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WO2018178559A1 - Method for producing a coloured laminated mirror - Google Patents

Method for producing a coloured laminated mirror Download PDF

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Publication number
WO2018178559A1
WO2018178559A1 PCT/FR2018/050739 FR2018050739W WO2018178559A1 WO 2018178559 A1 WO2018178559 A1 WO 2018178559A1 FR 2018050739 W FR2018050739 W FR 2018050739W WO 2018178559 A1 WO2018178559 A1 WO 2018178559A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymeric layer
interlayer
layer
colored
glass sheet
Prior art date
Application number
PCT/FR2018/050739
Other languages
French (fr)
Inventor
Silvia MARIANI
François COMPOINT
Original Assignee
Saint-Gobain Glass France
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 filed Critical Saint-Gobain Glass France
Publication of WO2018178559A1 publication Critical patent/WO2018178559A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B17/10706—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 being photo-polymerized
    • 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
    • B32B17/10036—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 two outer glass sheets
    • 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
    • B32B17/10651—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 comprising colorants, e.g. dyes or pigments
    • 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
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10899—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin
    • B32B17/10908—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin in liquid form

Definitions

  • the present invention relates to a method of manufacturing a colored laminated mirror, as well as to the mirror obtainable by this method.
  • the mirrors have a very high luminous reflectivity in the visible and independent of the wavelength.
  • the mirrors are almost perfect reflectors and present a very neutral tain and not very warm.
  • Colored mirrors which make it possible to modify the hue of the reflected image, are often sought, for example for applications in the field of decoration and also for functional use with regard to a subject to think about.
  • laminated glazing is commonly used in the automotive, aerospace or building sector, since it has the advantage of being so-called "security" glazing. They consist of two sheets of glass bonded together by a thermoplastic interlayer. One of the glass sheets constituting the glazing can be coated with a reflective layer, and thus the entire glazing is a laminated mirror, also security.
  • the reflective layer is generally metallic, such as silver or aluminum.
  • the metal is deposited on one side of a glass sheet by known deposition processes, vapor phase or wet. Deposition techniques of the reflective layer are well known to those skilled in the art and are not described here in detail.
  • Deposition techniques of the reflective layer are well known to those skilled in the art and are not described here in detail.
  • the present invention provides a manufacturing method to ensure low manufacturing costs but also a wide variety of possible colors and a very good homogeneity of the color throughout the entire surface of the mirror, even when it is large.
  • the method according to the present invention is a method of manufacturing a colored laminated mirror comprising at least two sheets of glass, at least one of the sheets comprises a reflective layer, the two sheets of glass being bonded together by a transparent thermoplastic interlayer, not colored before the final assembly step of the mirror, and which stains during the manufacture of the latter.
  • the method of manufacturing a colored laminated mirror comprising a first and a second sheet of glass bonded together by a thermoplastic interlayer, said first sheet and said second sheet of glass each having an inner face in contact with said thermoplastic interlayer, and a external face, at least one of said sheets being coated on its outer surface with a reflective metal layer, comprises the following steps:
  • the reflective metal layer may be on the first or second glass sheet. Preferably, the reflective metal layer is on the second glass sheet.
  • the method according to the present invention makes it possible to use a thermoplastic interlayer that is not initially colored, and therefore less expensive than the solutions implementing the use of already colored thermoplastic interlayer. Staining is provided by the presence of the polymeric layer, easy to apply by liquid and inexpensive, on at least one of the inner faces of one of the glass sheets constituting the laminated mirror.
  • the term "internal face" of a sheet of glass is understood to mean the face of the sheet which, after assembly, is in contact with the thermoplastic interlayer.
  • the internal faces in a laminated glazing unit comprising two glass sheets are often called face 2 and face 3, the face 2 belonging to the first sheet and the face 3 to the second sheet of glass.
  • the internal faces are those on which the polymeric layer is deposited.
  • This layer may be deposited on the inner face of one of the two glass sheets constituting the laminated mirror or possibly on the inner face of each of the glass sheets constituting the laminated mirror.
  • the metal layer is located on one of the outer faces, that is to say on the face 1 of the first glass sheet or on the side 4 of the second glass sheet.
  • the radiation reflected by the metal layer thus passes through the colored interlayer, so that the hue of the reflected image is changed.
  • the metal layer is preferably located on the outer face of the second glass sheet.
  • the reflective metal layer is preferably silver.
  • the deposit is preferably made by silvering.
  • Silvering means the process conventionally used for the manufacture of mirrors, and comprising the liquid deposition of a silver salt and a reducing agent.
  • the reflective metal layer, especially silver preferably has a physical thickness ranging from 50 to 200 nm. To reduce its corrosion, the layer silver metal is advantageously coated with an opaque paint layer.
  • the polymeric layer is a liquid-applicable layer.
  • the polymer can be dissolved in a solvent to make the liquid deposit possible.
  • a polymeric polyvinylbutyral layer polyethylene, ethylene-vinyl acetate dissolved in a solvent.
  • the colored polymeric layer is a layer obtained from a composition comprising epoxy compounds or (meth) acrylate compounds .
  • the polymeric layer is for example obtained from a liquid composition comprising (meth) acrylate compounds chosen from monomers, oligomers, or polymers comprising at least one methacrylate function.
  • (meth) acrylate is meant an acrylate or a methacrylate.
  • the liquid composition preferably comprises at least one aliphatic urethane-acrylate oligomer, at least one mono, bi or trifunctional (meth) acrylate monomer, at least one polymerization initiator and at least one coloring agent.
  • the (meth) acrylate monomer is mono- or bifunctional and therefore comprises at most two reactive sites.
  • the relatively low functionality of the monomers used to polymerize the polymeric layer facilitates migration of the coloring agent within the layer.
  • the liquid composition advantageously comprises, as a weight percentage relative to the total weight of the (meth) acrylate compounds, from 30 to 80% by weight of at least one aliphatic urethane-acrylic oligomer and from 20 to 70% by weight of at least a mono or bifunctional (meth) acrylate monomer.
  • the coloring agent preferably represents between 0.01 and 10% by weight relative to the total mass of the polymeric compounds.
  • the coloring agent is an organic compound. It is preferably inserted into the polymeric composition in the molecular state, i.e. it is dissolved in the composition and does not form solid particles.
  • the dye has acid-base properties which make it possible to increase its affinity with the thermoplastic interlayer.
  • the dye is an organic Lewis acid type compound
  • the thermoplastic interlayer is a base, which makes it possible to promote the migration of the dye from the polymeric layer to the thermoplastic interlayer.
  • derivatives of the anthraquinone family Acid Blue 25, Alizarin, Anthrapurpurin, Carminic acid, 1,4-Diamino-2,3-dihydroanthraquinone, 7,14-Dibenzpyrenequinone, Dibromoanthanthrone, 1, 3- Dihydroxyanthraquinone, 1, 4-
  • Metal particles may also be dispersed in the liquid composition for obtaining the polymeric layer.
  • the polymer layer may comprise in its composition an adhesion promoter, such as, for example, a silane or any other metal-based adhesion promoter compound such as titanium, zirconium, tin or aluminum.
  • the deposition of the polymeric layer is preferably carried out, on one side of at least one of the glass sheets, by application at ambient temperature of said liquid composition, by roll coating, by spraying, by dipping, by curtain coating or by by spraying.
  • the application of the liquid composition is carried out by roll or curtain coating.
  • the polymeric layer After being deposited on the inner face of at least one glass sheet, the polymeric layer is dried and / or cured, preferably at a temperature below 200 ° C. If the deposited polymeric layer contains a solvent, the latter will be evaporated during the drying step. The polymer layer may also be cured during this step which leads to a firing / crosslinking, for example by UV, or by electron beam.
  • the thickness of the cured polymer layer is preferably between 1 and 200 ⁇ .
  • the step of depositing the polymeric layer can be carried out directly on the laminated mirror manufacturing line and then constitutes the first step during manufacture in the factory.
  • the deposition step can also be performed on another production line than that of the laminated mirror. In this case, the glass sheet or sheets coated with the polymer layer arrive on the assembly line of the laminated mirrors with the dried and / or cured polymeric coating.
  • the glass sheet thus coated with the polymeric layer is then assembled with the thermoplastic interlayer and with a second glass sheet to make the laminated mirror.
