EP2010384A1

EP2010384A1 - Laminated glazing and sealing and peripheral reinforcing means for same

Info

Publication number: EP2010384A1
Application number: EP07731875A
Authority: EP
Inventors: Emmanuel Valentin; Xavier Fanton; Samuel Dubrenat
Original assignee: Saint Gobain Glass France SAS; Compagnie de Saint Gobain SA
Current assignee: Saint Gobain Glass France SAS; Compagnie de Saint Gobain SA
Priority date: 2006-04-10
Filing date: 2007-04-04
Publication date: 2009-01-07
Also published as: CA2648396A1; KR20080108110A; RU2008144182A; US20090181203A1; RU2435672C2; FR2899631A1; BRPI0710488A2; FR2899631B1; JP2009533248A; CN101415550A; WO2007116184A1

Abstract

The invention concerns a laminated glazing comprising two substrates (S1, S2) between which is arranged an active system (3), characterized in that the glazing is provided with first means for peripheral sealing (10) of said active system (3), in particular against water in vapour form, comprising at least one joint based on thermosetting polymer(s) selected among the following polymer families: ethylene vinylacetetate, polyisobutylene, butylic rubber, polyamide, and second sealing means (11), in particular against liquid water, said second sealing means (11) being positioned between the substrates and peripherally relative to the first sealing means (10).

Description

LAMINATED GLAZING AND ITS MEANS FOR SEALING AND PERIPHERAL REINFORCEMENT

The present invention relates to laminated glazings, and more particularly those which have functionalities conferred by one or more layers and / or one or more discontinuous elements that may be of organic, mineral or hybrid organic / mineral nature. The laminated glazings usually consist of two rigid substrates between which is disposed a sheet or a superposition of polymer sheets of the thermoplastic type. The invention also includes so-called "asymmetrical" laminated glazings using a single rigid glass-type substrate associated with several polymer sheets, generally at least one based on polyurethane. The invention also includes laminated glazings having at least one interlayer sheet based on a single or double-sided adhesive polymer of the elastomer type (that is to say not requiring a lamination operation in the conventional sense of the term, laminating imposing heating generally under pressure to soften and adhere the thermoplastic interlayer sheet).

The discontinuous layers or elements mentioned above are generally arranged against one of the rigid substrates (or against the single rigid substrate) between said substrate and the sheet or one of the flexible sheets based on polymer. They can also be arranged between two flexible or semi-flexible substrates themselves associated with a rigid substrate or arranged between two rigid substrates. They will be referred to as "active systems". The glazing may include several.

The first types of active system of interest to the invention are electrochemical systems in general, and more particularly electrically controllable systems of the glazing type with variable energy and / or optical properties. They also include photovoltaic and electroluminescent systems. These systems have very different applications: photovoltaic cells convert solar energy into light energy.

The electrically controllable systems make it possible, in particular, to obtain glazing which can be modified at will obscuration / degree of vision or filtration of thermal / solar radiation. This is for example viologen windows, which adjust the transmission or light absorption, such as those described in US-5,239,406 and EP-612 82.

Electroluminescent systems directly convert electrical energy into light, an example being described in FR-2,770,222.

There are also electrochromic glazings, which can modulate the light and heat transmission. They are described, in particular, in patents EP-253 713 and EP-670 346, the electrolyte being in the form of a polymer or a gel and the other layers being of mineral type. Another type is described in patents EP-867,752, EP-831,360, PCT / FR00 / 00675, PCT / FR99 / 01653, the electrolyte being this time in the form of an essentially mineral layer, all layers of the system then being essentially mineral: this type of electrochromic system is commonly referred to as "all-solid" electrochromic. There are also electrochromic systems where all the layers are of polymer type, this is called "all-polymer" electrochromic.

In general, the electrochromic systems comprise two layers of electrochromic material separated by an electrolyte layer and framed by two electroconductive layers.

There are also systems called "optical valves": they are polymer-based films in which are arranged microdroplets containing particles able to be placed in a preferred direction under the action of an electric field. An example is described in WO93 / 09460.

There are also liquid crystal systems, operating in a similar way to the previous ones: they use a polymer film placed between two conductive layers and in which are dispersed liquid crystal droplets, especially nematic with positive dielectric anisotropy. When the film is energized, the liquid crystals are oriented along a preferred axis, which allows vision. Off, the movie becomes broadcast. Examples thereof are described in patents EP-238 164, US-4,435,047, US-4,806,922 and US-4,732,456. Cholesteric liquid crystal polymers, such as those described in the WO92 / patent, may also be mentioned. 19695.

