EP0921940A1 - Laminated glass resistant to uv radiation - Google Patents

Laminated glass resistant to uv radiation

Info

Publication number
EP0921940A1
EP0921940A1 EP98928421A EP98928421A EP0921940A1 EP 0921940 A1 EP0921940 A1 EP 0921940A1 EP 98928421 A EP98928421 A EP 98928421A EP 98928421 A EP98928421 A EP 98928421A EP 0921940 A1 EP0921940 A1 EP 0921940A1
Authority
EP
European Patent Office
Prior art keywords
polyester film
resin
glazing according
glazing
filter
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Withdrawn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
EP98928421A
Other languages
German (de)
French (fr)
Inventor
Laury Heldt
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.)
Glace Controle
Original Assignee
Glace Controle
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 Glace Controle filed Critical Glace Controle
Publication of EP0921940A1 publication Critical patent/EP0921940A1/en
Withdrawn legal-status Critical Current

Links

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
    • 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
    • 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
    • B32B17/10247—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons
    • B32B17/10256—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons created by printing techniques
    • B32B17/10284—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons created by printing techniques on intermediate layer
    • 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 present invention relates to laminated glazing resistant to UV rays.
  • laminated glazings comprising at least two rigid plates between which is inserted at least one layer of flexible plastic material (s).
  • the rigid plate is most often made of glass, but can also be made of rigid plastic.
  • the presence of the layer (s) of flexible plastic material (s) in the laminated glazing has the function of improving the mechanical properties of the glazing, in particular the impact resistance, and the thermal and acoustic insulation properties.
  • laminated glazings consisting of two rigid outer plates, between which are disposed a polyester film and at least one layer of poly (vinylbutyral) (PVB).
  • PVB poly (vinylbutyral)
  • STADIP poly (vinylbutyral)
  • the polyester film is generally introduced as a film carrying a graphic, holographic, metallized or metallized holographic representation; and PVB is introduced not only as a bonding resin on either side of the polyester film but also as a reinforcing resin to improve the mechanical properties of the glazing.
  • PVB has filter properties against UV rays and protects the polyester film from aging due to UV rays, that is to say from yellowing and hardening. In addition, the PVB protects the representation, which is possibly supported by the polyester film. Unfortunately, PVB has four drawbacks.
  • the first of these drawbacks is that it does not provide optimal impact resistance; the second drawback is that its range of thermal stability is low, hence uncertain for safety; the third drawback is that it requires significant equipment for its implementation: in fact PVB is used in the form of flexible plates that one places between two rigid plates of laminated glazing and the adhesion to said plates is obtained by a heat treatment under pressure; the fourth drawback is that it is sensitive to water, which results in bleaching and a reduction in its attachment properties on the rigid plates to which it adheres. If the PVB layer is replaced by a polyester layer, it is necessary to add a UV filter to the said layer because the polyester does not by itself have UV filtering properties.
  • the polymerization must be carried out in situ to ensure bonding; this results in three major drawbacks: first, a hardener must be added to the monomer resin, hence a risk of heterogeneity of the mixture and a risk of causing irregularities in the glazing, which are liable to disturb the homogeneity glazing and deforming the images seen through the glazing or the image of the representation carried by the polyester film; secondly, the implementation is always delicate because, after mixing the hardener, the manufacturer of the product has only a fairly limited time to pour the resin between the rigid plates of the laminated glazing; thirdly, the fact of adding a UV filter to the mixture before polymerization always causes a clouding of the transparency which is very troublesome for the optical qualities of the laminated glazing obtained.
  • a polyester film containing UV filters is used. Indeed, if a polyester film is produced containing a UV filter: - or else, the film is mixed with the resin after polymerization and before extrusion; - Or, the film is treated after extrusion; but, in both cases, the polymerization of the polyester is not carried out in the presence of the filter and it results therefrom that no transparency disorder is observed.
  • the use of such a film makes it possible not only to avoid the degradation of the polyester film, but also to avoid, in all cases, the degradation of the performance supported by the polyester film.
  • the graphic representation is made in the mass of the polyester film and, in this case, surprisingly, the presence of the UV filter in the film prevents degradation; or else the graphic representation is carried by the film on its face not directly irradiated by UV rays; or else the graphic representation is carried by the film on its face situated on the side of the UV irradiation and, in this case, the graphic representation is covered by a polyester film comprising a UV filter thereby forming a sandwich film.
  • the present invention therefore relates to a laminated glazing comprising two external plates of rigid transparent material, at least one polyester film disposed between the two above-mentioned external plates and at least one layer of resin forming a flexible interlayer between the two plates.
  • external characterized in that the resin of a resin layer does not, by itself, have UV filter properties and that the polyester film contains at least one UV filter.