  • the second glass sheet may also comprise, on its internal face, a polymeric layer. This layer may be identical to that deposited on the first glass sheet or slightly different, especially in terms of coloring.
  • the method according to the invention may comprise a step of treatment of the surface of the glass sheet on which is deposited the colored polymeric layer and / or the surface of the thermoplastic interlayer side in contact with the polymeric layer by an adhesion promoter.
  • thermoplastic interlayer is preferably polyvinyl butyral, polyethylene, ethylene vinyl acetate, or any other thermoplastic material.
  • the interlayer may be composed of several layers associated with each other, the underlayer in contact with the polymeric layer being an undercoat of organic nature.
  • the method according to the invention advantageously makes it possible to prepare colored laminated mirrors without requiring modification of the assembly phases of the laminated mirror. From the moment when the glass sheet (s) constituting the laminated mirror are coated with the colored polymeric layer, they are assembled with the thermoplastic interlayer in the usual way by a heat treatment at a temperature of between 100 and 200 ° C., under empty and / or under pressure. This heat treatment may for example be carried out in an autoclave at a temperature of between 135 and 15 ° C. under a pressure of between 5 and 14 bar.
  • the invention also relates to a laminated mirror that can be obtained by the process described above.
  • This mirror can be used in the field of building, decorative use in particular.
  • the laminated mirrors obtained have the desired mechanical strength for this type of application and can be considered as safety mirrors.
  • a liquid composition comprising a Sartomer acrylate oligomer CN9002 (bi-functional aliphatic urethane-acrylate oligomer), CN131 B (aromatic monoacrylate monomer) or SR610 (polyethylene glycol acrylate oligomer) and monomer SR 410 (monofunctional aromatic acrylic monomer) is prepared with an oligomeric / monomeric weight ratio of 50/50.
  • An anthraquinone dye is added to the acrylate formulation in a proportion of 0.5% by weight relative to the total of the matrix.
  • 5% by weight of a photoinitiator of the type Speedcure 500 is added to the preceding mixture so as to allow the start of the polymerization.
  • the liquid composition thus obtained is deposited by liquid by roll coating on the inner face of a glass substrate.
  • the parameters of the roller are adjusted so as to obtain a wet thickness of 40 ⁇ (application roller speed between 15 and 25 m / min).
  • the layer thus obtained is cured by UV irradiation (UVB dose of about 280 mJ / cm 2 , travel speed of 16 m / min).
  • the thickness of the dry color layer is about 30 ⁇ .
  • a non-colored PVB interlayer is placed on the inner face of the glass sheet coated with the colored layer, and a second glass sheet comprising a silver reflective metal layer (itself coated with an opaque paint layer) is placed on the interlayer so as to close the laminated mirror, having the reflective metal layer on an outer face (face 4 of the second glass sheet).
  • the whole is placed under an autoclave for 30 minutes, at 145 ° C. under a pressure of 10 bars.
  • a liquid composition comprising a Sartomer acrylate oligomer CN9002 (bi-functional aliphatic urethane-acrylate oligomer), CN131 B (aromatic monoacrylate monomer) or SR610 (polyethylene glycol acrylate oligomer) and monomer SR 410 (monofunctional aromatic acrylic monomer) is prepared with an oligomeric / monomeric weight ratio of 50/50.
  • An anthraquinone dye is added to the acrylate formulation in a proportion of 0.5% by weight relative to the total of the matrix.
  • a quantity of 5% by weight of a Speedcure 500 photoinitiator is added to the above mixture so as to allow the start of the polymerization.
  • the liquid composition thus obtained is deposited by liquid by roll coating on a glass substrate.
  • the roller settings are adjusted to obtain a wet thickness of 15 m (application roller speed between 15 and 25 m / min).
  • the layer thus obtained is cured by UV irradiation (UVB dose of about 280 mJ / cm 2 , scroll speed of 16m / min).
  • the thickness of the dry colored layer is about 5 ⁇ .
  • a non-colored PVB interlayer is placed on the glass sheet coated with the colored layer and a second glass sheet comprising a reflective silver metal layer is placed on the interlayer so as to close the laminated glazing. The whole is placed under an autoclave for 30 minutes at 15 ° C. under a pressure of 10 bar.
  • a colored laminated mirror is obtained.
  • the molecular migration of the dye from the colored layer to the PVB interlayer is homogeneous over the entire portion of the PVB interlayer.
  • a liquid composition comprising an acrylate oligomer of the type
  • Sartomer CN9002 (bi-functional aliphatic urethane-acrylate oligomer), CN131 B (aromatic monoacrylate monomer) or SR610 (polyethylene glycol acrylate oligomer) and monomer SR 410 (monofunctional aromatic acrylic monomer) is prepared with an oligomeric / monomer weight ratio of 50 / 50.
  • An anthraquinone dye is added to the acrylate formulation in an amount of 0.13% by weight.
  • 5% by weight of a photoinitiator of Speedcure 500 type is added to the preceding mixture so as to allow the start of the polymerization.
  • the liquid composition thus obtained is deposited by liquid coating by bar coater (mechanical film) on a glass substrate.
  • the parameters are set to obtain a wet layer of 40 ⁇ thick.
  • the layer thus obtained is cured by UV irradiation (UVB dose of about 250 mJ / cm 2 , travel speed of 10 m / min).
  • the thickness of the dry color layer is about 150 ⁇ .
  • a non-colored PVB interlayer is placed on the glass sheet coated with the colored layer and a second glass sheet comprising a reflective silver metal layer is placed on the interlayer so as to close the laminated glazing.
  • the whole is placed under an autoclave for 45 minutes, at 140 ° C. under a pressure of 10 bars. At the exit of the autoclave, a colored laminated mirror is obtained.
  • the molecular migration of the dye from the colored layer to the PVB interlayer is homogeneous over the entire portion of the PVB interlayer.
  • a liquid composition comprising a Sartomer acrylate oligomer CN9002 (bi-functional aliphatic urethane-acrylate oligomer), CN131 B (aromatic monoacrylate monomer) or SR610 (polyethylene glycol acrylate oligomer) and monomer SR 410 (monofunctional aromatic acrylic monomer) is prepared with an oligomeric / weight weight ratio of 50/50.
  • An anthraquinone dye is added to the acrylate formulation in an amount of 0.13% by weight.
  • 5% by weight of a photoinitiator of Speedcure 500 type is added to the preceding mixture so as to allow the start of the polymerization.
  • the liquid composition thus obtained is deposited by liquid coating by bar coater (mechanical film) on a glass substrate.
  • the parameters are set so as to obtain a wet layer 20 ⁇ thick.
  • the layer thus obtained is cured by UV irradiation (UVB dose of about 250 mJ / cm 2 , travel speed of 10 m / min).
  • UVB dose of about 250 mJ / cm 2 , travel speed of 10 m / min.
  • the thickness of the dry colored layer is about 20 ⁇ .
  • a non-colored PVB interlayer is placed on the glass sheet coated with the colored layer and a second glass sheet comprising a reflective silver metal layer is placed on the interlayer so as to close the laminated mirror. The whole is placed under an autoclave for 45 minutes, at 140 ° C. under a pressure of 10 bars.
  • a colored laminated mirror is obtained.
  • the molecular migration of the dye from the colored layer to the PVB interlayer is homogeneous over the entire portion of the PVB interlayer.
  • Charpy impact strength tests were carried out on about ten samples obtained according to Examples 1 to 4 described above. These impact tests consist in releasing from a given height a pendulum equipped with a steel spherical impactor, with an energy of 2.3 J on samples of laminated glazing with a surface of 49 cm 2 made up of thickness of two sheets of glass of 2 mm, the colored layer of a few ⁇ and the interlayer PVB of 0.8 mm, and to measure the mass loss of the glazing after the shock.

