) emissions problems at the factory are limited.
  • the preformed films reported on the mirror are manufactured by conventional methods known to those skilled in the art.
  • the sheath blowing process also called “film blowing” in English
  • the flat film extrusion process also called “film casting” in English
  • Blow lines used in a sheath blowing process make it possible to produce multilayer structures.
  • three types of resin are used: a resin as a mechanical structure, a resin as a binder and a resin with barrier properties.
  • the molten polymer feeds an annular die.
  • the tube obtained at the outlet of the die is stretched longitudinally and simultaneously air is blown into the interior, which produces a biaxial stretching.
  • the inflated tube is cooled until the polymer reaches its crystallization temperature and solidifies.
  • the resulting film passes through a system of rollers and is laid flat before being cut.
  • Flat film extrusion involves extruding a polymer in the molten state through a flat die, stretching it in the air for a short distance and cooling it rapidly on a thermostatic roll.
  • the resulting film is then stabilized in contact with successive rolls and then wound. Any inorganic layers are deposited by physical vapor deposition (PVD) or chemical vapor deposition (CVD) techniques.
  • the protective film may be self-adhesive or heat-adhesive.
  • the invention also relates to the method of manufacturing a mirror as described above.
  • the method of manufacturing a mirror according to the present invention comprises the following steps:
  • Deposition of the reflective layer on the glass sheet is performed by techniques known to those skilled in the art. We can mention the techniques of vapor deposition (CVD, PVD, magnetron) or liquid. Optionally, according to the deposition technique employed, a surface preparation can be carried out.
  • an adhesion primer can be applied to the reflective layer or the inorganic barrier layer if it is present.
  • This adhesion primer may be of silane type, coated, hot wax, resin, for example epoxy, paraffin, glue or any other type of material conventionally used to allow adhesion of a polymer-based film on a substrate .
  • the film is advantageously directly applied to the reflecting layer of the mirror.
  • the film may be directly attached to an inorganic barrier layer, for example of the SiN x or SiO x type , possibly present on the reflecting layer of the mirror and deposited by conventional techniques such as CVD, PECVD (plasma assisted) or PVD (for example magnetron) as described in patent application WO 2010/001061 A2.
  • an inorganic barrier layer for example of the SiN x or SiO x type , possibly present on the reflecting layer of the mirror and deposited by conventional techniques such as CVD, PECVD (plasma assisted) or PVD (for example magnetron) as described in patent application WO 2010/001061 A2.
  • the adhesion primer optionally present between the reflective layer or the inorganic barrier layer and the protective film, may be applied by liquid means.
  • the application of the film is performed by all the known techniques for depositing a flexible film on a rigid substrate.
  • the film can be applied by a lamination process, cold or hot depending on the nature of the adhesion layer if it is present. It can also be applied by a vacuum lamination process.
  • the lamination temperature is advantageously less than 200 ° C., preferably at a temperature of between 50 and 150 ° C. It is therefore possible to prepare the protective coating at temperatures below the temperatures usually used when the protective coatings are based on paint. If the film comprises a self-adhesive adhesion layer, the film adheres directly to the substrate at room temperature and does not require heat treatment.
  • the application of the film is carried out in a vacuum chamber, which allows in particular to eliminate bubbles present between the mirror and the protective film.
  • the problems associated with the deposition of paint layers, which for example cause the formation of bubbles, heterogeneity and complex cleaning can thus be avoided.
  • the protective coating based on an added film provides excellent performance in the protection of the reflective layer against corrosion and mechanical aggression such as scratches.
  • the product obtained remains light and easily transformable compared to rolled mirrors which comprise a counter-glass or a metal sheet.
  • the mirrors according to the present invention can be used in the field of building, outdoors or indoors for domestic applications, as a solar mirror or in the automotive field.
  • EXAMPLE 1 A flat clear glass substrate of the soda-lime-calcium type marketed under the trade name Planilux® by the applicant is coated with a layer of silver deposited by a silvering technique conventionally employed consisting in chemically reducing the salts of dicarboxylic acid. silver solution, after sensitization of the substrate with a solution of SnCl 2 . This The 80 nm thick layer almost completely reflects the visible radiation and can therefore be used as a mirror.
  • a multilayer film, with a total thickness of 450 ⁇ , consisting of an EVA adhesive layer with a thickness of 400 ⁇ and an ETFE barrier layer with a thickness of 50 ⁇ , cut to the dimensions of the mirror is placed between the mirror and a support against glass.
  • the set is enclosed in a vacuum bag. Outside the pocket, the medium is maintained at atmospheric pressure.
  • the temperature is maintained at 145 ° C for about 15 minutes, which allows the film to adhere to the mirror.
  • the media is removed before cooling the system.
  • the permeance of the film with respect to the water vapor, taking into account its thickness is 0.2 / m 2 / day.
  • the permeance is 2000 g / m 2 / day.
  • the corrosion tests required by EN ISO 1036 have been performed. After 120 hours in the Cupro Acetic salt spray test prepared according to the EN ISO 9227 standard, the mirror comprising the protective film described above has in its face less than 2 pinholes of diameter less than 3 mm per dm 2 .
  • the protective film applied to the mirror described above respects the adhesion properties described in the EN ISO 2409 standard with a value of less than 2, over a value ranging from 1 to 5 in which optimal adhesion corresponds to the value 1.
  • a mirror is prepared as described in Example 1.
  • An adhesive film consisting of a PET film (polyethylene terephthalate) 25 mm thick and a pressure-sensitive acrylic adhesion layer ("PSA" type) of 25 m, is deposited directly on the metal layer of a silver mirror. Deposition is by lamination at room temperature using a bonding technique in the presence of water to prevent air bubbles. Corrosion tests were also performed. At the end of the test, the mirror comprising the protective film described above has in the face less than 2 pits of diameter less than 3 mm per dm 2 .
  • PSA pressure-sensitive acrylic adhesion layer
  • the film also respects the adhesion properties required by the En 1036 standard with a grid value of less than 2.
  • a mirror is prepared as described in Example 1.
  • a PET film polyethylene terephthalate
  • a two-component epoxy adhesive is coated on the treated face of the PET film so as to obtain a thickness of 20 ⁇ .
  • the film with the adhesive thus obtained is finally laminated directly onto the silvering of the mirror. Hardening of the adhesive takes 1 to 3 hours at room temperature or can be accelerated by heating the system.