A second type of active system to which the invention is concerned relates to layers or stacks of layers whose properties change without power supply, under the effect of heat or light: there may be mentioned thermochromic layers, particularly at Vanadium oxide base, thermotropic layers or photochromic layers. In the context of the present invention and throughout the present text, it is necessary to take the term "layer" in its broadest sense: it can be both inorganic materials and organic-type materials, particularly polymers. which may be in the form of polymer films or even gel films. This is particularly the case of thermotropic gels, for example those described in patents EP 639 450, US 5 615 040, WO 94/20294 and EP 878 296.

A third type of active system to which the invention relates concerns elements in the form of wires or heating networks, or heating conductive layers, by Joule effect (it may be son encrusted on the surface of the thermoplastic sheet as described especially in EP-785 700, EP-553025, EP-506 521 and EP-496 669).

A fourth type of active system to which the invention is concerned layers or stacks of solar control properties, low-emissive, in particular based on one or more layers of silver interposed by dielectric layers. These stacks can be deposited on one of the rigid substrates or be deposited on a flexible substrate of the PET (polyethylene terephthalate) type that is available between two sheets of thermoplastic polymer of the type PVB (polyvinyl butyral) coming to assemble the two rigid substrates of the glass type. Examples are found in patents EP-638,528, EP-718,250, EP-724,955, EP-758,583 and EP-847,965.

Some of these systems require electrical connection means to an external power source that must be designed to avoid short circuits. All these systems have in common the fact that they can, on a greater or lesser scale, be sensitive to mechanical, chemical, water contact and external exchanges. These are the reasons why, to preserve their proper functioning, these active systems are usually arranged against at least one protective carrier substrate. They are most often placed between two protective substrates, for example glass, rigid or semi-rigid or flexible polymer, either by direct contact or via thermoplastic type joining polymer sheet (s). This is most often the laminated structure described above. Peripheral sealing means are often provided, the purpose of which is to isolate the active system as far as possible from the outside.

Such sealing means are described in French Patent No. 2,815,374 which refers to a seal system. This joint system consists of a set of elements added to the periphery of the glazing for the purpose of isolating gases, liquids, dust, possibly to provide a mechanical reinforcement or an interface with the mounting frame (the bodywork in the case of automotive glazing). The joint system is often composed of several elements in order to simultaneously perform all the functions. As described in this patent, the seal system combines a polyisobutylene (gas barrier) seal, referred to as a butyl seal, and a polysulfide or polyurethane seal (liquid barrier). Furthermore, in this French patent, the butyl seal is preferably placed between the two substrates, for at least two reasons. On the one hand, its very low glass transition temperature Tg confers on it insufficient thermomechanical properties in the usual temperatures of use and it must not be in direct contact with the external environment because it could be degraded for example by tearing. On the other hand, it is in contact with the inner face of each of the substrates and this ensures the continuity of the gas barrier all around the glazing.

This system of joints is effective for substrates whose thickness is conventional (of the order of a few mm) and poses problems for so-called thin substrates (thickness less than mm)

Indeed, this set of rigid substrate / flexible interlayer / rigid substrate can be excessively mechanically stressed during the lamination operation (which is usually under pressure and generally hot). Indeed, the edges of the rigid substrates, in the area where the peripheral groove of the active system is located, are cantilevered and tend to bend under the pressure relative to the more central part of said substrates. This will result in optical distortion effects, visible in reflection and / or transmission.

In the case of rigid glass-type substrate, a risk of breakage exists. There will also be a risk of incomplete adhesion, possibly signified by the presence of bubbles on the periphery. In addition, the thin substrates do not have sufficient mechanical properties to withstand the compression forces generated by the molds during the post-laminating encapsulation operation and incur a risk of breakage at the periphery, thereby resulting in non-compliance of the device incorporating the active system. As indicated in patent FR 2 815 374, it is possible to insert mechanical reinforcement means inside butyl seal as steel balls or to add a metal frame at the periphery, but all these elements have the disadvantage of presenting a behavior thermomechanical different from the laminating polymer, and therefore to increase the risk of optical deformation or breakage. In addition, in the case of the metal frame, it does not flicker on the substrates and the adhesion between the two substrates at the periphery is zero.