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  • Laminated Bodies (AREA)
  • Joining Of Glass To Other Materials (AREA)

Abstract

The invention relates to a method for producing a coloured laminated mirror comprising a first glass sheet and a second glass sheet which are connected to one another by a thermoplastic interlayer, each of said first and second glass sheets having an inner face that is in contact with the thermoplastic interlayer and an outer face. At least one of the glass sheets is coated with a reflective metal layer on the outer face thereof. The method comprises the steps of: depositing a polymer layer on the inner face of a first glass sheet using a wet process, said polymer layer comprising an organic colouring agent and polymer compounds; drying and optionally hardening the polymer layer; assembling the glass sheet that has been coated with the coloured polymer layer with a colourless transparent thermoplastic interlayer and with the second glass sheet, such that the coloured polymer layer is in direct contact with the interlayer and such that the interlayer is in contact with the inner face of the first and second sheets; degassing, during which the air trapped between the glass sheets and the thermoplastic interlayer is removed; and heat-treating the laminated mirror, under pressure and/or vacuum, at a temperature of between 60 and 200°C, during which the colouring agent in the polymer layer migrates towards the thermoplastic interlayer and the laminated mirror is assembled.

Description

PROCEDE DE FABRICATION D' UN MIROIR FEUILLETE COLORE  METHOD FOR MANUFACTURING A COLOR LAMINATED MIRROR
La présente invention porte sur un procédé de fabrication d'un miroir feuilleté coloré, ainsi que sur le miroir susceptible d'être obtenu par ce procédé. The present invention relates to a method of manufacturing a colored laminated mirror, as well as to the mirror obtainable by this method.
Les miroirs présentent une réflectivité lumineuse dans le visible très élevée et indépendante de la longueur d'onde. Les miroirs sont des réflecteurs quasi parfaits et présentent un tain très neutre et peu chaleureux. Les miroirs colorés, qui permettent de modifier la teinte de l'image réfléchie, sont souvent recherchés, par exemple pour des applications dans le domaine de la décoration et également pour un usage fonctionnel au regard d'un sujet à réfléchir. De façon générale, les vitrages feuilletés sont couramment utilisés dans le domaine de l'automobile, de l'aéronautique ou du bâtiment, puisqu'ils présentent l'avantage d'être des vitrages dits de « sécurité ». Ils sont constitués de deux feuilles de verre liées entre elles par une couche intercalaire thermoplastique. Une des feuilles de verre constitutives du vitrage peut être revêtue d'une couche réfléchissante, et ainsi l'ensemble du vitrage constitue un miroir feuilleté, également de sécurité. La couche réfléchissante est généralement métallique, comme en argent ou en aluminium. Le métal est déposé sur une des faces d'une feuille de verre par des procédés de dépôts connus, en phase vapeur ou par voie humide. Les techniques de dépôt de la couche réfléchissante sont bien connues de l'homme de l'art et ne sont pas décrites ici de façon détaillée. Lorsqu'on souhaite obtenir des verres feuilletés colorés, une des possibilités consiste à utiliser une couche intercalaire qui est elle-même colorée. La coloration est ainsi apportée lors du procédé de fabrication de l'intercalaire, comme ce qui est par exemple décrit dans la demande EP 1483319. Cette solution reste coûteuse et peu flexible pour l'utilisateur final. La coloration (niveau de teinte et choix de la couleur) est en effet imposée par le fabricant de la couche intercalaire.  The mirrors have a very high luminous reflectivity in the visible and independent of the wavelength. The mirrors are almost perfect reflectors and present a very neutral tain and not very warm. Colored mirrors, which make it possible to modify the hue of the reflected image, are often sought, for example for applications in the field of decoration and also for functional use with regard to a subject to think about. In general, laminated glazing is commonly used in the automotive, aerospace or building sector, since it has the advantage of being so-called "security" glazing. They consist of two sheets of glass bonded together by a thermoplastic interlayer. One of the glass sheets constituting the glazing can be coated with a reflective layer, and thus the entire glazing is a laminated mirror, also security. The reflective layer is generally metallic, such as silver or aluminum. The metal is deposited on one side of a glass sheet by known deposition processes, vapor phase or wet. Deposition techniques of the reflective layer are well known to those skilled in the art and are not described here in detail. When it is desired to obtain colored laminated glasses, one of the possibilities is to use an interlayer which is itself colored. Staining is thus provided during the method of manufacturing the interlayer, as described for example in EP 1483319. This solution remains expensive and not very flexible for the end user. The coloration (level of hue and choice of color) is indeed imposed by the manufacturer of the interlayer.
On cherche donc à mettre un point un procédé de fabrication de miroirs feuilletés colorés qui soit simple, qui puisse être opéré sur des lignes de fabrication de miroirs feuilletés existantes, et qui permet de réduire les coûts de fabrication en utilisant des couches intercalaires thermoplastiques transparentes non colorées. C'est dans ce cadre que s'inscrit la présente invention qui propose un procédé de fabrication permettant de garantir des coûts de fabrication bas mais également une grande variété de couleurs possibles et une très bonne homogénéité de la coloration sur la totalité de la superficie du miroir, même lorsque celui-ci est de grande taille. It is therefore sought to provide a point of a simple process for manufacturing colored laminated mirrors, which can be operated on existing laminated mirror manufacturing lines, and which makes it possible to reduce manufacturing costs by using thermoplastic interlayer layers. transparent, unstained. It is in this context that the present invention provides a manufacturing method to ensure low manufacturing costs but also a wide variety of possible colors and a very good homogeneity of the color throughout the entire surface of the mirror, even when it is large.
Le procédé selon la présente invention est un procédé de fabrication d'un miroir feuilleté coloré comprenant au moins deux feuilles de verre dont au moins une des feuilles comprend une couche réfléchissante, les deux feuilles de verre étant liées entre elles par un intercalaire thermoplastique transparent, non coloré avant l'étape d'assemblage finale du miroir, et qui se colore pendant la fabrication du ce dernier.  The method according to the present invention is a method of manufacturing a colored laminated mirror comprising at least two sheets of glass, at least one of the sheets comprises a reflective layer, the two sheets of glass being bonded together by a transparent thermoplastic interlayer, not colored before the final assembly step of the mirror, and which stains during the manufacture of the latter.
Le procédé de fabrication d'un miroir feuilleté coloré comprenant une première et une deuxième feuille de verre liées entre elles par un intercalaire thermoplastique, ladite première feuille et ladite deuxième feuille de verre possédant chacune une face interne en contact avec ledit intercalaire thermoplastique, et une face externe, au moins une desdites feuilles étant revêtue sur sa face externe d'une couche métallique réfléchissante, comprend les étapes suivantes :  The method of manufacturing a colored laminated mirror comprising a first and a second sheet of glass bonded together by a thermoplastic interlayer, said first sheet and said second sheet of glass each having an inner face in contact with said thermoplastic interlayer, and a external face, at least one of said sheets being coated on its outer surface with a reflective metal layer, comprises the following steps:
- dépôt par voie liquide sur la face interne d'une première feuille de verre d'une couche polymérique comprenant un agent colorant organique et des composés polymériques,  depositing, by liquid means, on the inner face of a first glass sheet with a polymeric layer comprising an organic coloring agent and polymeric compounds,
- séchage et éventuellement durcissement de la couche polymérique, drying and optionally curing of the polymeric layer,
- assemblage de la feuille de verre revêtue de la couche polymérique colorée avec un intercalaire thermoplastique transparent non coloré, et avec la deuxième feuille de verre, de telle sorte que la couche polymérique colorée soit en contact direct avec ledit intercalaire et que ledit intercalaire soit en contact avec la face interne desdites première et deuxième feuilles,assembling the glass sheet coated with the colored polymeric layer with a non-colored transparent thermoplastic interlayer, and with the second glass sheet, so that the colored polymeric layer is in direct contact with said interlayer and that said interlayer is in contact with the inner face of said first and second sheets,
- dégazage pendant lequel l'air piégé entre les feuilles de verre et l'intercalaire thermoplastique est éliminé, et degassing during which air trapped between the glass sheets and the thermoplastic interlayer is removed, and
- traitement thermique sous pression et/ou sous vide du miroir feuilleté à une température comprise entre 60 et 200° C pendant lequel l'agent colorant présent dans la couche polymérique migre vers l'intercalaire thermoplastique et pendant lequel l'assemblage du miroir feuilleté est effectué. La couche métallique réfléchissante peut être sur la première ou la deuxième feuille de verre. De façon préférée, la couche métallique réfléchissante est sur la deuxième feuille de verre. heat treatment under pressure and / or under vacuum of the laminated mirror at a temperature of between 60 and 200 ° C. during which the coloring agent present in the polymeric layer migrates towards the thermoplastic interlayer and during which the assembly of the laminated mirror is made. The reflective metal layer may be on the first or second glass sheet. Preferably, the reflective metal layer is on the second glass sheet.