  • the protective film still satisfies the corrosion and adhesion tests and the values obtained are identical to those of Examples 1 and 2

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to a mirror comprising a coating for protecting against chemical attack, in particular for corrosion and mechanical attack, such as for example scratching, consisting of a polymer based add-on film and its method of manufacture. The protective film comprises at least one polymer based layer having a barrier effect to corrosion agents.

Description

MIROIR COMPRENANT UN FILM RAPPORTE A BASE DE POLYMERE  MIRROR COMPRISING A POLYMER-BASED REPORTED FILM
L'invention concerne un miroir comprenant un revêtement de protection contre les agressions chimiques et mécaniques constitué d'un film rapporté à base de polymère et son procédé de fabrication. The invention relates to a mirror comprising a protective coating against chemical and mechanical attack consisting of a polymer-based film and its method of manufacture.
Un miroir comprend habituellement un substrat transparent et rigide sur lequel a été déposée une couche réfléchissante. La couche réfléchissante souvent en métal comme l'argent ou l'aluminium a tendance à se corroder à l'air ambiant en raison de la présence de polluants présents dans l'atmosphère tels que les sulfures et les chlorures et il est, par conséquent, nécessaire de le protéger pour augmenter sa durée de vie. Le plus souvent, une ou plusieurs couches de peinture sont déposées sur l'argenture des miroirs pour les protéger contre les agressions chimiques et/ou mécaniques extérieures. Ces peintures sont généralement du type acrylique, alkyde, époxy ou polyuréthane. Elles contiennent le plus souvent des quantités importantes de pigments minéraux ou organiques et généralement sont cuites en usine à des températures élevées, souvent supérieures à 170°C. Afin d'obtenir une qualité satisfaisante pour les applications souhaitées, il est souvent nécessaire de jouer également sur la durée de cuisson. On peut citer par exemple la demande de brevet FR 2 936 240 qui décrit un miroir comprenant un revêtement de protection combinant deux types de peinture ne contenant pas de plomb, l'une étant de type alkyde et l'autre de type polyuréthane. La demande US 2009/0220685 propose d'appliquer une couche de peinture époxy sur le substrat argenté. A mirror usually comprises a transparent and rigid substrate on which a reflective layer has been deposited. The reflective layer often made of metal such as silver or aluminum tends to corrode in the ambient air due to the presence of pollutants in the atmosphere such as sulphides and chlorides and is therefore necessary to protect it to increase its life. Most often, one or more layers of paint are deposited on the silvering mirrors to protect them against chemical and / or external mechanical aggression. These paints are generally of the acrylic, alkyd, epoxy or polyurethane type. They most often contain significant amounts of inorganic or organic pigments and are usually fired in the factory at high temperatures, often above 170 ° C. In order to obtain a satisfactory quality for the desired applications, it is often necessary to also play on the cooking time. For example, patent application FR 2 936 240 describes a mirror comprising a protective coating combining two types of paint that do not contain lead, one being of alkyd type and the other of polyurethane type. US application 2009/0220685 proposes to apply a layer of epoxy paint on the silver substrate.
Les peintures sont généralement à base solvantée, ce qui n'est pas sans poser de problèmes au niveau sanitaire et environnemental en raison des émissions de composés organiques volatils ou COV, ainsi qu'au niveau de la sécurité (risque d'incendies) et des coûts (traitement et évacuation des solvants). D'importants problèmes sont également rencontrés concernant la durabilité des produits lors de leur exposition extérieure. La diminution du taux de plomb imposée actuellement dans les peintures est telle que leur durabilité en est fortement impactée. The paints are generally solvent-based, which is not without problems at the sanitary and environmental level because of emissions of volatile organic compounds or VOCs, as well as at the level of safety (risk of fires) and costs (treatment and disposal of solvents). Important problems are also encountered regarding the durability of the products during their external exposure. The reduction in the level of lead currently imposed in paints is such that their durability is strongly impacted.
Une autre méthode de protection de la couche d'argenture consiste à laminer le miroir avec un contre-verre ou une feuille métallique, par exemple en aluminium. Une couche de liaison est généralement utilisée pour faciliter l'adhésion des deux parties. La demande EP 0882997 décrit l'utilisation d'un matériau en polyuréthane à base de polyéther comme couche de liaison. Toutefois l'ajout d'un contre-verre ou d'une feuille métallique alourdit le produit final, le rend difficilement manipulable et transformable. De plus, pour réaliser le feuilletage, un film d'encapsulant type PVB, d'une épaisseur de l'ordre de plusieurs centaines de μιτι, doit être utilisé pour gommer les aspérités de surface, ce qui pose des problèmes de corrosion au niveau des bords des miroirs. Another method of protecting the silvering layer is to laminate the mirror with a counter-glass or a metal foil, for example aluminum. A tie layer is generally used to facilitate the adhesion of both parties. EP 0882997 discloses the use of a polyether-based polyether material as a tie layer. However the addition of a counter-glass or a metal sheet weighs the final product, makes it difficult to manipulate and transformable. In addition, to make the lamination, a PVB encapsulant film, with a thickness of the order of several hundred μιτι, must be used to erase the surface asperities, which poses corrosion problems at the level of edges of the mirrors.
L'invention pâlie aux problèmes susmentionnés en proposant de recouvrir la couche réfléchissante d'un film rapporté comprenant au moins une couche à base de polymère protégeant contre la corrosion et les agressions mécaniques telles que les rayures et de conserver un produit léger et facilement découpable. The invention paves the above-mentioned problems by proposing to cover the reflective layer with an attached film comprising at least one polymer-based layer protecting against corrosion and mechanical aggression such as scratches and to retain a light and easily cuttable product.
Le miroir selon la présente invention comprenant une feuille de verre et au moins une couche réfléchissante, de préférence métallique, appliquée sur le verre comprend un revêtement externe de protection de la couche réfléchissante contre la corrosion et les agressions mécaniques, constitué d'un film rapporté, dont l'épaisseur est comprise entre 5 et 500 μιτι, le dit film comprenant au moins une couche à base de polymère. The mirror according to the present invention comprising a glass sheet and at least one reflecting layer, preferably metal, applied to the glass comprises an outer protective coating of the reflective layer against corrosion and mechanical aggression, consisting of an attached film , whose thickness is between 5 and 500 μιτι, said film comprising at least one layer based on polymer.