The purpose of the invention is therefore to improve the design of the systems said laminated glazing joints, in particular with respect to their chemical properties and / or their mechanical properties, and / or their implementation and / or their configuration relative to the substrates protecting the active systems. Butyl rubber gaskets associated with silicone or polysulfide gaskets are generally used.

However, these joints are likely to improve in several ways. Indeed, these joints must best meet at least three requirements that are not necessarily compatible: - as we have seen, they must isolate the active system from the outside.

They must therefore act as a barrier as effectively as possible, particularly with respect to water or any other solvent, and in its vapor form and / or in its liquid form.

However, the seals used so far, including those described in FR 2,815,374 in particular based on butyl rubber, are not entirely satisfactory on this point, it constitutes a generally satisfactory barrier to water in the form of steam but not to water in liquid form.

- their implementation, the way they are placed on the edge of devices is not necessarily the simplest on the industrial level,

- and finally, their mechanical properties can be much lower than what would be required.

Document US Pat. No. 6,001,487 also discloses laminated glazing comprising two substrates between which an active system is disposed, said glazing being provided with a peripheral sealing means comprising a polyisobutylene-based seal.

More particularly, when the active system is interposed between two thin substrates (thickness of each of the substrates substantially close to 3 mm, or even much less (between 0.4 mm and 1.8 mm, preferably 0.7 mm), the peripheral sealing means which must provide a liquid water barrier and is generally reported by an encapsulation technique that may damage the glazing, because thin substrates do not have mechanical sufficient to withstand the compressive forces generated by the molds and incur a risk of breakage periphery, resulting in a non-compliance of the device incorporating the active system.

Furthermore, the use of so-called thin laminate substrates greatly reduces the contact surfaces for attachment of the peripheral seal. Indeed, the optimal attachment of a peripheral seal reported by an extrusion technique and / or encapsulation is conditioned by the thickness of the glass sheet. It is understood that for a thin substrate, the edge of the glass sheet is almost a line, which is obviously too small a thickness to allow optimum attachment of the seal.

The purpose of the invention is therefore to improve the design of the peripheral sealing seals of the aforementioned laminated glazings, in particular as regards their chemical properties and / or their mechanical properties, and / or their implementation and / or their configuration. compared to substrates protecting active systems.

The invention firstly relates to a laminated glazing unit, the various structures of which have been described above, and comprising an "active system" among one of those mentioned above which is disposed between two thin substrates of said glazing unit. The invention consists in providing this glazing with a first means of peripheral sealing of the active system, particularly with respect to water in vapor form, comprising at least one seal based on a polymer (s) hot melt (s) ) chosen from at least one of the following families of polymers: ethylene vinyl acetate, polyisobutylene (butyl rubber), polyamide, and a second sealing means, in particular with respect to liquid water, this second sealing means being positioned between the substrates and peripherally with respect to the first sealing means.

It is indeed important not only to choose an inherently tight polymer, but which also adheres very well to the materials with which it is in contact, so as to avoid creating diffusion paths at the joint interface / material to be sealed, in order to avoid any delamination of the joint. In place of or in addition to the use of such sticky agent, one can also play on the distribution of the molar masses present in the hot-melt polymer, especially in the case of polyisobutylenes: mixing several molar masses makes it possible to have a good creep resistance in temperature (for the high masses) and d also have good adhesion to the materials to be sealed, a good "tack" (for low molar masses).

Overall, the first sealing means and within the meaning of the invention is hot melt. It has a softening point at room temperature, a soft appearance and because of its viscosity, at this temperature, it can be liquefied to ask / shape at acceptable temperatures industrially.

They also have a viscosity of between 0.1 and 20 Pa.s, especially between 0.8 and 8 Pa.s, measured at 190 ° C.

Finally, they have a water permeability in vapor form of less than or equal to 5 or 4 or 3 g / m ² / 24h, in particular less than or equal to 1 g / m ² / 24h according to ASTM standard E 9663 T: this means that they are particularly impervious to water.

The hot-melt polymers of the joints described above can be substituted by mastics, which are hot-acting polymers such as hot melt polymers, but whose transformation from the solid phase to the liquid phase is not reversible, unlike hot melt (because it is thermosetting). The advantage of being able to put them in place in the liquid phase glazing also exists for this family of sealants, provided to select those of them that crosslink only after their establishment.