De façon avantageuse, le procédé selon la présente invention permet d'utiliser un intercalaire thermoplastique non coloré initialement, et donc moins onéreux que les solutions mettant en œuvre l'utilisation d'intercalaire thermoplastique déjà coloré. La coloration est apportée par la présence de la couche polymérique, facile à appliquer par voie liquide et peu coûteuse, sur au moins une des faces internes d'une des feuilles de verre constitutives du miroir feuilleté.  Advantageously, the method according to the present invention makes it possible to use a thermoplastic interlayer that is not initially colored, and therefore less expensive than the solutions implementing the use of already colored thermoplastic interlayer. Staining is provided by the presence of the polymeric layer, easy to apply by liquid and inexpensive, on at least one of the inner faces of one of the glass sheets constituting the laminated mirror.
Au sens de la présente invention, on comprend par « face interne » d'une feuille de verre la face de la feuille qui se retrouve, après assemblage, en contact avec l'intercalaire thermoplastique. Les faces internes dans un vitrage feuilleté comprenant deux feuilles de verre sont souvent appelées face 2 et face 3, la face 2 appartenant à la première feuille et la face 3 à la seconde feuille de verre.  For the purposes of the present invention, the term "internal face" of a sheet of glass is understood to mean the face of the sheet which, after assembly, is in contact with the thermoplastic interlayer. The internal faces in a laminated glazing unit comprising two glass sheets are often called face 2 and face 3, the face 2 belonging to the first sheet and the face 3 to the second sheet of glass.
Dans le procédé selon la présente invention, les faces internes (ou encore face 2 ou 3) sont celles sur lesquelles est déposée la couche polymérique. Cette couche peut être déposée sur la face interne d'une des deux feuilles de verre constituant le miroir feuilleté ou éventuellement sur la face interne de chacune des feuilles de verre constituant le miroir feuilleté.  In the process according to the present invention, the internal faces (or face 2 or 3) are those on which the polymeric layer is deposited. This layer may be deposited on the inner face of one of the two glass sheets constituting the laminated mirror or possibly on the inner face of each of the glass sheets constituting the laminated mirror.
La couche métallique se situe sur une des faces externes, c'est-à-dire sur la face 1 de la première feuille de verre ou sur la face 4 de la deuxième feuille de verre. Dans le produit final, le rayonnement réfléchi par la couche métallique passe donc dans l'intercalaire coloré, de sorte que la teinte de l'image réfléchie est modifiée. Pour des raisons de simplicité de procédé, la couche métallique se situe de préférence sur la face externe de la deuxième feuille de verre.  The metal layer is located on one of the outer faces, that is to say on the face 1 of the first glass sheet or on the side 4 of the second glass sheet. In the final product, the radiation reflected by the metal layer thus passes through the colored interlayer, so that the hue of the reflected image is changed. For reasons of process simplicity, the metal layer is preferably located on the outer face of the second glass sheet.
La couche métallique réfléchissante est de préférence en argent. Le dépôt est de préférence réalisé par argenture. On entend par argenture le procédé classiquement utilisé pour la fabrication de miroirs, et comprenant le dépôt par voie liquide d'un sel d'argent et d'un agent réducteur. La couche métallique réfléchissante, notamment d'argent, possède de préférence une épaisseur physique allant de 50 à 200 nm. Pour réduire sa corrosion, la couche métallique d'argent est avantageusement revêtue d'une couche de peinture opaque. The reflective metal layer is preferably silver. The deposit is preferably made by silvering. Silvering means the process conventionally used for the manufacture of mirrors, and comprising the liquid deposition of a silver salt and a reducing agent. The reflective metal layer, especially silver, preferably has a physical thickness ranging from 50 to 200 nm. To reduce its corrosion, the layer silver metal is advantageously coated with an opaque paint layer.
Lors du procédé de fabrication du miroir, et en particulier pendant l'assemblage des différentes parties constitutives, un phénomène de migration de l'agent colorant se produit de façon uniforme sur la totalité de l'épaisseur de l'intercalaire polymérique. L'homogénéité de la coloration est ainsi garantie, même sur des substrats de grande taille, à partir d'un procédé simple à mettre en œuvre ne demandant pas de modifier les étapes classiques des procédés de fabrication d'un vitrage feuilleté (assemblage des différentes parties, dégazage et traitement thermique en vue du collage final). De façon surprenante, ce procédé permet d'obtenir des miroirs feuilletés d'une coloration homogène, sans nécessiter une qualité dite « optique » de la couche polymérique teintée. La phase d'assemblage et de traitement thermique corrige les imperfections de coloration qui peuvent éventuellement exister dans la couche polymérique colorée.  During the mirror manufacturing process, and in particular during the assembly of the various constituent parts, a phenomenon of migration of the coloring agent occurs uniformly over the entire thickness of the polymeric interlayer. The homogeneity of the coloration is thus guaranteed, even on large substrates, from a simple process to implement that does not require modification of the conventional steps of the processes for manufacturing laminated glazing (assembly of different parts, degassing and heat treatment for final bonding). Surprisingly, this method makes it possible to obtain laminated mirrors of homogeneous coloration, without requiring an so-called "optical" quality of the tinted polymeric layer. The assembly and heat treatment phase corrects the color imperfections that may possibly exist in the colored polymeric layer.
La couche polymérique est une couche applicable par voie liquide. Le polymère peut être dissous dans un solvant pour rendre le dépôt par voie liquide possible. On peut citer par exemple une couche polymérique à base de polyvinyle butyrale, de polyéthylène, de l'éthylène-acétate de vinyle dissous dans un solvant. De préférence, dans l'objectif d'utiliser des formulations de polymères avec le moins de solvant possible pour des aspects EHS, la couche polymérique colorée est une couche obtenue à partir d'une composition comprenant des composés époxyde ou des composés (méth)acrylates. La couche polymérique est par exemple obtenue à partir d'une composition liquide comprenant des composés (méth)acrylates choisis parmi des monomères, des oligomères, ou des polymères comprenant au moins une fonction méthacrylate.  The polymeric layer is a liquid-applicable layer. The polymer can be dissolved in a solvent to make the liquid deposit possible. For example, a polymeric polyvinylbutyral layer, polyethylene, ethylene-vinyl acetate dissolved in a solvent. Preferably, for the purpose of using polymer formulations with the least possible solvent for EHS aspects, the colored polymeric layer is a layer obtained from a composition comprising epoxy compounds or (meth) acrylate compounds . The polymeric layer is for example obtained from a liquid composition comprising (meth) acrylate compounds chosen from monomers, oligomers, or polymers comprising at least one methacrylate function.
Par (méth)acrylate, on entend un acrylate ou un méthacrylate. On entend par « composés (méth)acrylate », les esters de l'acide acrylique ou méthacrylique comportant au moins une fonction acroyle (CH2=CH-CO-) ou méthacroyle (CH2=CH(CH3)-CO-). Ces esters peuvent être des monomères, des oligomères, des pré-polymères ou des polymères. Ces composés (méth)acrylate, lorsqu'ils sont soumis aux conditions de polymérisation, donnent un réseau polymère doté d'une structure solide. La composition liquide comprend de préférence au moins un oligomère uréthane-acrylate aliphatique, au moins un monomère (méth)acrylate mono, bi ou tri-fonctionnel, au moins un initiateur de polymérisation et au moins un agent colorant. De façon préférée, le monomère (méth)acrylate est mono- ou bi-fonctionnel et donc il comporte au plus deux sites réactifs. La fonctionnalité relativement basse des monomères utilisés pour polymériser la couche polymérique facilite la migration de l'agent colorant au sein de la couche. By (meth) acrylate is meant an acrylate or a methacrylate. The term "(meth) acrylate compounds" means esters of acrylic or methacrylic acid containing at least one acroyl function (CH 2 = CH-CO-) or methacroyl (CH 2 = CH (CH 3 ) -CO-) . These esters may be monomers, oligomers, prepolymers or polymers. These (meth) acrylate compounds, when subjected to polymerization conditions, provide a polymeric network with a solid structure. The liquid composition preferably comprises at least one aliphatic urethane-acrylate oligomer, at least one mono, bi or trifunctional (meth) acrylate monomer, at least one polymerization initiator and at least one coloring agent. Preferably, the (meth) acrylate monomer is mono- or bifunctional and therefore comprises at most two reactive sites. The relatively low functionality of the monomers used to polymerize the polymeric layer facilitates migration of the coloring agent within the layer.