La couche réfléchissante du miroir est recouverte d'un revêtement contre la corrosion et les agressions mécaniques, ledit revêtement étant un film rapporté dont l'épaisseur est comprise entre 5 et 500 μιτι, et comprenant au moins une couche à base de polymère. Au sens de la présente invention, le film rapporté formant le revêtement protecteur est fabriqué de façon indépendante du miroir et est prêt à être utilisé. Le film est par conséquent auto-supporté. The reflective layer of the mirror is coated with a coating against corrosion and mechanical aggression, said coating being an added film whose thickness is between 5 and 500 μιτι, and comprising at least one polymer-based layer. For the purposes of the present invention, the added film forming the protective coating is manufactured independently of the mirror and is ready for use. The film is therefore self-supporting.
Il est constitué d'une ou plusieurs couches, empilées les unes sur les autres. Le revêtement de protection est dit « externe » puisqu'il constitue la face externe du miroir, au contact de l'air ambiant. Aucune couche ou autre revêtement n'est déposé sur le revêtement protecteur externe.  It consists of one or more layers, stacked on top of each other. The protective coating is called "external" since it constitutes the outer face of the mirror, in contact with the ambient air. No layer or other coating is deposited on the outer protective coating.
L'épaisseur du film est celle mesurée une fois que le film protecteur est appliqué sur le miroir. The thickness of the film is that measured once the protective film is applied to the mirror.
La couche réfléchissante peut être une couche d'argent, d'aluminium, d'étain, de chrome, de cuivre ou de leurs alliages. The reflective layer may be a layer of silver, aluminum, tin, chromium, copper or their alloys.
Le miroir peut comprendre au moins une couche inorganique barrière à l'eau et aux gaz entre la couche réfléchissante et le film rapporté. The mirror may include at least one inorganic water and gas barrier layer between the reflective layer and the attached film.
Tous les polymères connus par l'homme du métier et pouvant former des films ayant un effet barrière aux agents de corrosion pourront être utilisés comme constituant de base du film rapporté. All polymers known to those skilled in the art and capable of forming films having a barrier effect to corrosion agents can be used as a base component of the reported film.
Le film comprend au moins une couche à base d'un polymère choisi parmi :The film comprises at least one layer based on a polymer chosen from:
- les polyesters, comme le poly(éthylènetéréphtalate) ou PET, le poly(éthylènenaphtalate) ou PEN, l'acide polyglycolique ou PGA, l'acide polylactique ou PLA, la poly(caprolactone) ou PCL, le poly(éthylène adipate) ou PEA, le poly(butylène téréphatalate) ou PBT, le poly(triméthylène téréphtalate) ou PTT, le poly(hydroxyalcanoate) ou PHA, polyesters, such as poly (ethyleneterephthalate) or PET, poly (ethylenenaphthalate) or PEN, polyglycolic acid or PGA, polylactic acid or PLA, poly (caprolactone) or PCL, poly (ethylene adipate) or PEA, poly (butylene terephthalate) or PBT, poly (trimethylene terephthalate) or PTT, poly (hydroxyalkanoate) or PHA,
- les polymères halogénés comme le poly(chlorure de vinyle) ou PVC, le poly(fluorure de vinyle) ou PVF, le poly(fluorure de vinylidène) ou PVDF, le poly(tétrafluoroéthylène) ou PTFE, le poly(chlorotrifluoroéthylène ou PCTFE, le perfluoroalkoxy ou PFA, l'éthylène tétrafluoroéthylène ou ETFE, l'éthylène propylène fluoré ou FEP, le poly(éthylènechlorotrifluoroéthylène) ou ECTFE, le perfluoropolyéther ou PFPE, le poly(chlorure de vinylidène) ou PVDC, polychloroprène  halogenated polymers such as polyvinyl chloride or PVC, polyvinyl fluoride or PVF, polyvinylidene fluoride or PVDF, polytetrafluoroethylene or PTFE, poly (chlorotrifluoroethylene or PCTFE), perfluoroalkoxy or PFA, ethylene tetrafluoroethylene or ETFE, fluorinated ethylene propylene or FEP, poly (ethylenechlorotrifluoroethylene) or ECTFE, perfluoropolyether or PFPE, polyvinylidene chloride or PVDC, polychloroprene
- les polymères vinyliques comme, le poly(acétate de vinyle) ou PVAC, polystyrène ou PS, l'éthylène-acétate de vinyle ou EVA - les polymères acryliques comme le poly(méthacrylate de méthyle) ou PMMA, l'éthylène-acrylate d'éthyle ou EEA, l'éthylène-acrylate de méthyle ou EMA,vinyl polymers such as polyvinyl acetate or PVAC, polystyrene or PS, ethylene vinyl acetate or EVA acrylic polymers such as poly (methyl methacrylate) or PMMA, ethylene-ethyl acrylate or EEA, ethylene-methyl acrylate or EMA,
- les polyoléfines comme le polypropylène ou PP, le polyéthylène ou PE, le poly(méthylpentène) ou PMP, le polyisobutylène ou PIB, polyolefins such as polypropylene or PP, polyethylene or PE, poly (methylpentene) or PMP, polyisobutylene or PIB,
- les polyamides ou PA, polyamides or PAs,
- les polyimides ou PI,  polyimides or PIs,
- les polycarbonates,  polycarbonates,
- les polymères à base de cellulose comme les hydrates ou les nitrate de cellulose ou  cellulose-based polymers such as hydrates or cellulose nitrates or
- les polymères époxyde. epoxy polymers.
Les agents de corrosion sont notamment l'eau, les gaz tels que l'oxygène ou le S02 et les molécules de petite taille comme les sulfures ou les chlorures. Il est nécessaire que le film protecteur joue le rôle de couche barrière aux agents de corrosion. Selon le polymère choisi dans la liste précitée, l'effet barrière à l'eau, aux gaz et/ou aux molécules de petite taille sera plus ou moins important. The corrosion agents are in particular water, gases such as oxygen or SO 2 and small molecules such as sulphides or chlorides. It is necessary that the protective film acts as a barrier layer to the corrosion agents. Depending on the polymer chosen from the above-mentioned list, the barrier effect on water, gases and / or small molecules will be more or less important.