  • the polyester film participates in the impact resistance of laminated glazing; the fact of having incorporated a UV filter makes it possible to maintain the properties of the laminated glazing thus formed over time.
  • the laminated glazing comprises two external plates of rigid material: it can comprise at least one similar plate interposed between the external plates.
  • This rigid material is, as explained above, glass or a transparent rigid plastic, such as a polymethacrylate, in particular polymethyl methacrylate.
  • the resin in a resin layer is a transparent polymer capable of forming a flexible film and having no UV screening properties. It preferably comprises a high impact resistance: it is advantageously capable of being crosslinked by irradiation with UV rays. It can be chosen from the group formed by unsaturated polyesters, poly carbonates, polymethacrylates or polyacrylates, in particular acrylic urethane polymers. Among the resins which can be used in particular, mention may be made of the resin sold under the trade name "CONLOC" by the company "BOHLE” or under the trade name "VITRALIT" by the company "CVA".
  • the polyester film is advantageously a poly (ethyl col terephthalate) film.
  • the polyester film used contains at least one UV filter.
  • This UV filter can be introduced into the polyester film by any known means, such as grafting of molecules on the surface, deposition on the surface or addition in the mass.
  • the UV filter is, for example, a benzophenone, a benzotriazole, a substituted acrylonitrile or a phenol-nickel complex, these compounds being well known to those skilled in the art. Mention may more particularly be made of the UV filters sold under the name "UV-SHIELD" by the company "GAMCOLOR”.
  • the amount of UV filter used varies depending on the UV filter and the polyester. It is generally between 0.1 and 1.5% by weight relative to the weight of the polyester film.
  • the polyester film can be uniformly colored or bear a graphic or holographic representation.
  • the UV filter is introduced into said film.
  • the representation can be a graphic printing set up in any way, in particular by screen printing; optionally, the polyester film can be mass-dyed.
  • graphic representation is meant according to the present invention any drawing, pattern or inscription obtained by any process.
  • the polyester film can be glued.
  • the film is fixed by the glued part against a plate of transparent rigid material of the glazing; it can in particular be fixed by gluing on the internal face of one of the two external plates of the glazing.
  • the polyester film bears a graphic representation, such bonding is provided on the internal face of the external plate which receives UV radiation, the layer of resin, which forms a flexible interlayer, being disposed between the non-glued side of the film.
  • polyester and the rigid plate that does not receive UV radiation. It is advantageous to use an acrylic type adhesive which promotes UV filtration.
  • polyester film When the polyester film is not glued, it is preferably placed between two layers of resin forming flexible interlayer.
  • Laminated glazing can be prepared by any known process.
  • the first external rigid plate is placed on a horizontal table and a double-sided adhesive strip is applied around the periphery of the plate. It is understood that one could use any other material capable of sticking to the rigid plates and of forming between them a bead of uniform thickness.
  • This adhesive strip defines the spacing between the external plates of the glazing and therefore the thickness of the layer of resin forming flexible interlayer; the strip serves as a seal.
  • a second rigid external plate is deposited on the adhesive strip and the two rigid plates are pressed against each other.
  • the protective layer of the adhesive strip has been maintained over a certain length so as to provide at least one opening allowing the introduction of the resin between the two external plates and an opening so that air can escape; these two openings can form only one as long as it is large enough.
  • the resin is then injected into the volume formed between the two rigid plates.
  • the resin When the resin is mixed with a catalyst and / or hardener, it is injected between the rigid plates and allowed to crosslink.
  • the glazing is passed through a UV oven equipped with appropriate lamps.
  • the process for manufacturing the laminated glazing takes place as described above, the polyester film being bonded to the side facing inwards of one of the rigid plates.
  • the preparation is carried out on a vertical table and the polyester film is suspended under tension, parallel to the rigid plates: the resin is poured on either side of the polyester film to constitute two layers of resin forming flexible inserts on either side of the polyester film.
  • a double-sided adhesive strip sold under the name “3M No. 4910" by the company “3M” is attached to the periphery of this plate.
  • the protective film was removed from the adhesive strip except over a length of 1 cm located at one of the upper corners of the first glass plate.
  • Parallel to the first plate is suspended a poly (ethyl glycol terephthalate) film containing 0.1% by weight of an UV filter sold under the trade name "TINUVIN 571" by the company "CIBA-GEIGY”.
  • An image was printed by screen printing on one side of this film using organic inks from one of the ranges:
  • a second glass plate identical to the first is then applied to the adhesive strip.
  • the table is tilted in a horizontal position and the air escapes through the injection opening. After filling, the injection opening is sealed using a hot-melt adhesive.
  • the resin is then polymerized in a tunnel oven equipped with UV-A lamps.
  • the residence time of the plate is 20 seconds.

Landscapes

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

Abstract

The invention concerns a laminated glass comprising two external plates in rigid transparent material, and at least a polyester film provided between said external plates and a resin layer forming a flexible spacer between the two external plates, characterised in that the resin of the resin layer does not have, by itself, anti-UV filter and the polyester film contains at least one UV filter.