Polyurethane-based sealants are particularly preferred, whose water permeability in vapor form is less than or equal to 4 g / m ² / 24h or even close to 2. PU-based sealants meeting the desired criteria ( especially having a permeability to water in vapor form lower or equal to 5 g / m ^2/24 h) are sealants marketed under the reference IS442 by Tremco company (permeability of 5 g / m ^2/24 h) and under the reference PU 3189/2 by the company SEAL FRENCH (permeability of 4 g / m ^2/24 h). The advantage of these particular mastics is that they can ensure both a good water vapor and liquid water impermeability, while it is preferable to "double" the hot melt polymer joints of a second gasket to serve as a barrier to liquid water. It can also be mastics based on polysulfide or silicone.

In conclusion on the chemical nature of the polymers used in the first sealing means according to the invention, these hot-melt polymers were known in very different applications, in particular in the shoe and cardboard industry, and it turned out that they were particularly interesting in any other technical field which concerns the invention.

Another aspect of the invention relates to the way in which the mechanical resistance of the seals for these laminated glazings can also be improved from so-called thin glass sheet, in particular but not exclusively, the hot-melt joints described above: Another subject of the invention is the same type of substrate, provided with a first peripheral sealing means, particularly with respect to water in vapor form, which comprises at least one polymer-based seal and which is associated with a second sealing means providing both means of mechanical reinforcement and / or calibration of the spacing between the two substrates between which is the active system and a water seal in liquid form.

Indeed, it is necessary in a number of cases, that the seal has a significant mechanical strength. This is particularly the case when the device is in the form of a laminated glazing comprising two rigid or semi-rigid substrates, the thickness of which can be described as thin (between 0.4 mm and 1.8 mm) between which the active system and one or more sheets of polymer assembly. In this case, a convenient configuration is to provide that the sheet (s) of assembly polymer (as well as the active system itself) are smaller than those of the two substrates. This creates at the periphery of the glazing a groove where we will be able to accommodate the second sealing means or. Thanks to that configuration, one can use however a hot melt (which provides no mechanical reinforcement) due to the simultaneous use of a second peripheral seal mechanical strength property and water barrier. The use under these conditions of one or more peripheral joints will be able to maintain the appropriate spacing between the two thin substrates at their periphery, in opposition to their tendency to bend in the "critical" peripheral zone of the groove, during the assembly operation at least. According to one embodiment of the second sealing and reinforcing / sizing means, the latter may be in the form of a frame, in particular of thermoplastic material, of the lamination interlayer type, low melting point. The section of the frame can be square, rectangular, etc. This frame can be one piece, or be in several parts that is put end to end during installation. This second peripheral sealing means may take the form of a thermoplastic polymer gasket, for example polyvinyl butyral PVB, ethylene vinyl acetate EVA, based on sulfur-based polymer, based on polyethylene acrylate, EPDM that the extruded as the first butyl-based sealing means, or certain polyurethanes. Advantageously, this seal may be in fact of the same chemical nature, or of a similar chemical nature, as that of the thermoplastic interlayer sheets used for laminating the glazing.

It is thus possible to approach the structure of the frames / spacers which serve to maintain the spacing between the lenses of the standard double glazings.

It has thus cut back the interleaf or sheets with respect to the two glasses, in order to create a peripheral groove to accommodate the joint or joints, and we can ensure that the groove is provided with one or two joints such as described above. Then, we completed the "fill" with a strip of thermoplastic polymer of the same origin as the interlayers. These strips indeed provide the role of sealing liquid, and are in a material already available since it is used to make the interleaves: it is a simple and effective solution, that of "diverting" thus thermoplastic sheets to make them play the role of complementary joints. This thermoplastic seal is preferably continuous all around the glazing. It can also be discontinuous. He thus "imprison" the other or joints arranged before him in the peripheral groove.

In this case, preferably the first and second sealing means of the device comprise seals which are contiguous. Co-injection / co-extrusion can be done, for example, of two types of joints of different chemical formulations. It is also possible to deposit side by side two pre-extruded or pre-cast or pre-cut cords. It is possible to ensure that all the joints are housed in the peripheral groove described above. We then have a device whose sealing is flush, and does not "overflow" substrates, which is both aesthetic and practical for the mounting of the substrate in motor vehicles, aircraft (use as a porthole) or buildings, or in screens or "displays".