Le matériau constitutif du film peut notamment être caractérisé par une perméabilité à la vapeur d'eau inférieure à 200 g.mm/m2/jour, à une température de 25 °C et avec une hygrométrie relative de 95%, et une perméabilité à l'oxygène inférieure à 100 g.mm/m2/jour/atm, à une température de 23 °C et avec une hygrométrie relative de 85%. Les mesures des flux d'eau et d'oxygène sont respectivement effectués selon les normes ASTM F1249 et ASTM D3985. The material constituting the film may especially be characterized by a permeability to water vapor of less than 200 g / mm 2 / day, at a temperature of 25 ° C. and with a relative humidity of 95%, and a permeability to oxygen less than 100 g.mm/m 2 / day / atm, at a temperature of 23 ° C and with a relative humidity of 85%. The water and oxygen flow measurements are respectively performed according to ASTM F1249 and ASTM D3985.
Avantageusement, la variation de la perméabilité du film en fonction de l'humidité est faible.  Advantageously, the variation of the permeability of the film as a function of the humidity is low.
L'adhésion du film rapporté sur son support, c'est-à-dire sur la couche métallique ou sur une couche inorganique barrière si celle-ci est présente, peut se faire soit par le dépôt d'un primaire d'adhésion avant l'application dudit film, soit directement par l'intermédiaire du film rapporté. Avantageusement, le film rapporté est directement placé sur la couche réfléchissante ou sur la couche inorganique barrière lorsque celle-ci est présente, l'adhésion dudit film étant réalisée par un primaire d'adhésion recouvrant tout ou partie de la couche réfléchissante ou de la couche inorganique barrière. The adhesion of the attached film on its support, that is to say on the metal layer or on an inorganic barrier layer if it is present, can be done either by the deposition of an adhesion primer before the application of said film, either directly via the attached film. Advantageously, the attached film is directly placed on the reflecting layer or on the inorganic barrier layer when it is present, the adhesion of said film being formed by an adhesion primer covering all or part of the reflective layer or layer inorganic barrier.
Le primaire d'adhésion utilisé peut être de type silane, enduit, cire à chaud, résine, par exemple époxy, paraffine, colle ou tout autre type de matériau classiquement utilisé pour permettre l'adhésion d'un film à base de polymère sur un substrat. The adhesion primer used may be of silane type, coating, hot wax, resin, for example epoxy, paraffin, glue or any other type of material conventionally used to allow the adhesion of a polymer-based film to a substrate. substrate.
Selon un autre mode de réalisation, le film rapporté est un film multicouche et comprend en outre au moins une couche d'adhésion. La couche d'adhésion est la couche extérieure du film rapporté qui est directement en contact avec le miroir, c'est-à-dire avec la couche métallique ou avec la couche barrière inorganique si celle-ci est présente, et qui permet l'adhérence du film protecteur sur le miroir. Selon ce mode de réalisation particulier, la présence d'un primaire d'adhésion est optionnelle. La couche d'adhésion permet de fixer le film rapporté sur le miroir. Elle peut notamment être constituée de polymère et être par exemple en polyvinyle butyral ou PVB, en copolymère d'éthylène et d'acétate de vinyle ou EVA, en polyuréthane ou PU, en poly(méthacrylate de méthyle)ou PMMA, en polyéthylène ou PE. According to another embodiment, the attached film is a multilayer film and further comprises at least one adhesion layer. The adhesion layer is the outer layer of the attached film which is in direct contact with the mirror, that is to say with the metal layer or with the inorganic barrier layer if present, and which allows the adhesion of the protective film on the mirror. According to this particular embodiment, the presence of an adhesion primer is optional. The adhesion layer makes it possible to fix the attached film on the mirror. It may especially consist of polymer and be for example polyvinyl butyral or PVB, copolymer of ethylene and vinyl acetate or EVA, polyurethane or PU, poly (methyl methacrylate) or PMMA, polyethylene or PE .
Lorsque le film rapporté est du type multicouche, il peut comprendre, en plus de la couche d'adhésion, une ou plusieurs couches inorganiques, permettant d'améliorer les propriétés barrières contre les agents de corrosion. Les couches inorganiques peuvent être des couches métalliques, comme par exemple en aluminium, ou bien des couches d'oxydes comme les oxynitrures de silicium et/ou oxycarbures de silicium, et également des couches de nitrure de silicium. Le film protecteur peut éventuellement n'être constitué que d'une seule couche, et cette dernière peut jouer à la fois le rôle de couche d'adhésion et de couche barrière. When the attached film is of the multilayer type, it may comprise, in addition to the adhesion layer, one or more inorganic layers, to improve the barrier properties against the corrosion agents. The inorganic layers may be metal layers, for example aluminum, or oxide layers such as silicon oxynitrides and / or silicon oxycarbides, and also silicon nitride layers. The protective film may optionally consist of only one layer, and the latter may act both as a bonding layer and a barrier layer.
Le film rapporté peut par exemple être un film de polyéthylène.  The attached film may for example be a polyethylene film.
L'épaisseur du film est avantageusement comprise entre 10 et 200 μητι. The thickness of the film is advantageously between 10 and 200 μητι.
Selon un mode de réalisation, il est possible d'utiliser des films polymères multicouches dont au moins une couche est optiquement active. Sous le terme « optiquement active » on comprend que la couche modifie la nature de la lumière transmise. La couche peut être par exemple colorée et/ou opaque. According to one embodiment, it is possible to use multilayer polymeric films in which at least one layer is optically active. Under the term "optically active" it is understood that the layer modifies the nature of the transmitted light. The layer may for example be colored and / or opaque.
Le film rapporté permet de protéger la couche réfléchissante des miroirs, sans mettre en œuvre de solvant. Ainsi les risques d'incendie et les problèmes d'émissions de composés organiques volatils (COV) en usine sont limités. The added film protects the reflective layer of the mirrors, without the use of solvent. As a result, fire risks and volatile organic compound (VOC) emissions problems at the factory are limited.
Les possibilités d'empilement des multicouches sont nombreuses et l'ingénierie développée autour de ces couches est très importante. The stacking possibilities of multilayers are numerous and the engineering developed around these layers is very important.
Les films préformés rapportés sur le miroir sont fabriqués par des procédés classiques connus de l'homme de l'art. On citera par exemple le procédé de soufflage de gaine (encore appelé « film blowing » en anglais), ou le procédé par extrusion de film à plat (encore appelé « film casting » en anglais). The preformed films reported on the mirror are manufactured by conventional methods known to those skilled in the art. For example, the sheath blowing process (also called "film blowing" in English), or the flat film extrusion process (also called "film casting" in English).