Description

VITRAGE FEUILLETÉ RÉSISTANT AUX RAYONS UVLAMINATED GLASS RESISTANT TO UV RAYS
La présente invention concerne un vitrage feuilleté résistant aux rayons UV.The present invention relates to laminated glazing resistant to UV rays.
Il est connu, notamment par FR-A-2 706 446, de fabriquer des vitrages feuilletés comportant au moins deux plaques rigides entre lesquelles est insérée au moins une couche de matière(s) plastique(s) souple(s). La plaque rigide est le plus souvent en verre, mais peut également être en matière plastique rigide. La présence de la (ou des) couche(s) de matière(s) plastique(s) souple(s) dans le vitrage feuilleté a pour fonction d'améliorer les propriétés mécaniques du vitrage, en particulier la résistance aux chocs, et les propriétés d'isolation thermique et acoustique.It is known, in particular from FR-A-2 706 446, to manufacture laminated glazings comprising at least two rigid plates between which is inserted at least one layer of flexible plastic material (s). The rigid plate is most often made of glass, but can also be made of rigid plastic. The presence of the layer (s) of flexible plastic material (s) in the laminated glazing has the function of improving the mechanical properties of the glazing, in particular the impact resistance, and the thermal and acoustic insulation properties.
Il est plus particulièrement connu de fabriquer des vitrages feuilletés constitués de deux plaques extérieures rigides, entre lesquelles sont disposés un film de polyester et au moins une couche de poly(vinylbutyral) (PVB). Un tel vitrage feuilleté est, par exemple, commercialisé par la Société "ST GOBAIN VITRAGES" sous la dénomination "STADIP". On sait aussi réaliser des vitrages feuilletés du type ci-dessus indiqué en remplaçant la couche de PVB par une couche de polyester.It is more particularly known to manufacture laminated glazings consisting of two rigid outer plates, between which are disposed a polyester film and at least one layer of poly (vinylbutyral) (PVB). Such laminated glazing is, for example, sold by the company "ST GOBAIN VITRAGES" under the name "STADIP". It is also known to produce laminated glazings of the type indicated above by replacing the layer of PVB with a layer of polyester.
Le film de polyester est généralement introduit comme film porteur d'une représentation graphique, holographique, métallisée ou métallisée holographique ; et le PVB est introduit non seulement, comme résine de liaison de part et d'autre du film de polyester mais également, comme résine renforçante pour améliorer les propriétés mécaniques du vitrage.The polyester film is generally introduced as a film carrying a graphic, holographic, metallized or metallized holographic representation; and PVB is introduced not only as a bonding resin on either side of the polyester film but also as a reinforcing resin to improve the mechanical properties of the glazing.
Le PVB a des propriétés de filtre contre les rayons UV et protège le film de polyester du vieillissement dû aux rayons UV, c'est- à-dire du jaunissement et du durcissement. Par ailleurs, le PVB protège la représentation, qui est éventuellement supportée par le film de polyester. Malheureusement, le PVB présente quatre inconvénients. Le premier de ces inconvénients est qu'il n'apporte pas une résistance aux chocs optimale ; le second inconvénient est que sa plage de stabilité thermique est faible d'où incertain pour la sécurité ; le troisième inconvénient est qu'il nécessite pour sa mise en oeuvre un matériel important : en effet le PVB est utilisé sous forme de plaques souples que l'on met en place entre deux plaques rigides d'un vitrage feuilleté et l'adhérence sur lesdites plaques est obtenue par un traitement thermique sous pression ; le quatrième inconvénient est qu'il est sensible à l'eau, qui entraîne un blanchiment et une réduction de ses propriétés d'accrochage sur les plaques rigides sur lesquelles il adhère. Si l'on remplace la couche de PVB par une couche de polyester, il est nécessaire d'ajouter dans ladite couche un filtre UV car le polyester n'a pas par lui-même des propriétés de filtration des rayons UV. Or, si l'on met en oeuvre une couche de polyester, il faut réaliser la polymérisation in situ pour assurer l'accrochage ; il en résulte trois inconvénients majeurs : en premier lieu, on doit ajouter à la résine monomère un durcisseur d'où un risque d'hétérogénéité du mélange et un risque de faire apparaître des irrégularités dans le vitrage, qui sont susceptibles de perturber l'homogénéité du vitrage et de déformer les images vues à travers le vitrage ou l'image de la représentation portée par le film de polyester ; en second lieu, la mise en oeuvre est toujours délicate car, après le mélange du durcisseur, le fabricant du produit ne dispose que d'un temps assez limité pour couler la résine entre les plaques rigides du vitrage feuilleté ; en troisième lieu, le fait d'ajouter un filtre UV au mélange avant polymérisation entraîne toujours un trouble de la transparence ce qui est très gênant pour les qualités optiques du vitrage feuilleté obtenu.PVB has filter properties against UV rays and protects the polyester film from aging due to UV rays, that is to say from yellowing and hardening. In addition, the PVB protects the representation, which is possibly supported by the polyester film. Unfortunately, PVB has four drawbacks. The first of these drawbacks is that it does not provide optimal impact resistance; the second drawback is that its range of thermal stability