Generally, these means of sealing and mechanical reinforcement are placed on one of the substrates of the device, before its assembly with the other substrate (case of cords mentioned above).

One can also use a single joint, from the moment when its chemical nature makes it impermeable to both liquid water and steam water satisfactorily.

Advantageously, the sealing and reinforcing means used in the context of the invention are arranged so as to have no contact with the electroconductive layers of the active system.

The invention will be described below in more detail with the following nonlimiting examples using FIGS. 1, 2 and 3. These figures represent, very schematically, a sealed electrochromic laminated glazing unit according to the invention. The examples all relate to electrochromic glazing "all solid". In the accompanying drawings, some elements may be represented in larger or smaller dimensions than in reality, in order to facilitate understanding of the figures.

The example illustrated in FIGS. 1, 2 relates to electrochromic glazing 1. It comprises successively, from the inside to the outside of the passenger compartment, two thin glasses S1, S2, which are clear glasses (they can also be tinted) silico-soda-lime, of respectively 0.4 mm and 1.8 mm d thickness for example.

The glasses S1 and S2 are of the same size and their dimensions are 150 mm x 150 mm.

The glass S1 is laminated to the glass S2 by a thermoplastic sheet of polyurethane (PU) 0.8 mm thick (it can be replaced by a sheet of ethylenevinylacetate (EVA) or polyvinylbutyral (PVB) by trapping a stack 3 thin layers of electrochromic type.

The stack of thin electrochromic layers may be of the "all solid" type and it comprises for example an active stack 3 placed between two electronic conductive materials also called current collectors 2 and 4. The collector 2 is intended to be in contact with the 2. The collectors 2 and 4 and the active stack 3 may be of substantially identical dimensions and shapes, or of substantially different dimensions and shapes, and it will be understood that the path of the collectors 2 and 4 will be adapted in accordance with FIGS. function of the configuration. Furthermore, the dimensions of the substrates in particular Sl can be substantially greater than those of 2, 4 and 3.

The collectors 2 and 4 are of metallic type or of the type TCO (Transparent Conductive Oxide) in In ₂ O ₃ : Sn (ITO), SnO ₂ : F, ZnO: A1, or be a TCO / metal / type multi-layer. TCO (these TCOs may be chosen from those mentioned above), and the metal being chosen in particular from silver, gold, platinum, copper. It may also be a multi-layer type NiCr / metal / NiCr, the metal being also chosen in particular from silver, gold, platinum, copper. According to the configurations, they can be suppressed and in this case current leads are directly in contact with the active stack 3.

The glazing 1 incorporates current leads 8, 9 which control the active system via a power supply. These current leads are of the type used for heated glazing (ie foil, wire or the like).

A preferred embodiment of the collector 2 consists in depositing on the face 2 (the numbering system of the faces will be recalled: 1 outer face of Sl, 2 inner face of Sl, 3 inner face of S2, 4 outer face of S2 directed towards inside an enclosure) a first SiOC layer of 50 nm. surmounted by a second SnO2: F layer of 400 nm (two layers preferably deposited successively by CVD on the float glass before cutting). A second embodiment of the collector 2 consists in depositing in face 2 a bilayer constituted by a first SiO 2 -based doped or non-doped layer (in particular doped with aluminum or boron) of approximately 20 nm surmounted by a second layer of ITO of about 100 to 600 nm (two layers preferably deposited successively, under vacuum, by magnetic field assisted sputtering and reactive in the presence of oxygen optionally in hot).

Another embodiment of the collector 2 consists in depositing on the face 2 a monolayer consisting of ITO of approximately 100 to 600 nm (a layer preferably deposited, under vacuum, by magnetic field assisted sputtering and reactive in the presence of oxygen possibly hot)

The collector 4 is a 100 to 500 nm ITO layer also deposited by magnetic field assisted reactive sputtering on the active stack. The active stack 3 is broken down as follows according to a first variant embodiment:

A layer of anodic electrochromic material of nickel oxide of 100 to 300 nm, alloyed or not with other metals, A layer of hydrated tantalum oxide or of hydrated silica oxide or of hydrated zirconium oxide of 100 nm or a mixture of these,

A layer of cathodic electrochromic material based on tungsten oxide of 200 to 500 nm, preferably 300 and 400 nm, especially close to 370 nm.

According to a second variant embodiment, the active stack 3 is broken down as follows:

• a layer of anodic electrochromic material in nickel oxide from 100 to 300 nm, alloyed or not with other metals.