Les lignes de soufflage utilisées dans un procédé de soufflage de gaine permettent de produire des structures multicouches. En général, trois types de résine sont utilisés : une résine servant de structure mécanique, une résine servant de liant et une résine offrant des propriétés barrières. Blow lines used in a sheath blowing process make it possible to produce multilayer structures. In general, three types of resin are used: a resin as a mechanical structure, a resin as a binder and a resin with barrier properties.
Le polymère fondu alimente une filière annulaire. Le tube obtenu en sortie de filière est étiré longitudinalement et simultanément de l'air est soufflé dans l'intérieur, ce qui produit un étirage bi-axial. Le tube gonflé est refroidi jusqu'à ce que le polymère atteigne sa température de cristallisation et se solidifie. Le film obtenu passe au travers d'un système de rouleaux et est mis à plat avant d'être découpé. L'extrusion de film à plat consiste à extruder un polymère à l'état fondu à travers une filière plate, à l'étirer dans l'air sur une courte distance et à le refroidir de façon rapide sur un rouleau thermostaté. Le film obtenu est ensuite stabilisé au contact de rouleaux successifs puis enroulé. Les éventuelles couches inorganiques sont déposées par les techniques de dépôt physique par phase vapeur (Physical Vapor Déposition ou PVD) ou dépôt chimique par phase vapeur (Chemical Vapor Déposition ou CVD). The molten polymer feeds an annular die. The tube obtained at the outlet of the die is stretched longitudinally and simultaneously air is blown into the interior, which produces a biaxial stretching. The inflated tube is cooled until the polymer reaches its crystallization temperature and solidifies. The resulting film passes through a system of rollers and is laid flat before being cut. Flat film extrusion involves extruding a polymer in the molten state through a flat die, stretching it in the air for a short distance and cooling it rapidly on a thermostatic roll. The resulting film is then stabilized in contact with successive rolls and then wound. Any inorganic layers are deposited by physical vapor deposition (PVD) or chemical vapor deposition (CVD) techniques.
Le film protecteur peut être auto-adhésif ou thermo-adhésif. The protective film may be self-adhesive or heat-adhesive.
L'invention porte également sur le procédé de fabrication d'un miroir tel que décrit précédemment. The invention also relates to the method of manufacturing a mirror as described above.
Le procédé de fabrication d'un miroir selon la présente invention comprend les étapes suivantes : The method of manufacturing a mirror according to the present invention comprises the following steps:
- le dépôt d'une couche réfléchissante sur une feuille de verre,  depositing a reflective layer on a sheet of glass,
- éventuellement le dépôt d'au moins une couche inorganique barrière à l'eau et aux gaz sur la couche réfléchissante, et  optionally the deposition of at least one inorganic barrier layer to water and gases on the reflective layer, and
- l'application du côté de la couche réfléchissante d'un film protecteur comprenant au moins une couche à base de polymère.  applying the side of the reflective layer of a protective film comprising at least one polymer-based layer.
Le dépôt de la couche réfléchissante sur la feuille de verre est effectué par des techniques connues de l'homme du métier. On peut citer les techniques de dépôt en phase vapeur (CVD, PVD, magnétron) ou par voie liquide. Éventuellement, selon la technique de dépôt employée, une préparation de la surface peut être effectuée. Deposition of the reflective layer on the glass sheet is performed by techniques known to those skilled in the art. We can mention the techniques of vapor deposition (CVD, PVD, magnetron) or liquid. Optionally, according to the deposition technique employed, a surface preparation can be carried out.
Lorsque la couche réfléchissante est une couche d'argent, elle a typiquement une épaisseur comprise entre 50 et 200 nm. Selon un mode de réalisation, un primaire d'adhésion peut être appliqué sur la couche réfléchissante ou la couche barrière inorganique si elle est présente. Ce primaire d'adhésion peut être de type silane, enduit, cire à chaud, résine, par exemple époxy, paraffine, colle ou tout autre type de matériau classiquement utilisé pour permettre l'adhésion d'un film à base de polymère sur un substrat. When the reflective layer is a silver layer, it typically has a thickness between 50 and 200 nm. According to one embodiment, an adhesion primer can be applied to the reflective layer or the inorganic barrier layer if it is present. This adhesion primer may be of silane type, coated, hot wax, resin, for example epoxy, paraffin, glue or any other type of material conventionally used to allow adhesion of a polymer-based film on a substrate .
Le film est avantageusement directement appliqué sur la couche réfléchissante du miroir. The film is advantageously directly applied to the reflecting layer of the mirror.
Selon un autre mode de réalisation, le film peut être rapporté directement sur une couche barrière inorganique, par exemple de type SiNx ou SiOx, éventuellement présente sur la couche réfléchissante du miroir et déposée par des techniques classiques telles que les dépôts CVD, PECVD (assistée par plasma) ou PVD (par exemple magnétron) comme décrit dans la demande de brevet WO 2010/001061 A2. According to another embodiment, the film may be directly attached to an inorganic barrier layer, for example of the SiN x or SiO x type , possibly present on the reflecting layer of the mirror and deposited by conventional techniques such as CVD, PECVD (plasma assisted) or PVD (for example magnetron) as described in patent application WO 2010/001061 A2.
Dans ce cas, il est envisageable d'utiliser un film rapporté dont les propriétés barrières sont moindres. Le primaire d'adhésion, éventuellement présent entre la couche réfléchissante ou la couche inorganique barrière et le film protecteur, peut être appliqué par voie liquide.  In this case, it is possible to use a reported film whose barrier properties are lower. The adhesion primer, optionally present between the reflective layer or the inorganic barrier layer and the protective film, may be applied by liquid means.
L'application du film est réalisée par toutes les techniques connues permettant de déposer un film souple sur un substrat rigide. The application of the film is performed by all the known techniques for depositing a flexible film on a rigid substrate.
On peut notamment appliquer le film par un procédé de lamination, à froid ou à chaud en fonction de la nature de la couche d'adhésion si elle est présente. Il peut également être appliqué par un procédé de lamination sous vide. In particular, the film can be applied by a lamination process, cold or hot depending on the nature of the adhesion layer if it is present. It can also be applied by a vacuum lamination process.