is low, hence uncertain for safety; the third drawback is that it requires significant equipment for its implementation: in fact PVB is used in the form of flexible plates that one places between two rigid plates of laminated glazing and the adhesion to said plates is obtained by a heat treatment under pressure; the fourth drawback is that it is sensitive to water, which results in bleaching and a reduction in its attachment properties on the rigid plates to which it adheres. If the PVB layer is replaced by a polyester layer, it is necessary to add a UV filter to the said layer because the polyester does not by itself have UV filtering properties. However, if a polyester layer is used, the polymerization must be carried out in situ to ensure bonding; this results in three major drawbacks: first, a hardener must be added to the monomer resin, hence a risk of heterogeneity of the mixture and a risk of causing irregularities in the glazing, which are liable to disturb the homogeneity glazing and deforming the images seen through the glazing or the image of the representation carried by the polyester film; secondly, the implementation is always delicate because, after mixing the hardener, the manufacturer of the product has only a fairly limited time to pour the resin between the rigid plates of the laminated glazing; thirdly, the fact of adding a UV filter to the mixture before polymerization always causes a clouding of the transparency which is very troublesome for the optical qualities of the laminated glazing obtained.
Si on cherche à remplacer le PVB par une autre résine qui n'ait pas des propriétés de filtre UV, le film de résine polyester n'est plus protégé des rayons UV et se dégrade ; cette dégradation peut aller jusqu'à entraîner la destruction du vitrage feuilleté par décohésion. L'adjonction d'un filtre UV dans la résine de liaison n'est pas envisageable pour une résine polyester, comme il a été ci-dessus exposé. Si, comme il est aussi connu, on propose d'utiliser comme couche de résine du vitrage feuilleté, une résine polymérisable aux rayons UV, il est évidemment impossible d'y ajouter un filtre UV qui empêcherait la polymérisation et il devient donc impossible de protéger le film de polyester de la dégradation. Or, si l'on utilise une polymérisation par rayonnement UV, l'infrastructure nécessaire à la mise en oeuvre est considérablement réduite par rapport à celle requise pour le traitement du PVB. Selon la présente invention, pour résoudre le problème exposé ci-dessus, c'est-à-dire pour pouvoir utiliser à la place du PVB une matière plastique qui, à la fois, donne une bonne résistance mécanique au vitrage, une bonne transparence et une bonne homogénéité optique du produit, une mise en oeuvre aisée et une bonne résistance à l'eau tout en conservant une protection du film de polyester contre les UV, on utilise un film de polyester contenant des filtres contre les UV. En effet, si l'on fabrique un film de polyester contenant un filtre UV : - ou bien, on mélange le film à la résine après polymérisation et avant extrusion ; - ou bien, on traite le film après extrusion ; mais, dans les deux cas, la polymérisation du polyester ne s'effectue pas en présence du filtre et il en résulte que l'on n'observe aucun trouble de la transparence. On a constaté que l'utilisation d'un tel film permettait non seulement d'éviter la dégradation du film de polyester, mais également d'éviter, dans tous les cas, la dégradation de la représentation supportée par le film de polyester. En effet, ou bien la représentation graphique est réalisée dans la masse du film polyester et, dans ce cas, de façon surprenante, la présence du filtre UV dans le film évite la dégradation ; ou bien la représentation graphique est portée par le film sur sa face non directement irradiée par les rayons UV ; ou bien la représentation graphique est portée par le film sur sa face située du côté de l'irradiation UV et, dans ce cas, on recouvre la représentation graphique par un film polyester comportant un filtre UV en formant ainsi un film sandwich.If it is sought to replace PVB with another resin which does not have UV screening properties, the polyester resin film is no longer protected from UV rays and degrades; this degradation can go so far as to destroy the laminated glazing by decohesion. The addition of a UV filter in the bonding resin cannot be envisaged for a polyester resin, as has been explained above. If, as it is also known, it is proposed to use as a resin layer of laminated glazing, a resin polymerizable with UV rays, it is obviously impossible to add a UV filter which would prevent polymerization and it therefore becomes impossible to protect the polyester film of degradation. However, if UV polymerization is used, the infrastructure required for implementation is considerably reduced compared to that required for the treatment of PVB. According to the present invention, to solve the problem described above, that is to say to be able to use instead of PVB a plastic material which, at the same time, gives good mechanical resistance to the glazing, good transparency and good optical homogeneity of the product, easy implementation and good resistance to water while retaining protection of the polyester film against UV, a polyester film containing UV filters is used. Indeed, if a polyester film is produced containing a UV filter: - or else, the film is mixed with the resin after polymerization and before extrusion; - Or, the film is treated after extrusion; but, in