La composition liquide comprend avantageusement en pourcentage massique par rapport à la masse totale des composés (méth)acrylates, de 30 à 80% en masse d'au moins un oligomère uréthane-acrylique aliphatique et de 20 à 70% en masse d'au moins un monomère (méth)acrylate mono ou bi- fonctionnel. L'agent colorant représente de préférence entre 0,01 et 10% en masse par rapport à la masse totale des composés polymériques. L'agent colorant est un composé organique. Il est de préférence inséré dans la composition polymérique à l'état moléculaire, c'est-à-dire qu'il est dissout dans la composition et ne forme pas de particules solides. De façon très avantageuse, le colorant possède des propriétés acido-basiques permettant d'augmenter son affinité avec l'intercalaire thermoplastique. Ainsi à titre d'exemple, le colorant est un composé organique de type acide de Lewis, et l'intercalaire thermoplastique est une base, ce qui permet de favoriser la migration du colorant depuis la couche polymérique vers l'intercalaire thermoplastique. On peut par exemple citer comme colorant les dérivés de la famille des anthraquinones (Acid Blue 25, Alizarin, Anthrapurpurin, Carminic acid, 1 ,4-Diamino-2,3-dihydroanthraquinone, 7, 14-Dibenzpyrenequinone, Dibromoanthanthrone, 1 ,3-Dihydroxyanthraquinone, 1 ,4- The liquid composition advantageously comprises, as a weight percentage relative to the total weight of the (meth) acrylate compounds, from 30 to 80% by weight of at least one aliphatic urethane-acrylic oligomer and from 20 to 70% by weight of at least a mono or bifunctional (meth) acrylate monomer. The coloring agent preferably represents between 0.01 and 10% by weight relative to the total mass of the polymeric compounds. The coloring agent is an organic compound. It is preferably inserted into the polymeric composition in the molecular state, i.e. it is dissolved in the composition and does not form solid particles. Very advantageously, the dye has acid-base properties which make it possible to increase its affinity with the thermoplastic interlayer. Thus, by way of example, the dye is an organic Lewis acid type compound, and the thermoplastic interlayer is a base, which makes it possible to promote the migration of the dye from the polymeric layer to the thermoplastic interlayer. For example, derivatives of the anthraquinone family (Acid Blue 25, Alizarin, Anthrapurpurin, Carminic acid, 1,4-Diamino-2,3-dihydroanthraquinone, 7,14-Dibenzpyrenequinone, Dibromoanthanthrone, 1, 3- Dihydroxyanthraquinone, 1, 4-
Dihydroxyanthraquinone, Disperse Red 9, Disperse Red 11 , Indanthrone blue, Morindone, Oil Blue 35, Oil Blue A, Parietin, Quinizarine Green SS, Remazol Brilliant Blue R, Solvent Violet 13, 1 ,2,4-Trihydroxyanthraquinone, Vat Orange 1 , Vat Yellow 1 ) ou les produits des gammes Neozapon®, Irgasperse®, Basantol®, Orasol®, commercialisés par la société BASF. Dihydroxyanthraquinone, Disperse Red 9, Disperse Red 11, Indanthrone blue, Morindone, Blue Oil 35, Oil Blue A, Parietin, Quinizarin Green SS, Remazol Brilliant Blue R, Solvent Violet 13, 1, 2,4-Trihydroxyanthraquinone, Vat Orange 1, Vat Yellow 1) or the products of the Neozapon®, Irgasperse®, Basantol® and Orasol® ranges marketed by BASF.
Des particules métalliques peuvent également être dispersées dans la composition liquide permettant d'obtenir la couche polymérique. La couche polymerique peut comprendre dans sa composition un agent promoteur d'adhésion, comme par exemple un silane ou tout autre composé promoteur d'adhésion à base d'un métal comme le titane, le zirconium, l'étain ou l'aluminium. Metal particles may also be dispersed in the liquid composition for obtaining the polymeric layer. The polymer layer may comprise in its composition an adhesion promoter, such as, for example, a silane or any other metal-based adhesion promoter compound such as titanium, zirconium, tin or aluminum.
Le dépôt de la couche polymérique est de préférence effectué, sur une face d'au moins une des feuilles de verre, par application à température ambiante de ladite composition liquide, par enduction au rouleau, par aspersion, par trempage, par enduction au rideau ou par pulvérisation. De préférence, l'application de la composition liquide est effectuée par enduction au rouleau ou au rideau.  The deposition of the polymeric layer is preferably carried out, on one side of at least one of the glass sheets, by application at ambient temperature of said liquid composition, by roll coating, by spraying, by dipping, by curtain coating or by by spraying. Preferably, the application of the liquid composition is carried out by roll or curtain coating.
Après avoir été déposée sur la face interne d'au moins une feuille de verre, la couche polymérique est séchée et/ou durcie, de préférence à une température inférieure à 200 °C. Si la couche polymérique déposée contient un solvant, ce dernier va être évaporé lors de l'étape de séchage. La couche polymérique peut également être durcie lors de cette étape qui entraîne une cuisson/réticulation par exemple par UV, ou par faisceau d'électrons.  After being deposited on the inner face of at least one glass sheet, the polymeric layer is dried and / or cured, preferably at a temperature below 200 ° C. If the deposited polymeric layer contains a solvent, the latter will be evaporated during the drying step. The polymer layer may also be cured during this step which leads to a firing / crosslinking, for example by UV, or by electron beam.
L'épaisseur de la couche polymérique durcie est de préférence comprise entre 1 et 200 μητι.  The thickness of the cured polymer layer is preferably between 1 and 200 μητι.
L'étape de dépôt de la couche polymérique peut être effectuée directement sur la ligne de fabrication de miroir feuilleté et constitue alors la première étape lors de la fabrication en usine. L'étape de dépôt peut également être effectuée sur une autre ligne de fabrication que celle du miroir feuilleté. Dans ce cas, la ou les feuilles de verre revêtues de la couche de polymère arrivent sur la ligne d'assemblage des miroirs feuilletés avec le revêtement polymérique séché et/ou durci.  The step of depositing the polymeric layer can be carried out directly on the laminated mirror manufacturing line and then constitutes the first step during manufacture in the factory. The deposition step can also be performed on another production line than that of the laminated mirror. In this case, the glass sheet or sheets coated with the polymer layer arrive on the assembly line of the laminated mirrors with the dried and / or cured polymeric coating.
La feuille de verre ainsi revêtue de la couche polymérique est ensuite assemblée avec l'intercalaire thermoplastique et avec une deuxième feuille de verre pour faire le miroir feuilleté. La deuxième feuille de verre peut également comprendre, sur sa face interne, une couche polymérique. Cette couche peut être identique à celle déposée sur la première feuille de verre ou légèrement différente, notamment en termes de coloration.  The glass sheet thus coated with the polymeric layer is then assembled with the thermoplastic interlayer and with a second glass sheet to make the laminated mirror. The second glass sheet may also comprise, on its internal face, a polymeric layer. This layer may be identical to that deposited on the first glass sheet or slightly different, especially in terms of coloring.
Afin d'améliorer l'adhésion entre les différents éléments constituants le miroir feuilleté, à savoir entre les feuilles de verre et l'intercalaire thermoplastique, le procédé selon l'invention peut comprendre une étape de traitement de la surface de la feuille de verre sur laquelle est déposée la couche polymérique colorée et/ou de la surface de la face de l'intercalaire thermoplastique en contact avec la couche polymérique par un agent promoteur d'adhésion. In order to improve the adhesion between the various constituent elements of the laminated mirror, namely between the glass sheets and the thermoplastic interlayer, the method according to the invention may comprise a step of treatment of the surface of the glass sheet on which is deposited the colored polymeric layer and / or the surface of the thermoplastic interlayer side in contact with the polymeric layer by an adhesion promoter.