A layer of hydrated tungsten oxide of 100 nm,

A layer of hydrated tantalum oxide or of hydrated silica oxide or of hydrated zirconium oxide of 100 nm or a mixture of these, a layer of cathodic electrochromic material based on tungsten oxide hydrate of 200 to 500 nm, preferably 300 and 400 nm, especially close to 370 nm.

According to a third variant embodiment, the active stack 3 is broken down as follows: a layer of anodic electrochromic material of iridium oxide 70 at 100 nm, alloyed or not with other metals.

A layer of hydrated tungsten oxide of 100 nm,

A layer of hydrated tantalum oxide or of hydrated silica oxide or of hydrated zirconium oxide of 100 nm or a mixture of these,

A layer of cathodic electrochromic material based on hydrated tungsten oxide of 200 to 500 nm, preferably 300 and 400 nm, in particular close to 370 nm.

The active stack 3 may be incised on all or part of its periphery grooves made by mechanical means or by laser radiation attack, possibly pulsed, and this in order to limit peripheral electrical leakage as described in the application French FR-2 781 084.

According to other variants, the active stack 3 "all solid" can be replaced by other families of electrochromic polymer type.

Thus, for example, a first portion formed of a layer of electrochromic material or otherwise called active layer, poly (3,4-ethylene-dioxythiophene) from 10 to 10000 nm, preferably from 50 to 500 nm; alternatively it may be one of the derivatives of this polymer, is deposited by known techniques of liquid deposition (spraying or "spray coating", soaking or "dip coating", rotary spraying or "spin coating" or by casting), or by electrodeposition, on a substrate coated with its current collector, this current collector may be a lower or upper conductive layer forming the electronic conductor (anode or cathode), optionally provided with wires or Similar. Whatever the polymer constituting this active layer, this polymer is particularly stable, especially with UV, and operates by insertion-deinsertion of lithium ions (Li ⁺ ) or alternatively of H ⁺ ions.

A second part acting as an electrolyte, and formed of a layer of thickness between 50 nm to 2000 μm, and preferably between 50 nm to 1000 μm, is deposited by a known technique of liquid deposition ( spraying or "spray coating", dip coating or "dip coating", rotary spraying or "spin coating" or casting, between the first and third parts on the first part or by injection.This second part is based on polyoxyalkylene, in particular polyoxyethylene and may be associated with a mineral-type electrolyte layer, based for example on hydrated oxide of tantalum, zirconium or silicon.

This second portion of electrolyte deposited on the layer of active electrochromic material, itself supported by the glass substrate or the like, is then coated with a third part whose constitution is similar to the first part, namely this third part is broken down into a substrate, coated with a current collector (conducting wires, conducting wires + conductive layer, conductive layer only), this current collector being itself covered by an active layer.

This example corresponds to a glazing operating by proton transfer. It consists of a first Sl glass substrate, of 0.8 mm soda-lime glass, then successively:

A first 300 nm Snn2: F electroconductive layer,

A first layer of NiO _x Hy hydrated nickel oxide electrochromic material of 185 nm (it could be replaced by a 55 nm layer of hydrated iridium oxide), an electrolyte decomposing into a first oxide layer; of 70 nm of hydrated tantalum, a second layer of polyoxyethylene solid solution with POE-HsPO ₄ phosphoric acid of 100 microns or alternatively a solid solution of polyethylene imine with phosphoric acid PEI-H 3 PO 4, combined with a hydrated tantalum oxide or hydrated silica oxide or hydrated zirconium oxide layer of 100 nm or a mixture thereof,

A second layer of 350 nm tungsten oxide cathodic electrochromic material; a second 300 nm SnO 2: F layer and then a second glass substrate identical to the first one.

Thus, in this example, there is a bi-layer electrolyte polymer-based usually used in this type of glazing, which is "doubled" with a layer of hydrated tantalum oxide sufficiently conductive not to penalize the transfer of protons via the polymer and which protects the counter electrode of anodic electrochromic material from direct contact with the latter, the intrinsic acidity of which would be detrimental to it.