A titre d'exemple, lorsque l'application du film est effectuée par lamination sous vide, la température de lamination est avantageusement inférieure à 200°C, de préférence à une température comprise entre 50 et 150°C. Il est donc possible de préparer le revêtement de protection à des températures inférieures aux températures habituellement utilisées lorsque les revêtements de protection sont à base de peinture. Si le film comprend une couche d'adhésion auto-adhésive, le film adhère directement sur le substrat à température ambiante et ne nécessite pas de traitement thermique. By way of example, when the film is applied by vacuum lamination, the lamination temperature is advantageously less than 200 ° C., preferably at a temperature of between 50 and 150 ° C. It is therefore possible to prepare the protective coating at temperatures below the temperatures usually used when the protective coatings are based on paint. If the film comprises a self-adhesive adhesion layer, the film adheres directly to the substrate at room temperature and does not require heat treatment.
Avantageusement, l'application du film est réalisée dans une enceinte sous- vide, ce qui permet notamment d'éliminer les bulles présentes entre le miroir et le film protecteur. Les problèmes liés aux dépôts des couches de peinture, qui entraînent par exemple la formation de bulles, d'hétérogénéité et de nettoyage complexes peuvent ainsi être évités. Le revêtement de protection à base d'un film rapporté permet d'atteindre d'excellentes performances concernant la protection de la couche réfléchissante face à la corrosion et aux agressions mécaniques comme les rayures. Advantageously, the application of the film is carried out in a vacuum chamber, which allows in particular to eliminate bubbles present between the mirror and the protective film. The problems associated with the deposition of paint layers, which for example cause the formation of bubbles, heterogeneity and complex cleaning can thus be avoided. The protective coating based on an added film provides excellent performance in the protection of the reflective layer against corrosion and mechanical aggression such as scratches.
Le produit obtenu reste léger et facilement transformable par rapport aux miroirs laminés qui comprennent un contre-verre ou une feuille métallique.  The product obtained remains light and easily transformable compared to rolled mirrors which comprise a counter-glass or a metal sheet.
Les miroirs selon la présente invention peuvent être utilisés dans le domaine du bâtiment, en extérieur ou en intérieur pour des applications domestiques, comme miroir solaire ou dans le domaine de l'automobile. The mirrors according to the present invention can be used in the field of building, outdoors or indoors for domestic applications, as a solar mirror or in the automotive field.
Exemple 1 : Un substrat de verre clair plan de type silico-sodo-calcique commercialisé sous la marque Planilux® par la demanderesse est revêtu d'une couche d'argent déposée par une technique d'argenture classiquement employée consistant à réduire chimiquement des sels d'argent en solution, après une sensibilisation du substrat à l'aide d'une solution à base de SnCl2. Cette couche, dont l'épaisseur est de 80 nm, réfléchit presque intégralement le rayonnement visible et peut donc être employée comme miroir. EXAMPLE 1 A flat clear glass substrate of the soda-lime-calcium type marketed under the trade name Planilux® by the applicant is coated with a layer of silver deposited by a silvering technique conventionally employed consisting in chemically reducing the salts of dicarboxylic acid. silver solution, after sensitization of the substrate with a solution of SnCl 2 . This The 80 nm thick layer almost completely reflects the visible radiation and can therefore be used as a mirror.
Un film multicouche, d'une épaisseur totale de 450 μιτι, constitué d'une couche d'adhésion en EVA d'une épaisseur de 400 μητι et une couche barrière en ETFE d'une épaisseur de 50 μιτι, découpé aux dimensions du miroir est placé entre le miroir et un support en contre-verre. L'ensemble est enfermé dans une poche sous vide. A l'extérieur de la poche, le milieu est maintenu à la pression atmosphérique. La température est maintenue à 145 ° C pendant environ 15 minutes, ce qui permet l'adhésion du film au miroir. Le support est retiré avant refroidissement du système. A multilayer film, with a total thickness of 450 μιτι, consisting of an EVA adhesive layer with a thickness of 400 μητι and an ETFE barrier layer with a thickness of 50 μιτι, cut to the dimensions of the mirror is placed between the mirror and a support against glass. The set is enclosed in a vacuum bag. Outside the pocket, the medium is maintained at atmospheric pressure. The temperature is maintained at 145 ° C for about 15 minutes, which allows the film to adhere to the mirror. The media is removed before cooling the system.
La perméance du film par rapport à la vapeur d'eau, tenant compte de son épaisseur est de 0,2 /m2/jour. A titre de comparaison, pour une couche de peinture de 100 \irr , la perméance est de 2000g/m2/jour. The permeance of the film with respect to the water vapor, taking into account its thickness is 0.2 / m 2 / day. By way of comparison, for a paint layer of 100 μm, the permeance is 2000 g / m 2 / day.
Les tests de corrosion exigés par la norme EN ISO 1036 ont été réalisés. Après 120h au test Brouillard Salin Cupro Acétique préparé selon la norme EN ISO 9227, le miroir comprenant le film protecteur décrit ci-dessus présente en pleine face moins de 2 piqûres de diamètre inférieur à 3 mm par dm2. The corrosion tests required by EN ISO 1036 have been performed. After 120 hours in the Cupro Acetic salt spray test prepared according to the EN ISO 9227 standard, the mirror comprising the protective film described above has in its face less than 2 pinholes of diameter less than 3 mm per dm 2 .
Comme exigé par la norme EN 1036, le film protecteur appliqué sur le miroir décrit ci-dessus respecte les propriétés d'adhérence décrites dans la norme EN ISO 2409 avec une valeur inférieure à 2, sur une valeur allant de 1 à 5 dans laquelle l'adhérence optimale correspond à la valeur 1 . As required by the EN 1036 standard, the protective film applied to the mirror described above respects the adhesion properties described in the EN ISO 2409 standard with a value of less than 2, over a value ranging from 1 to 5 in which optimal adhesion corresponds to the value 1.
Exemple 2 : Example 2
Un miroir est préparé comme décrit dans l'exemple 1 .  A mirror is prepared as described in Example 1.
Un film adhésif constitué d'un film en PET (polyéthylène téréphtalate) de 25 Mm d'épaisseur et d'une couche d'adhésion acrylique sensible à la pression (type « PSA » selon l'acronyme anglais « pressure sensitive adhesive ») de 25 m, est déposé directement sur la couche métallique d'un miroir à l'argent. Le dépôt se fait par lamination à température ambiante en utilisant une technique de collage en présence d'eau pour éviter les bulles d'air. Les tests de corrosion ont également été réalisés. A l'issu du test, le miroir comprenant le film protecteur décrit ci-dessus présente en pleine face moins de 2 piqûres de diamètre inférieur à 3 mm par dm2. An adhesive film consisting of a PET film (polyethylene terephthalate) 25 mm thick and a pressure-sensitive acrylic adhesion layer ("PSA" type) of 25 m, is deposited directly on the metal layer of a silver mirror. Deposition is by lamination at room temperature using a bonding technique in the presence of water to prevent air bubbles. Corrosion tests were also performed. At the end of the test, the mirror comprising the protective film described above has in the face less than 2 pits of diameter less than 3 mm per dm 2 .