both cases, the polymerization of the polyester is not carried out in the presence of the filter and it results therefrom that no transparency disorder is observed. It has been found that the use of such a film makes it possible not only to avoid the degradation of the polyester film, but also to avoid, in all cases, the degradation of the performance supported by the polyester film. Indeed, either the graphic representation is made in the mass of the polyester film and, in this case, surprisingly, the presence of the UV filter in the film prevents degradation; or else the graphic representation is carried by the film on its face not directly irradiated by UV rays; or else the graphic representation is carried by the film on its face situated on the side of the UV irradiation and, in this case, the graphic representation is covered by a polyester film comprising a UV filter thereby forming a sandwich film.
La présente invention a, par conséquent, pour objet un vitrage feuilleté comportant deux plaques externes de matériau transparent rigide, au moins un film de polyester disposé entre les deux plaques externes précitées et au moins une couche de résine formant un intercalaire souple entre les deux plaques externes, caractérisé par le fait que la résine d'une couche de résine ne présente pas, par elle- même, des propriétés de filtre UV et que le film de polyester contient au moins un filtre UV. On sait que le film de polyester participe à la résistance aux chocs du vitrage feuilleté ; le fait d'y avoir incorporé un filtre UV permet de maintenir au cours du temps les propriétés du vitrage feuilleté ainsi constitué.The present invention therefore relates to a laminated glazing comprising two external plates of rigid transparent material, at least one polyester film disposed between the two above-mentioned external plates and at least one layer of resin forming a flexible interlayer between the two plates. external, characterized in that the resin of a resin layer does not, by itself, have UV filter properties and that the polyester film contains at least one UV filter. It is known that the polyester film participates in the impact resistance of laminated glazing; the fact of having incorporated a UV filter makes it possible to maintain the properties of the laminated glazing thus formed over time.
Selon l'invention, le vitrage feuilleté comporte deux plaques externes de matériau rigide : il peut comporter au moins une plaque analogue intercalée entre les plaques externes. Ce matériau rigide est, comme expliqué ci-dessus, du verre ou une matière plastique rigide transparente, telle qu'un polyméthacrylate, notamment le polyméthacrylate de méthyle.According to the invention, the laminated glazing comprises two external plates of rigid material: it can comprise at least one similar plate interposed between the external plates. This rigid material is, as explained above, glass or a transparent rigid plastic, such as a polymethacrylate, in particular polymethyl methacrylate.
La résine d'une couche de résine est un polymère transparent susceptible de former un film souple et n'ayant pas de propriétés de filtre anti-UV. Elle comporte, de préférence, une résistance aux chocs élevée : elle est, avantageusement, susceptible d'être réticulée par irradiation aux rayons UV. Elle peut être choisie dans le groupe formé par les polyesters insaturés, les poly carbonates, les polyméthacrylates ou polyacrylates, en particulier les polymères uréthane acryliques. Parmi les résines particulièrement utilisables, on peut citer la résine commercialisée sous la dénomination commerciale "CONLOC" par la Société "BOHLE" ou sous la dénomination commerciale "VITRALIT" par la Société "CVA" . Le film de polyester est, avantageusement, un film de poly (téréphtalate d ' éthy lgly col) .The resin in a resin layer is a transparent polymer capable of forming a flexible film and having no UV screening properties. It preferably comprises a high impact resistance: it is advantageously capable of being crosslinked by irradiation with UV rays. It can be chosen from the group formed by unsaturated polyesters, poly carbonates, polymethacrylates or polyacrylates, in particular acrylic urethane polymers. Among the resins which can be used in particular, mention may be made of the resin sold under the trade name "CONLOC" by the company "BOHLE" or under the trade name "VITRALIT" by the company "CVA". The polyester film is advantageously a poly (ethyl col terephthalate) film.
Le film de polyester utilisé contient au moins un filtre UV. Ce filtre anti-UV peut être introduit dans le film de polyester par tout moyen connu, tel que greffage de molécules en surface, dépôt en surface ou addition dans la masse. Le filtre anti-UV est, par exemple, une benzophénone, un benzotriazole, un acrylonitrile substitué ou un complexe phénol-nickel, ces composés étant bien connus de l'homme de métier. On peut plus particulièrement citer les filtres UV vendus sous la dénomination "UV-SHIELD" par la Société "GAMCOLOR" . La quantité de filtre anti-UV utilisée varie selon le filtre anti-UV et le polyester. Elle est, de façon générale, comprise entre 0,1 et 1 ,5 % en poids par rapport au poids du film de polyester.The polyester film used contains at least one UV filter. This UV filter can be introduced into the polyester film by any known means, such as grafting of molecules on the surface, deposition on the surface or addition in the mass. The UV filter is, for example, a benzophenone, a benzotriazole, a substituted acrylonitrile or a phenol-nickel complex, these compounds being well known to those skilled in the art. Mention may more particularly be made of the UV filters sold under the name "UV-SHIELD" by the company "GAMCOLOR". The amount of UV filter used varies depending on the UV filter and the polyester. It is generally between 0.1 and 1.5% by weight relative to the weight of the polyester film.