L'intercalaire thermoplastique est de préférence du polyvinyle butyrale, du polyéthylène, de l'éthylène-acétate de vinyle, ou tout autre matériau thermoplastique. L'intercalaire peut être composé de plusieurs couches associées entre elles, la sous-couche en contact avec la couche polymérique étant une sous-couche de nature organique.  The thermoplastic interlayer is preferably polyvinyl butyral, polyethylene, ethylene vinyl acetate, or any other thermoplastic material. The interlayer may be composed of several layers associated with each other, the underlayer in contact with the polymeric layer being an undercoat of organic nature.
Le procédé selon l'invention permet avantageusement de préparer des miroirs feuilletés colorés sans nécessiter de modification des phases d'assemblage du miroir feuilleté. A partir du moment où la ou les feuilles de verre constitutives du miroir feuilleté sont revêtues de la couche polymérique colorée, elles sont assemblées avec l'intercalaire thermoplastique de façon usuelle par un traitement thermique à une température comprise entre 100 et 200° C, sous vide et/ou sous pression. Ce traitement thermique peut par exemple être effectué dans un autoclave à une température comprise entre 135 et 1 5°C, sous une pression comprise entre 5 et 14 bars.  The method according to the invention advantageously makes it possible to prepare colored laminated mirrors without requiring modification of the assembly phases of the laminated mirror. From the moment when the glass sheet (s) constituting the laminated mirror are coated with the colored polymeric layer, they are assembled with the thermoplastic interlayer in the usual way by a heat treatment at a temperature of between 100 and 200 ° C., under empty and / or under pressure. This heat treatment may for example be carried out in an autoclave at a temperature of between 135 and 15 ° C. under a pressure of between 5 and 14 bar.
L'invention porte également sur un miroir feuilleté susceptible d'être obtenu par le procédé décrit ci-avant. Ce miroir peut être utilisé dans le domaine du bâtiment, à usage décoratif notamment. Les miroirs feuilletés obtenus possèdent la résistance mécanique souhaitée pour ce type d'application et peuvent être considérés comme des miroirs de sécurité.  The invention also relates to a laminated mirror that can be obtained by the process described above. This mirror can be used in the field of building, decorative use in particular. The laminated mirrors obtained have the desired mechanical strength for this type of application and can be considered as safety mirrors.
Exemple 1 selon l'invention : Example 1 according to the invention
Une composition liquide comprenant un oligomère acrylate de type Sartomer CN9002 (oligomère uréthane-acrylate aliphatique bi-fonctionnel), CN131 B (monomère monoacrylate aromatique) ou SR610 (oligomère acrylate polyéthylène glycol) et de monomère SR 410 (monomère acrylique aromatique monofonctionel) est préparée avec un ratio pondéral oligomère/monomère de 50/50. Un colorant de type anthraquinone est ajoutée à la formulation d'acrylate, dans une proportion de 0.5% en poids par rapport au total de la matrice. Une quantité de 5 % en poids d'un photo-initiateur de type Speedcure 500 est ajouté au mélange précédent de sorte à permettre le démarrage de la polymérisation. La composition liquide ainsi obtenue est déposée par voie liquide par dépôt au rouleau (roll coating) sur la face interne d'un substrat en verre. Les paramètres du rouleau sont réglés de façon à obtenir une épaisseur humide de 40 μητι (vitesse du rouleau applicateur comprise entre 15 et 25 m/min). La couche ainsi obtenue est durcie par irradiation UV (dose d'UVB de 280 mJ/cm2 environ, vitesse de défilement de 16 m/min). L'épaisseur de la couche colorée sèche est d'environ 30 μητι. Un intercalaire en PVB non coloré est posé sur la face interne de la feuille de verre revêtue de la couche colorée, et une deuxième feuille de verre comprenant une couche métallique réfléchissante en argent (elle-même revêtue d'une couche de peinture opaque) est posée sur l'intercalaire de façon à refermer le miroir feuilleté, en ayant la couche métallique réfléchissante sur une face externe (face 4 de la deuxième feuille de verre). L'ensemble est placé sous autoclave pendant 30 minutes, à 145°C sous une pression de 10 bars. A liquid composition comprising a Sartomer acrylate oligomer CN9002 (bi-functional aliphatic urethane-acrylate oligomer), CN131 B (aromatic monoacrylate monomer) or SR610 (polyethylene glycol acrylate oligomer) and monomer SR 410 (monofunctional aromatic acrylic monomer) is prepared with an oligomeric / monomeric weight ratio of 50/50. An anthraquinone dye is added to the acrylate formulation in a proportion of 0.5% by weight relative to the total of the matrix. 5% by weight of a photoinitiator of the type Speedcure 500 is added to the preceding mixture so as to allow the start of the polymerization. The liquid composition thus obtained is deposited by liquid by roll coating on the inner face of a glass substrate. The parameters of the roller are adjusted so as to obtain a wet thickness of 40 μητι (application roller speed between 15 and 25 m / min). The layer thus obtained is cured by UV irradiation (UVB dose of about 280 mJ / cm 2 , travel speed of 16 m / min). The thickness of the dry color layer is about 30 μητι. A non-colored PVB interlayer is placed on the inner face of the glass sheet coated with the colored layer, and a second glass sheet comprising a silver reflective metal layer (itself coated with an opaque paint layer) is placed on the interlayer so as to close the laminated mirror, having the reflective metal layer on an outer face (face 4 of the second glass sheet). The whole is placed under an autoclave for 30 minutes, at 145 ° C. under a pressure of 10 bars.
A la sortie de l'autoclave, on obtient un miroir feuilleté coloré ayant une réflexion dans les tons rouge. L'observation au microscope de la tranche du miroir feuilleté ainsi obtenue montre que la coloration de l'intercalaire en PVB est homogène.  At the exit of the autoclave, a colored laminated mirror having a reflection in red tones is obtained. The observation under the microscope of the slice of the laminated mirror thus obtained shows that the coloration of the interlayer PVB is homogeneous.
Exemple 2 selon l'invention : Example 2 according to the invention
Une composition liquide comprenant un oligomère acrylate de type Sartomer CN9002 (oligomère uréthane-acrylate aliphatique bi-fonctionnel), CN131 B (monomère monoacrylate aromatique) ou SR610 (oligomère acrylate polyéthylène glycol) et de monomère SR 410 (monomère acrylique aromatique monofonctionel) est préparée avec un ratio pondéral oligomère/monomère de 50/50. Un colorant de type anthraquinone est ajoutée à la formulation d'acrylate, dans une proportion de 0.5% en poids par rapport au total de la matrice. Une quantité de 5 % en poids d'un photo-initiateur de type Speedcure 500 est ajoutée au mélange précédent de sorte à permettre le démarrage de la polymérisation. La composition liquide ainsi obtenue est déposée par voie liquide par dépôt au rouleau (roll coating) sur un substrat en verre. Les paramètres du rouleau sont réglés de façon à obtenir une épaisseur humide de 15 m (vitesse du rouleau applicateur comprise entre 15 et 25 m /min). La couche ainsi obtenue est durcie par irradiation UV (dose d'UVB de 280 mJ/cm2 environ, vitesse de défilement de 16m/min). L'épaisseur de la couche colorée sèche est d'environ 5 μητι. Un intercalaire en PVB non coloré est posé sur la feuille de verre revêtue de la couche colorée et une deuxième feuille de verre comprenant une couche métallique réfléchissante en argent est posée sur l'intercalaire de façon à refermer le vitrage feuilleté. L'ensemble est placé sous autoclave pendant 30 minutes, à 1 5°C sous une pression de 10 bars, A liquid composition comprising a Sartomer acrylate oligomer CN9002 (bi-functional aliphatic urethane-acrylate oligomer), CN131 B (aromatic monoacrylate monomer) or SR610 (polyethylene glycol acrylate oligomer) and monomer SR 410 (monofunctional aromatic acrylic monomer) is prepared with an oligomeric / monomeric weight ratio of 50/50. An anthraquinone dye is added to the acrylate formulation in a proportion of 0.5% by weight relative to the total of the matrix. A quantity of 5% by weight of a Speedcure 500 photoinitiator is added to the above mixture so as to allow the start of the polymerization. The liquid composition thus obtained is deposited by liquid by roll coating on a glass substrate. The roller settings are adjusted to obtain a wet thickness of 15 m (application roller speed between 15 and 25 m / min). The layer thus obtained is cured by UV irradiation (UVB dose of about 280 mJ / cm 2 , scroll speed of 16m / min). The thickness of the dry colored layer is about 5 μητι. A non-colored PVB interlayer is placed on the glass sheet coated with the colored layer and a second glass sheet comprising a reflective silver metal layer is placed on the interlayer so as to close the laminated glazing. The whole is placed under an autoclave for 30 minutes at 15 ° C. under a pressure of 10 bar.