Le film respecte aussi les propriétés d'adhésion demandé par la norme En 1036 avec une valeur de quadrillage inférieure à 2. The film also respects the adhesion properties required by the En 1036 standard with a grid value of less than 2.
Exemple 3 : Example 3
Un miroir est préparé comme décrit dans l'exemple 1. Un film PET (polyéthylène téréphtalate) de 50 μητι est activé au niveau d'une de ses faces par traitement plasma à oxygène. Un adhésif époxy bicomposant est enduit sur la face traitée du film de PET de manière à obtenir une épaisseur de 20 μιτι. Le film avec l'adhésif ainsi obtenu est finalement laminé directement sur l'argenture du miroir. Le durcissement de l'adhésif se fait en 1 à 3 heures à température ambiante ou peut être accéléré en chauffant le système. A mirror is prepared as described in Example 1. A PET film (polyethylene terephthalate) of 50 μητι is activated at one of its faces by oxygen plasma treatment. A two-component epoxy adhesive is coated on the treated face of the PET film so as to obtain a thickness of 20 μιτι. The film with the adhesive thus obtained is finally laminated directly onto the silvering of the mirror. Hardening of the adhesive takes 1 to 3 hours at room temperature or can be accelerated by heating the system.
Le film de protection répond encore bien aux tests de corrosion et d'adhésion et les valeurs obtenues sont identiques à celles des exemples 1 et 2 The protective film still satisfies the corrosion and adhesion tests and the values obtained are identical to those of Examples 1 and 2

Claims

REVENDICATIONS
1. Miroir comprenant une feuille de verre et au moins une couche réfléchissante, de préférence métallique, appliquée sur le verre, caractérisé en ce qu'il comprend un revêtement externe de protection de la couche réfléchissante contre la corrosion et les agressions mécaniques constitué d'un film rapporté, d'une épaisseur comprise entre 5 et 500 μιτι, ledit film comprenant au moins une couche à base de polymère. 1. Mirror comprising a glass sheet and at least one reflective layer, preferably metal, applied to the glass, characterized in that it comprises an outer protective coating of the reflective layer against corrosion and mechanical aggression consisting of an added film having a thickness of between 5 and 500 μιτι, said film comprising at least one polymer-based layer.
2. Miroir selon la revendication précédente caractérisé en ce qu'il comprend au moins une couche inorganique barrière à l'eau et aux gaz entre la couche réfléchissante et le film rapporté. 2. Mirror according to the preceding claim characterized in that it comprises at least one inorganic barrier layer to water and gas between the reflective layer and the attached film.
3. Miroir selon l'une des revendications précédentes caractérisé en ce que la couche est à base d'un polymère choisi parmi : 3. Mirror according to one of the preceding claims characterized in that the layer is based on a polymer selected from:
- les polyesters, comme le poly(éthylènetéréphtalate) ou PET, le poly(éthylènenaphtalate) ou PEN, l'acide polyglycolique ou PGA, l'acide polylactique ou PL.A, la poly(caprolactone) ou PCL, le poly(éthylène adipate) ou PEA, le poly(butylène téréphatalate) ou PBT, le poly(triméthylène téréphtalate) ou PTT, le poly(hydroxyalcanoate) ou PHA,  polyesters, such as poly (ethyleneterephthalate) or PET, poly (ethylenenaphthalate) or PEN, polyglycolic acid or PGA, polylactic acid or PL.A, poly (caprolactone) or PCL, poly (ethylene adipate) ) or PEA, poly (butylene terephthalate) or PBT, poly (trimethylene terephthalate) or PTT, poly (hydroxyalkanoate) or PHA,
- les polymères halogénés comme le poly(chlorure de vinyle) ou PVC, le poly(fluorure de vinyle) ou PVF, le poly(fluorure de vinylidène) ou PVDF, le poly(tétrafluoroéthylène) ou PTFE, le poly(chlorotrifluoroéthylène ou PCTFE, le perfluoroalkoxy ou PFA, l'éthylène tétrafluoroéthylène ou ETFE, l'éthylène propylène fluoré ou FEP, le poly(éthylènechlorotrifluoroéthylène) ou ECTFE, le perfluoropolyéther ou PFPE, le poly(chlorure de vinylidène) ou PVDC, polychloroprène,  halogenated polymers such as polyvinyl chloride or PVC, polyvinyl fluoride or PVF, polyvinylidene fluoride or PVDF, polytetrafluoroethylene or PTFE, poly (chlorotrifluoroethylene or PCTFE), perfluoroalkoxy or PFA, ethylene tetrafluoroethylene or ETFE, fluorinated ethylene propylene or FEP, poly (ethylenechlorotrifluoroethylene) or ECTFE, perfluoropolyether or PFPE, polyvinylidene chloride or PVDC, polychloroprene,
- les polymères vinyliques comme, le poly(acétate de vinyle) ou PVAC, polystyrène ou PS, l'éthylène-acétate de vinyle ou EVA,  vinyl polymers such as polyvinyl acetate or PVAC, polystyrene or PS, ethylene vinyl acetate or EVA,
- les polymères acryliques comme le poly(méthacrylate de méthyle) ou PMMA, l'éthylène-acrylate d'éthyle ou EEA, l'éthylène-acrylate de méthyle ou EMA,acrylic polymers such as poly (methyl methacrylate) or PMMA, ethylene-ethyl acrylate or EEA, ethylene-methyl acrylate or EMA,
- les polyoléfines comme le polypropylène ou PP, le polyéthylène ou PE, le poly(méthylpentène) ou PMP, le polyisobutylène ou PIB, polyolefins such as polypropylene or PP, polyethylene or PE, poly (methylpentene) or PMP, polyisobutylene or PIB,
- les polyamides ou PA, - les polyimides ou PI, polyamides or PAs, polyimides or PIs,
- les polycarbonates,  polycarbonates,
- les polymères à base de cellulose comme les hydrates ou les nitrate de cellulose ou  cellulose-based polymers such as hydrates or cellulose nitrates or
- les polymères époxyde. epoxy polymers.