Le film de polyester peut être coloré de façon uniforme ou porter une représentation graphique ou holographique. Lorsque le film de polyester sert de support à une représentation, le filtre anti-UV est introduit dans ledit film de polyester avant la mise en place de la représentation. La représentation peut être une impression graphique mise en place de façon quelconque, notamment par sérigraphie ; éventuellement, le film de polyester peut être teinté dans la masse. Par représentation graphique, on entend selon la présente invention tout dessin, motif ou inscription, obtenu par tout procédé.The polyester film can be uniformly colored or bear a graphic or holographic representation. When the polyester film serves as a support for a representation, the UV filter is introduced into said film. polyester before setting up the representation. The representation can be a graphic printing set up in any way, in particular by screen printing; optionally, the polyester film can be mass-dyed. By graphic representation is meant according to the present invention any drawing, pattern or inscription obtained by any process.
Le film de polyester peut être encollé. Dans ce cas, le film est fixé par la partie encollée contre une plaque de matériau rigide transparent du vitrage ; il peut notamment être fixé par collage sur la face interne de l'une des deux plaques externes du vitrage. Lorsque le film de polyester porte une représentation graphique, on prévoit un tel collage sur la face interne de la plaque externe qui reçoit le rayonnement UV, la couche de résine, qui forme un intercalaire souple, étant disposée entre la face non-encollée du film de polyester et la plaque rigide qui ne reçoit pas le rayonnement UV. On peut avantageusement utiliser une colle de type acrylique qui favorise la filtration UV.The polyester film can be glued. In this case, the film is fixed by the glued part against a plate of transparent rigid material of the glazing; it can in particular be fixed by gluing on the internal face of one of the two external plates of the glazing. When the polyester film bears a graphic representation, such bonding is provided on the internal face of the external plate which receives UV radiation, the layer of resin, which forms a flexible interlayer, being disposed between the non-glued side of the film. polyester and the rigid plate that does not receive UV radiation. It is advantageous to use an acrylic type adhesive which promotes UV filtration.
Lorsque le film de polyester n'est pas encollé, il est, de préférence, disposé entre deux couches de résine formant intercalaire souple.When the polyester film is not glued, it is preferably placed between two layers of resin forming flexible interlayer.
Le vitrage feuilleté peut être préparé par tout procédé connu.Laminated glazing can be prepared by any known process.
Par exemple, pour un vitrage comportant seulement deux plaques rigides, la première plaque rigide externe est placée sur une table horizontale et une bande adhésive double face est appliquée sur le pourtour de la plaque. Il est bien entendu que l'on pourrait utiliser tout autre matériau susceptible de coller aux plaques rigides et de former entre elles un bourrelet d'épaisseur uniforme. Cette bande adhésive définit l'écartement entre les plaques externes du vitrage et donc l'épaisseur de la couche de résine formant intercalaire souple ; la bande sert de joint d'étanchéité. Une deuxième plaque externe rigide est déposée sur la bande adhésive et les deux plaques rigides sont pressées l'une contre l'autre. La couche de protection de la bande adhésive a été maintenue sur une certaine longueur de façon à ménager au moins une ouverture permettant l'introduction de la résine entre les deux plaques externes et une ouverture pour que l'air puisse s'échapper ; ces deux ouvertures peuvent n'en former qu'une seule dans la mesure où elle est assez grande. On injecte ensuite la résine dans le volume ménagé entre les deux plaques rigides.For example, for glazing comprising only two rigid plates, the first external rigid plate is placed on a horizontal table and a double-sided adhesive strip is applied around the periphery of the plate. It is understood that one could use any other material capable of sticking to the rigid plates and of forming between them a bead of uniform thickness. This adhesive strip defines the spacing between the external plates of the glazing and therefore the thickness of the layer of resin forming flexible interlayer; the strip serves as a seal. A second rigid external plate is deposited on the adhesive strip and the two rigid plates are pressed against each other. The protective layer of the adhesive strip has been maintained over a certain length so as to provide at least one opening allowing the introduction of the resin between the two external plates and an opening so that air can escape; these two openings can form only one as long as it is large enough. The resin is then injected into the volume formed between the two rigid plates.