A la sortie de l'autoclave, on obtient un miroir feuilleté coloré. La migration moléculaire du colorant depuis la couche colorée vers l'intercalaire PVB est homogène sur toute la tranche de l'intercalaire en PVB. At the exit of the autoclave, a colored laminated mirror is obtained. The molecular migration of the dye from the colored layer to the PVB interlayer is homogeneous over the entire portion of the PVB interlayer.
Exemple 3 selon l'invention : Example 3 according to the invention
Une composition liquide comprenant un oligomère acrylate de type A liquid composition comprising an acrylate oligomer of the type
Sartomer CN9002 (oligomère uréthane-acrylate aliphatique bi-fonctionnel), CN131 B (monomère monoacrylate aromatique) ou SR610 (oligomère acrylate polyéthylène glycol) et de monomère SR 410 (monomère acrylique aromatique monofonctionel) est préparée avec un ratio pondéral oligomère/ monomère de 50/50. Un colorant de type anthraquinone est ajoutée à la formulation d'acrylate, dans une quantité de 0.13 % en poids. 5 % en poids d'un photoinitiateur de type Speedcure 500 est ajouté au mélange précédent de sorte à permettre le démarrage de la polymérisation. La composition liquide ainsi obtenue est déposée par voie liquide par enduction au bar coater (tire film) mécanique sur un substrat en verre. Les paramètres sont réglés de façon à obtenir une couche humide de 40 μητι d'épaisseur. La couche ainsi obtenue est durcie par irradiation UV (dose d'UVB de 250 mJ/cm2 environ, vitesse de défilement de 10 m/min). L'épaisseur de la couche colorée sèche est d'environ 150 μητι. Un intercalaire en PVB non coloré est posé sur la feuille de verre revêtue de la couche colorée et une deuxième feuille de verre comprenant une couche métallique réfléchissante en argent est posée sur l'intercalaire de façon à refermer le vitrage feuilleté. L'ensemble est placé sous autoclave pendant 45 minutes, à 140°C sous une pression de 10 bars. A la sortie de l'autoclave, on obtient un miroir feuilleté coloré. La migration moléculaire du colorant depuis la couche colorée vers l'intercalaire PVB est homogène sur toute la tranche de l'intercalaire en PVB. Sartomer CN9002 (bi-functional aliphatic urethane-acrylate oligomer), CN131 B (aromatic monoacrylate monomer) or SR610 (polyethylene glycol acrylate oligomer) and monomer SR 410 (monofunctional aromatic acrylic monomer) is prepared with an oligomeric / monomer weight ratio of 50 / 50. An anthraquinone dye is added to the acrylate formulation in an amount of 0.13% by weight. 5% by weight of a photoinitiator of Speedcure 500 type is added to the preceding mixture so as to allow the start of the polymerization. The liquid composition thus obtained is deposited by liquid coating by bar coater (mechanical film) on a glass substrate. The parameters are set to obtain a wet layer of 40 μητι thick. The layer thus obtained is cured by UV irradiation (UVB dose of about 250 mJ / cm 2 , travel speed of 10 m / min). The thickness of the dry color layer is about 150 μητι. A non-colored PVB interlayer is placed on the glass sheet coated with the colored layer and a second glass sheet comprising a reflective silver metal layer is placed on the interlayer so as to close the laminated glazing. The whole is placed under an autoclave for 45 minutes, at 140 ° C. under a pressure of 10 bars. At the exit of the autoclave, a colored laminated mirror is obtained. The molecular migration of the dye from the colored layer to the PVB interlayer is homogeneous over the entire portion of the PVB interlayer.
Exemple 4 selon l'invention : Example 4 according to the invention
Une composition liquide comprenant un oligomère acrylate de type Sartomer CN9002 (oligomère uréthane-acrylate aliphatique bi-fonctionnel), CN131 B (monomère monoacrylate aromatique) ou SR610 (oligomère acrylate polyéthylène glycol) et de monomère SR 410 (monomère acrylique aromatique monofonctionel) est préparée avec un ratio pondéral oligomère/pondéral de 50/50. Un colorant de type anthraquinone est ajoutée à la formulation d'acrylate, dans une quantité de 0.13 % en poids. 5 % en poids d'un photoinitiateur de type Speedcure 500 est ajouté au mélange précédent de sorte à permettre le démarrage de la polymérisation. La composition liquide ainsi obtenue est déposée par voie liquide par enduction au bar coater (tire film) mécanique sur un substrat en verre. Les paramètres sont réglés de façon à obtenir une couche humide de 20 μητι d'épaisseur. La couche ainsi obtenue est durcie par irradiation UV (dose d'UVB de 250 mJ/cm2 environ, vitesse de défilement de 10 m/min). L'épaisseur de la couche colorée sèche est d'environ 20 μητι. Un intercalaire en PVB non coloré est posé sur la feuille de verre revêtue de la couche colorée et une deuxième feuille de verre comprenant une couche métallique réfléchissante en argent est posée sur l'intercalaire de façon à refermer le miroir feuilleté. L'ensemble est placé sous autoclave pendant 45 minutes, à 140°C sous une pression de 10 bars. A liquid composition comprising a Sartomer acrylate oligomer CN9002 (bi-functional aliphatic urethane-acrylate oligomer), CN131 B (aromatic monoacrylate monomer) or SR610 (polyethylene glycol acrylate oligomer) and monomer SR 410 (monofunctional aromatic acrylic monomer) is prepared with an oligomeric / weight weight ratio of 50/50. An anthraquinone dye is added to the acrylate formulation in an amount of 0.13% by weight. 5% by weight of a photoinitiator of Speedcure 500 type is added to the preceding mixture so as to allow the start of the polymerization. The liquid composition thus obtained is deposited by liquid coating by bar coater (mechanical film) on a glass substrate. The parameters are set so as to obtain a wet layer 20 μητι thick. The layer thus obtained is cured by UV irradiation (UVB dose of about 250 mJ / cm 2 , travel speed of 10 m / min). The thickness of the dry colored layer is about 20 μητι. A non-colored PVB interlayer is placed on the glass sheet coated with the colored layer and a second glass sheet comprising a reflective silver metal layer is placed on the interlayer so as to close the laminated mirror. The whole is placed under an autoclave for 45 minutes, at 140 ° C. under a pressure of 10 bars.
A la sortie de l'autoclave, on obtient un miroir feuilleté coloré. La migration moléculaire du colorant depuis la couche colorée vers l'intercalaire PVB est homogène sur toute la tranche de l'intercalaire en PVB. Des tests de résistance mécanique par choc Charpy ont été réalisés sur une dizaine d'échantillons obtenus selon les exemples 1 à 4 décrits ci-avant. Ces tests d'impact consistent à lâcher depuis une hauteur déterminée un pendule équipé d'un impacteur sphérique en acier, avec une énergie de 2.3 J sur des échantillons de vitrage feuilleté d'une surface de 49 cm2 constitué en épaisseur de deux feuilles de verre de 2 mm, de la couche colorée de quelques μητι et de l'intercalaire PVB de 0.8 mm, et à mesurer la perte de masse du vitrage après le choc. La plupart des vitrages testés ont montré que la face sur laquelle la couche polymérique est déposée n'est pas cassée. D'autre part, les échantillons montrent que la perte de masse est toujours inférieure à 1%, voire, très souvent inférieure à 0.2%, ce qui traduit une très bonne résistance mécanique des échantillons testés. At the exit of the autoclave, a colored laminated mirror is obtained. The molecular migration of the dye from the colored layer to the PVB interlayer is homogeneous over the entire portion of the PVB interlayer. Charpy impact strength tests were carried out on about ten samples obtained according to Examples 1 to 4 described above. These impact tests consist in releasing from a given height a pendulum equipped with a steel spherical impactor, with an energy of 2.3 J on samples of laminated glazing with a surface of 49 cm 2 made up of thickness of two sheets of glass of 2 mm, the colored layer of a few μητι and the interlayer PVB of 0.8 mm, and to measure the mass loss of the glazing after the shock. Most of the glazings tested have shown that the face on which the polymeric layer is deposited is not broken. On the other hand, the samples show that the loss of mass is always less than 1%, or even, very often less than 0.2%, which reflects a very good mechanical strength of the samples tested.