4. Miroir selon l'une des revendications 1 à 3 caractérisé en ce que l'adhésion du film rapporté se fait à l'aide d'un primaire d'adhésion déposé sur tout ou partie de la couche à revêtir. 4. Mirror according to one of claims 1 to 3 characterized in that the adhesion of the attached film is done using an adhesion primer deposited on all or part of the layer to be coated.
5. Miroir selon l'une des revendications 1 à 4 caractérisé en ce que le film rapporté est un film multicouche et comprend en outre au moins une couche d'adhésion. 5. Mirror according to one of claims 1 to 4 characterized in that the attached film is a multilayer film and further comprises at least one adhesion layer.
6. Miroir selon l'une des revendications 1 à 4 caractérisé en ce qu'il ne comprend qu'une seule couche jouant à la fois le rôle de couche d'adhésion et de couche barrière. 6. Mirror according to one of claims 1 to 4 characterized in that it comprises a single layer playing both the role of adhesion layer and barrier layer.
7. Miroir selon la revendication 5 caractérisé en ce que la couche d'adhésion est en polyvinyle butyral (PVB), en copolymère d'éthylène et d'acétate de vinyle (EVA), en polyuréthane (PU), en poly(méthacrylate de méthyle) (PMMA) ou en polyéthylène (PE). 7. Mirror according to claim 5 characterized in that the adhesion layer is polyvinyl butyral (PVB), copolymer of ethylene and vinyl acetate (EVA), polyurethane (PU), poly (methacrylate). methyl) (PMMA) or polyethylene (PE).
8. Miroir selon l'une des revendications 5 à 7 caractérisé en ce que le film rapporté comprend en outre une ou plusieurs couches inorganiques, telles que des couches métalliques, des couches d'oxyde et/ou de nitrure de silicium. 8. Mirror according to one of claims 5 to 7 characterized in that the reported film further comprises one or more inorganic layers, such as metal layers, oxide layers and / or silicon nitride.
9. Miroir selon l'une des revendications 5 à 8 caractérisé en ce que le film rapporté comprend au moins une couche optiquement active. 9. Mirror according to one of claims 5 to 8 characterized in that the reported film comprises at least one optically active layer.
10. Miroir selon l'une des revendications précédentes caractérisé en ce que l'épaisseur du film rapporté est comprise entre 10 et 200 μητι. 10. Mirror according to one of the preceding claims characterized in that the thickness of the reported film is between 10 and 200 μητι.
1 1 . Procédé de fabrication d'un miroir selon l'une des revendications précédentes comprenant au moins les étapes suivantes: 1 1. A method of manufacturing a mirror according to one of the preceding claims comprising at least the following steps:
- le dépôt d'une couche réfléchissante sur une feuille de verre,  depositing a reflective layer on a sheet of glass,
- éventuellement le dépôt d'une couche inorganique barrière à l'eau et aux gaz sur la couche réfléchissante, et  optionally the deposition of an inorganic barrier layer to water and gases on the reflective layer, and
- l'application du côté de la couche réfléchissante d'un film protecteur comprenant au moins une couche à base de polymère.  applying the side of the reflective layer of a protective film comprising at least one polymer-based layer.
12. Procédé selon la revendication précédente comprenant en outre l'application d'un primaire d'adhésion sur tout ou partie de la couche réfléchissante ou sur la couche barrière inorganique si elle est présente. 12. Method according to the preceding claim further comprising the application of an adhesion primer on all or part of the reflective layer or on the inorganic barrier layer if it is present.
13. Procédé selon la revendication 1 1 dans lequel le film est appliqué directement sur la couche réfléchissante du miroir. 13. The method of claim 1 1 wherein the film is applied directly to the reflective layer of the mirror.
14. Procédé selon la revendication 1 1 dans lequel le film est appliqué directement sur la couche barrière inorganique déposée sur la couche réfléchissante. 14. The method of claim 1 1 wherein the film is applied directly to the inorganic barrier layer deposited on the reflective layer.
15. Procédé selon l'une des revendications 1 1 à 14 dans lequel l'application du film est réalisée par un procédé de lamination. 15. Method according to one of claims 1 1 to 14 wherein the application of the film is performed by a lamination process.
EP12810387.6A 2011-12-16 2012-12-11 Mirror comprising a polymer based add-on film Withdrawn EP2791715A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1161787A FR2984529B1 (en) 2011-12-16 2011-12-16 MIRROR COMPRISING A POLYMER-BASED REPORTED FILM
PCT/FR2012/052874 WO2013088055A1 (en) 2011-12-16 2012-12-11 Mirror comprising a polymer based add-on film

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EP2791715A1 true EP2791715A1 (en) 2014-10-22

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Publication number Priority date Publication date Assignee Title
FR3047732A1 (en) * 2016-02-16 2017-08-18 Saint Gobain MIRROR COMPRISING A SELF-CLEANING ANTI-CORROSION LAYER
NL2016772B1 (en) * 2016-05-13 2017-11-16 Air-Craftglass Inc A mirror comprising a glass laminate and a method for manufacturing same
CN108970944B (en) * 2018-08-01 2021-06-08 重庆大学 Method for preventing glass from being corroded by hydrogen fluoride in aluminum electrolysis industry

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US5215832A (en) * 1990-04-25 1993-06-01 Cardinal Ic Company Lead-free mirrors and environmentally safe manufacture thereof
US5959793A (en) 1997-06-06 1999-09-28 Globe-Amerada Glass Co. Laminated safety mirror with reflective coating adjacent the bonding layer
US6989924B1 (en) * 1998-08-06 2006-01-24 Midwest Research Institute Durable corrosion and ultraviolet-resistant silver mirror
EP1154289A1 (en) * 2000-05-09 2001-11-14 Alcan Technology & Management AG Reflector
WO2005003050A1 (en) 2003-06-18 2005-01-13 Glaverbel Mirror
FR2933394B1 (en) 2008-07-03 2011-04-01 Saint Gobain THIN FILM DEPOSITION METHOD AND PRODUCT OBTAINED
FR2936240B1 (en) 2008-09-22 2012-08-03 Saint Gobain CORROSION RESISTANT MIRROR
WO2011037061A1 (en) * 2009-09-28 2011-03-31 コニカミノルタオプト株式会社 Film mirror and reflecting device

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