Lorsque la résine est mélangée à un catalyseur et/ou durcisseur, on l'injecte entre les plaques rigides et on la laisse réticuler.When the resin is mixed with a catalyst and / or hardener, it is injected between the rigid plates and allowed to crosslink.
Lorsque la résine est une résine réticulable par un rayonnement UV, après avoir rempli le volume entre les deux plaques rigides, on fait passer le vitrage dans un four UV équipé de lampes appropriées. Lorsque le film de polyester est encollé, le procédé de fabrication du vitrage feuilleté se déroule comme décrit ci-dessus, le film de polyester étant collé sur la face tournée vers l'intérieur d'une des plaques rigides.When the resin is a resin crosslinkable by UV radiation, after filling the volume between the two rigid plates, the glazing is passed through a UV oven equipped with appropriate lamps. When the polyester film is glued, the process for manufacturing the laminated glazing takes place as described above, the polyester film being bonded to the side facing inwards of one of the rigid plates.
Lorsque le film de polyester n'est pas encollé, la préparation est effectuée sur une table verticale et le film de polyester est suspendu sous tension, parallèlement aux plaques rigides : on verse la résine de part et d'autre du film de polyester pour constituer deux couches de résine formant des intercalaires souples de part et d'autre du film de polyester. L'exemple de mise en oeuvre donné ci-après permettra de mieux comprendre l'invention.When the polyester film is not glued, the preparation is carried out on a vertical table and the polyester film is suspended under tension, parallel to the rigid plates: the resin is poured on either side of the polyester film to constitute two layers of resin forming flexible inserts on either side of the polyester film. The example of implementation given below will allow a better understanding of the invention.
On dispose sur une table verticale, susceptible de pivoter, une plaque rectangulaire de verre clair de type "float glass" d'une épaisseur de 4 mm, ayant des dimensions de 100 x 100 cm. On fixe sur la périphérie de cette plaque une bande adhésive double face commercialisée sous la dénomination "3 M n° 4910" par la Société "3M". On a enlevé la pellicule de protection de la bande adhésive sauf sur une longueur de 1 cm située à l'un des angles supérieurs de la première plaque de verre. On suspend parallèlement à la première plaque un film de poly(téréphtalate d'éthylglycol) contenant 0, 1 % en poids d'un filtre anti-UV vendu sous la dénomination commerciale "TINUVIN 571 " par la société "CIBA-GEIGY" . Une image a été imprimée par sérigraphie sur une des faces de ce film à l'aide des encres organiques de l'une des gammes :A rectangular plate of clear glass of the "float glass" type with a thickness of 4 mm, having dimensions of 100 × 100 cm, is placed on a vertical table capable of pivoting. A double-sided adhesive strip sold under the name "3M No. 4910" by the company "3M" is attached to the periphery of this plate. The protective film was removed from the adhesive strip except over a length of 1 cm located at one of the upper corners of the first glass plate. Parallel to the first plate is suspended a poly (ethyl glycol terephthalate) film containing 0.1% by weight of an UV filter sold under the trade name "TINUVIN 571" by the company "CIBA-GEIGY". An image was printed by screen printing on one side of this film using organic inks from one of the ranges:
- UVI-SPEED UX commercialisé par la Société "SERICOL" , - POLYPLAST commercialisé par la Société "SERICOL" ,- UVI-SPEED UX marketed by the company "SERICOL", - POLYPLAST marketed by the company "SERICOL",
- MD 8960.80.009 commercialisé par la société "MARCOLAC".- MD 8960.80.009 sold by the company "MARCOLAC".
On applique ensuite sur la bande adhésive une seconde plaque de verre identique à la première. On introduit entre les plaques, à l'aide d'une buse d'injection, une résine commercialisée sous la dénomination "CONLOC" par la Société "BOHL" : il s'agit d'une résine réticulable par irradiation aux rayons UV. On bascule la table en position horizontale et l'air s'échappe par l'ouverture d'injection. Après remplissage, l'ouverture d'injection est scellée à l'aide d'une colle thermofusible.A second glass plate identical to the first is then applied to the adhesive strip. Is introduced between the plates, using an injection nozzle, a resin sold under the name "CONLOC" by the company "BOHL": it is a resin crosslinkable by irradiation with UV rays. The table is tilted in a horizontal position and the air escapes through the injection opening. After filling, the injection opening is sealed using a hot-melt adhesive.
On effectue ensuite la polymérisation de la résine dans un four tunnel muni de lampes UV-A. Le temps de séjour de la plaque est de 20 secondes.The resin is then polymerized in a tunnel oven equipped with UV-A lamps. The residence time of the plate is 20 seconds.
On constate à la sortie du four que l'on obtient un verre feuilleté dans lequel la représentation graphique supportée par le film de polyester n'est pas modifiée. Après un stockage de 3 mois à l'atmosphère ambiante, le vitrage feuilleté ne s'est pas dégradé et l'image de la représentation graphique ne s'est pas modifiée. It is noted at the exit of the oven that a laminated glass is obtained in which the graphic representation supported by the polyester film is not modified. After storage for 3 months in the ambient atmosphere, the laminated glazing did not deteriorate and the image of the graphic representation did not change.