Les performances de sécurité du miroir feuilleté obtenu par le procédé selon la présente invention sont donc bien conservées.  The safety performance of the laminated mirror obtained by the process according to the present invention is therefore well preserved.

Claims

REVENDICATIONS
1. Procédé de fabrication d'un miroir feuilleté coloré comprenant une première et une deuxième feuille de verre liées entre elles par un intercalaire thermoplastique, ladite première feuille et ladite deuxième feuille de verre possédant chacune une face interne en contact avec ledit intercalaire thermoplastique, et une face externe, au moins une desdites feuilles étant revêtue sur sa face externe d'une couche métallique réfléchissante, ledit procédé comprenant les étapes suivantes : A method of manufacturing a colored laminated mirror comprising first and second sheets of glass bonded together by a thermoplastic interlayer, said first sheet and said second sheet of glass each having an inner face in contact with said thermoplastic interlayer, and an outer face, at least one of said sheets being coated on its outer face with a reflective metal layer, said method comprising the following steps:
- dépôt par voie liquide sur la face interne d'une première feuille de verre d'une couche polymérique comprenant un agent colorant organique et des composés polymériques,  depositing, by liquid means, on the inner face of a first glass sheet with a polymeric layer comprising an organic coloring agent and polymeric compounds,
- séchage et éventuellement durcissement de la couche polymérique, - assemblage de la feuille de verre revêtue de la couche polymérique colorée avec un intercalaire thermoplastique transparent non coloré et avec la deuxième feuille de verre, de telle sorte que la couche polymérique colorée soit en contact direct avec ledit intercalaire et que ledit intercalaire soit en contact avec la face interne desdites première et deuxième feuilles, - dégazage pendant lequel l'air piégé entre les feuilles de verre et l'intercalaire thermoplastique est éliminé, et  - drying and optionally curing of the polymeric layer, - assembly of the glass sheet coated with the colored polymeric layer with a non-colored transparent thermoplastic interlayer and with the second glass sheet, so that the colored polymeric layer is in direct contact with said interlayer and said spacer being in contact with the inner face of said first and second sheets, - degassing during which air trapped between the glass sheets and the thermoplastic interlayer is removed, and
- traitement thermique sous pression et/ou sous vide du miroir feuilleté à une température comprise entre 60 et 200° C pendant lequel l'agent colorant présent dans la couche polymérique migre vers l'intercalaire thermoplastique et pendant lequel l'assemblage du miroir feuilleté est effectué.  heat treatment under pressure and / or under vacuum of the laminated mirror at a temperature of between 60 and 200 ° C. during which the coloring agent present in the polymeric layer migrates towards the thermoplastic interlayer and during which the assembly of the laminated mirror is made.
2. Procédé selon la revendication précédente, caractérisé en ce que la couche polymérique colorée est une couche obtenue par durcissement d'une composition comprenant des composés époxyde ou des composés méthacrylate.  2. Method according to the preceding claim, characterized in that the colored polymeric layer is a layer obtained by curing a composition comprising epoxide compounds or methacrylate compounds.
3. Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que la couche polymérique est obtenue à partir d'une composition liquide comprenant des composés (méth)acrylates choisis parmi des monomères, des oligomères, ou des polymères comprenant au moins une fonction méthacrylate. 3. Method according to one of claims 1 or 2, characterized in that the polymeric layer is obtained from a liquid composition comprising (meth) acrylate compounds selected from monomers, oligomers, or polymers comprising at least one methacrylate function.
4. Procédé de fabrication selon la revendication 3, caractérisé en ce que la composition liquide comprend au moins un oligomère uréthane-acrylate aliphatique, au moins un monomère (méth)acrylate mono-, bi ou tri- fonctionnel, au moins un initiateur de polymérisation et au moins un agent colorant.  4. The manufacturing method according to claim 3, characterized in that the liquid composition comprises at least one aliphatic urethane-acrylate oligomer, at least one mono-, bi or trifunctional (meth) acrylate monomer, at least one polymerization initiator. and at least one coloring agent.
5. Procédé selon l'une des revendications 3 ou 4, caractérisé en ce que la composition liquide comprend en pourcentage massique par rapport à la masse totale des composés (méth)acrylates, de 30 à 80% en masse d'au moins un oligomère uréthane-acrylique aliphatique et de 20 à 70% en masse d'au moins un monomère (méth)acrylate mono ou bi-fonctionnel.  5. Method according to one of claims 3 or 4, characterized in that the liquid composition comprises in weight percentage relative to the total weight of the compounds (meth) acrylates, 30 to 80% by weight of at least one oligomer aliphatic urethane-acrylic and 20 to 70% by weight of at least one mono- or bi-functional (meth) acrylate monomer.
6. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'agent colorant représente entre 0,01 et 10% en masse par rapport à la masse totale des composés polymériques.  6. Method according to one of the preceding claims, characterized in that the coloring agent is between 0.01 and 10% by weight relative to the total mass of the polymeric compounds.
7. Procédé selon l'une des revendications précédentes, caractérisé en ce que la couche polymérique comprend un agent promoteur d'adhésion.  7. Method according to one of the preceding claims, characterized in that the polymeric layer comprises an adhesion promoter agent.
8. Procédé selon l'une des revendications précédentes, caractérisé en ce que le dépôt de la couche polymérique est effectué par application à température ambiante de ladite composition liquide, par enduction au rouleau, par aspersion, par trempage, par enduction au rideau ou par pulvérisation.  8. Method according to one of the preceding claims, characterized in that the deposition of the polymeric layer is performed by application at ambient temperature of said liquid composition, by roll coating, by spraying, by dipping, by curtain coating or by spray.
9. Procédé selon la revendication précédente, caractérisé en ce que l'application de la composition liquide est effectuée par enduction au rouleau ou au rideau.  9. Method according to the preceding claim, characterized in that the application of the liquid composition is carried out by coating with a roller or curtain.
10. Procédé selon l'une des revendications précédentes, caractérisé en ce que la couche polymérique est durcie par séchage à une température inférieure à 200° C, par réticulation UV, ou par faisceau d'électrons.  10. Method according to one of the preceding claims, characterized in that the polymeric layer is cured by drying at a temperature below 200 ° C, by UV crosslinking, or electron beam.
1 1 . Procédé selon l'une des revendications précédentes, caractérisé en ce que l'épaisseur de la couche polymérique durcie est comprise entre 1 et 200 Mm.  1 1. Method according to one of the preceding claims, characterized in that the thickness of the cured polymeric layer is between 1 and 200 Mm.
12. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'il comprend une étape de traitement de la surface de la feuille de verre sur laquelle est déposée la couche polymérique colorée et/ou de la surface de la face de l'intercalaire thermoplastique en contact avec la couche polymérique par un agent promoteur d'adhésion. 12. Method according to one of the preceding claims, characterized in that it comprises a step of treating the surface of the glass sheet on which is deposited the colored polymeric layer and / or the surface the face of the thermoplastic interlayer in contact with the polymeric layer by an adhesion promoter.
13. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'intercalaire thermoplastique est du polyvinyle butyrale, du polyéthylène, de l'éthylène-acétate de vinyle.  13. Method according to one of the preceding claims, characterized in that the thermoplastic interlayer is polyvinyl butyral, polyethylene, ethylene-vinyl acetate.
14. Miroir feuilleté susceptible d'être obtenu par le procédé selon l'une des revendications précédentes.  14. Laminated mirror obtainable by the method according to one of the preceding claims.
PCT/FR2018/050739 2017-03-29 2018-03-27 Method for producing a coloured laminated mirror WO2018178559A1 (en)

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WO2023222520A1 (en) 2022-05-16 2023-11-23 Saint-Gobain Glass France Laminated roof glazing for a motor vehicle

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