In place of the hydrated Ta2O5 layer may be used a hydrated Sb2θs or TaWO _x type layer. It is also possible to provide a tri-layer electrolyte with two layers of hydrated oxide, either on either side of the polymer layer, or superimposed on each other on the side of the layer of anode electrochromic material. Whatever the type of active system, the glazing shown in FIGS. 2,3 incorporates a first peripheral seal in contact with faces 2 and 3, this first seal 10 being adapted to provide a barrier against external chemical attack and a barrier water vapor.

An example of formulation for this first seal is the following:

a base of ethylene-vinyl acetate, of which from 5 to 40% of vinyl acetate and from 40 to 95% of ethylene (this is in particular 1 "VA marketed by National Starch under the name" Instant Pak 2300 "or the EVA marketed by the company TRL under the name "Thermelt 2147/2157), this base may contain at least one of the following additives:

- a tackifying resin

- a crosslinking agent - a load

With this type of formulation, a first seal 10 is obtained which is both remarkably impermeable to water in vapor form and very adherent to glass, which makes it very effective.

Alternatively, instead of the EVA-based gasket, a gasket based on polyamide or polyisobutylene or butyl rubber can be used.

In the above example, the seal is hot melt (it is a "hot melt" according to the English term). It is soft at room temperature or it can be melted and then injected under pressure into the peripheral groove of the glazing once assembled. It can also be placed on the periphery of the glass Sl before its assembly with the glass S2, the lamination operation calibrating it to the desired section under the effect of pressure and possibly heat.

A second peripheral seal 11 is in contact with the faces 2 and 3 of S1 and S2 and is positioned at the periphery of the first seal 10. It provides a sealing barrier with the liquid water and provides a reinforcement means of the peripheral groove, preventing thin substrates from breaking during lamination or during successive manipulations.

This second seal 11 surrounds the first seal 10 and serves to seal against the liquid water. We can deposit it:

by extrusion of polyurethane PU or any thermoplastic polymer elastomer TPE

- by reactive injection of PU (technique that is often referred to as "RIM" in English for "Reactive Injection Molding")

by thermoplastic injection of a PVC (polyvinyl chloride) / TPE mixture by injection and vulcanization of terpolymer of ethylene, propylene and an EPDM diene.

- By depositing a frame or a frame portion made of a thermoplastic material similar to that used for lamination interleaves.

It may also be a band of PU, EVA, PVB, polyethylene acrylate, for example of the same nature as that of the thermoplastic interlayer sheet.

The laying can be done simultaneously or consecutively with that of the first seal, before or after assembly of the glazing. It can be "overflowing", cover the edges of the two glasses, or come to stick to the first seal in the peripheral groove of the glazing so that all of the two joints are flush in the final laminated glazing.

The invention has therefore developed a new chemical seal formulation and a new means for reinforcing mechanically. These means of sealing and mechanical reinforcement are effective when it comes to protecting layers / elements between two substrates that are sensitive to water (liquid and / or vapor), or to gases such as oxygen and, in general, any exposure to the atmosphere.

The invention also makes it possible to simplify the manufacturing process, since the seals are positioned during the lamination operation, there is no longer any need to carry out the post-lamination encapsulation operation.

They can of course also be used for active system glazing operating in reflection (mirror-type electrochromic mirror for example), for glazing where the thermoplastic interlayer is replaced by a double-sided adhesive polymer film.

They also apply to non-glass substrates. They can also be applied to active systems requiring peripheral sealing but not in the form of laminated glazing (double glazing, system without rigid substrate ...).

Thus, it can also be applied to glazings for which the active stack occupies only a reduced portion of the total surface of the glazing (sun blind strip for example ....) or more generally any type of glazing in which the active system, including electrochromic, is only an accessory element in the entire glazing. In this case, the PU and its first peripheral sealing means are only necessary for the zones covered by the active system, the second sealing and reinforcing means, in particular based on EVA or PVB being sufficient for the zones. classics. According to yet another preferred variant of the invention, the laminated glazing previously described may be used as a facade in front of a vehicle dashboard. Positioned in front of the latter, when the active system is colored, it obscures the dashboard thus masking the information or the various dials (account turn, speed indicator, temperature, display screen, watch, ...) n not appearing at the dashboard level. This colored state of the active system makes it possible to have a particularly aesthetic rendering of the entire dashboard (in general this situation constitutes the stopping position of the vehicle).