Claims

REVENDICATIONS
1 - Vitrage feuilleté comportant deux plaques externes de matériau transparent rigide, au moins un film de polyester disposé entre les deux plaques externes précitées et au moins une couche de résine formant un intercalaire souple entre les deux plaques externes, caractérisé par le fait que la résine d'une couche de résine ne présente pas, par elle-même, des propriétés de filtre anti-UV et que le film de polyester contient au moins un filtre anti-UV.1 - Laminated glazing comprising two external plates of rigid transparent material, at least one polyester film placed between the two above-mentioned external plates and at least one layer of resin forming a flexible interlayer between the two external plates, characterized in that the resin of a resin layer does not, by itself, have UV filter properties and that the polyester film contains at least one UV filter.
2 - Vitrage selon la revendication 1 , caractérisé par le fait que le film de polyester sert de support à une représentation graphique, holographique, métallisée ou holographique métallisée.2 - Glazing according to claim 1, characterized in that the polyester film serves as a support for a graphic, holographic, metallized or holographic metallized representation.
3 - Vitrage selon l'une des revendications 1 ou 2, caractérisé par le fait que le matériau rigide est du verre ou une matière plastique rigide transparente. 4 - Vitrage selon l'une des revendications 1 à 3, caractérisé par le fait que la résine d'une couche de résine a une résistance aux chocs élevée.3 - Glazing according to one of claims 1 or 2, characterized in that the rigid material is glass or a transparent rigid plastic. 4 - Glazing according to one of claims 1 to 3, characterized in that the resin of a resin layer has a high impact resistance.
5 - Vitrage selon l'une des revendications 1 à 4, caractérisé par le fait que la résine d'une couche de résine est susceptible d'être polymérisée par irradiation aux rayons UV.5 - Glazing according to one of claims 1 to 4, characterized in that the resin of a resin layer is capable of being polymerized by irradiation with UV rays.
6 - Vitrage selon l'une des revendications 1 à 4, caractérisé par le fait que la résine d'une couche de résine est choisie dans le groupe formé par les polyesters insaturés, les polycarbonates, les polyméthacrylates, les polyacrylates et les polymères uréthane acryliques.6 - Glazing according to one of claims 1 to 4, characterized in that the resin of a resin layer is chosen from the group formed by unsaturated polyesters, polycarbonates, polymethacrylates, polyacrylates and acrylic urethane polymers .
7 - Vitrage selon l'une des revendications 1 à 6, caractérisé par le fait que le film de polyester est un film de poly(téréphtalate d'éthylglycol).7 - Glazing according to one of claims 1 to 6, characterized in that the polyester film is a poly (ethylene glycol terephthalate) film.
8 - Vitrage selon l'une des revendications 1 à 7, caractérisé par le fait que le film de polyester contient un filtre anti-UV choisi dans le groupe formé par les benzophénones, les benzotriazoles, les acrylonitriles substitués ou non ou les complexes phénol-nickel.8 - Glazing according to one of claims 1 to 7, characterized in that the polyester film contains an anti-UV filter selected from the group formed by benzophenones, benzotriazoles, acrylonitriles substituted or not or phenol complexes nickel.
9 - Vitrage selon l'une des revendications 1 à 8, caractérisé par le fait que la quantité de filtre anti-UV présente dans le film de polyester est comprise entre 0,1 et 1,5 % en poids par rapport au poids du film de polyester. 10 - Vitrage selon l'une des revendications 1 à 9, caractérisé par le fait que le film de polyester est encollé et est fixé par collage sur l'une des faces d'une plaque de matériau rigide transparent du vitrage. 11 - Vitrage selon la revendication 10, caractérisé par le fait que le film de polyester est fixé par collage sur la face interne de l'une des deux plaques externes du vitrage.9 - Glazing according to one of claims 1 to 8, characterized in that the amount of UV filter present in the polyester film is between 0.1 and 1.5% by weight relative to the weight of the film polyester. 10 - Glazing according to one of claims 1 to 9, characterized in that the polyester film is glued and is fixed by bonding to one of the faces of a plate of transparent rigid material of the glazing. 11 - Glazing according to claim 10, characterized in that the polyester film is fixed by gluing on the internal face of one of the two external plates of the glazing.
12 - Vitrage selon l'une des revendications 1 à 9, caractérisé par le fait que le film de polyester est disposé entre deux couches de résine.12 - Glazing according to one of claims 1 to 9, characterized in that the polyester film is disposed between two layers of resin.
13 - Vitrage selon la revendication 2, caractérisé par le fait que le film de polyester portant la représentation graphique est recouvert d'un film transparent contenant au moins un filtre anti-UV pour constituer avec lui un sandwich. 13 - Glazing according to claim 2, characterized in that the polyester film carrying the graphic representation is covered with a transparent film containing at least one UV filter to form with it a sandwich.
EP98928421A 1997-06-04 1998-06-03 Laminated glass resistant to uv radiation Withdrawn EP0921940A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9706896 1997-06-04
FR9706896A FR2764284B1 (en) 1997-06-04 1997-06-04 SHEET GLASS RESISTANT TO UV RAYS
PCT/FR1998/001115 WO1998055294A1 (en) 1997-06-04 1998-06-03 Laminated glass resistant to uv radiation

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EP0921940A1 true EP0921940A1 (en) 1999-06-16

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EP (1) EP0921940A1 (en)
AU (1) AU8025398A (en)
CA (1) CA2262589A1 (en)
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WO (1) WO1998055294A1 (en)

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Publication number Priority date Publication date Assignee Title
ES1050634Y (en) * 2001-11-28 2002-08-16 Curvados Cristales Sa SOLAR ATTENUATOR PLURILAMINATED GLASS
US6811841B1 (en) 2003-04-15 2004-11-02 3M Innovative Properties Company Light-stable structures
ES2353778B1 (en) * 2008-07-28 2011-10-03 Agustin Gifre Ramon DECORATIVE PANEL OF BACKLIGHTED MULTI-GLASS GLASS.

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FR2472547A1 (en) * 1979-05-17 1981-07-03 Bonnet Albert SELF-ADHESIVE SECURITY FILM FOR AUTOMOTIVE WINDSHIELD
FR2495130B1 (en) * 1980-12-03 1986-09-12 Solar Control France SAFETY GLASS IMPROVEMENTS
US4600627A (en) * 1984-04-24 1986-07-15 Bridgstone Corporation Sandwich glasses
JP2875547B2 (en) * 1989-05-01 1999-03-31 株式会社ブリヂストン Laminated glass
GB2264259B (en) * 1992-02-24 1995-12-20 Rankins Laminated glazing material
FR2706446B1 (en) * 1993-06-18 1995-08-25 Saint Gobain Vitrage Int Laminated glazing with an apparent pattern.

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Title
See references of WO9855294A1 *

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FR2764284A1 (en) 1998-12-11
CA2262589A1 (en) 1998-12-10
AU8025398A (en) 1998-12-21
WO1998055294A1 (en) 1998-12-10
FR2764284B1 (en) 1999-08-13

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