On the contrary, in a discolored state of the active system, the laminated glazing positioned in front of the dashboard does not hinder the driver's vision of information from the dashboard and the dashboard does not see its functionality affected. It may be noted that the invention has the particular advantage of allowing, compared to the solutions of the prior art generally constituted by tinted glass facades, to avoid oversizing, information systems of the dashboard which must nevertheless, to guarantee a visualization of this information despite the tinted facade, this oversizing resulting in over-consumption of the display devices, and overheating thereof.

It is also possible to use the laminated glazing according to the invention, always positioned in front of the screens of a dashboard, as a head-up display screen (in English HUD for Head Up Display).

In order to guarantee a correct visualization of the information projected on this screen, the laminated glazing is associated with a third counter-glass which is superimposed on it. In order to prevent the virtual image projected and displayed on this screen from being distorted given the different reflections inherent to the reflective properties of the glass

(Different faces), the relative position of the user relative to the plane of the image, the against-glass is superimposed with the laminated glazing object of the invention by interposing a sheet of PVB wedge (commonly called in English PVB Wedge).

The operation of the head-up display screen is as follows:

In a colored state of the active system, the projected image is reflected by the screen and becomes visible, without optical distortion, by the driver. In a faded state of the active system, the projected (or non-projected) image is not reflected by the screen positioned on the front of the dashboard, and the usual information from the indicators, counters, and the like edge, appear normally.

Claims

1. Laminated glazing comprising two thin substrates (S1, S2) between which is disposed an active system (3), characterized in that the glazing is provided with a first peripheral sealing means (10) of the active system, in particular screws with water in vapor form, comprising at least one seal based on thermofusible polymer (s) chosen from at least one of the following families of polymers: ethylene vinyl acetate, polyisobutylene, butyl rubber, polyamide, and a second sealing means (11), in particular with respect to the liquid water, this second sealing means being positioned between the substrates (Sl, S2) and peripherally with respect to the first sealing means (10), said second sealing means (11) being at least one frame portion made from a sheet of thermoplastic material.

2. Glazing according to claim 1, characterized in that the sheet of thermoplastic material is based on EVA, PU, PVB, polyethylene acrylate, sulfur polymers, in particular of the same nature as the (the) sheet (s) ) of intermediate polymer (s) for lamination of said glazing.

3. Glazing according to one of the preceding claims, characterized in that the active system (3) is an electrochemical system, including an electrically controllable system with variable energy / optical properties such as an electrochromic system all solid, polymer, an optical valve system , a liquid crystal system, a viologen system, a photovoltaic system or an electroluminescent system.

4. Glazing according to one of the preceding claims characterized in that the active system (3) is a layer or a stack of thermochromic layers, thermotropic, photochromic, solar control or low-emissive.

5. Glazing according to one of the preceding claims, characterized in that it is in the form of a laminated glazing, with two substrates (S1, S2) rigid or semi-rigid between which is the electroactive system (3) surmounted by at least one intermediate sheet (fl) based on thermoplastic polymer.

6. Glazing according to claim 5, characterized in that the intermediate sheet (s) (f) has (have) dimensions smaller than those of the two substrates (S1, S2), so as to create a peripheral groove between said substrates, the seal (s) of the first peripheral sealing means (10) and the second sealing means (11) being housed (s) at least partly, and preferably entirely, in said groove.

7. Glazing according to one of the preceding claims, characterized in that the (s) seal (s) of the first sealing means (10) peripheral has (s) a softening point at room temperature.

8. Glazing according to one of the preceding claims, characterized in that the (s) seal (s) of the first peripheral sealing means (10) has (s) a viscosity of between 0, 1 and 20 Pa.s, in particular between 0.8 and 8 Pa.s at 190 ⁰ C.

9. Glazing according to one of the preceding claims, characterized in that the (s) seal (s) of the first sealing means (10) peripheral has (s) a water permeability in vapor form less than or equal to 5 or 4 or 3 g / m ² / 24h according to ASTM E 9663 T.

10. Glazing according to one of the preceding claims, characterized in that the (s) seal (s) of the first peripheral sealing means (10) is (are) placed (s) by extrusion or injection in the liquid phase.

11. Glazing according to one of the preceding claims, characterized in that the first and second peripheral sealing means (10, 11) comprise joints which are contiguous.

12. Glazing according to one of the preceding claims, characterized in that all the joints of the peripheral means (10, 11) of sealing are housed in the peripheral groove present between the two substrates (Sl, S2) due to removal of the intermediate sheet or sheets based on thermoplastic polymer, in particular to obtain flush seals.

13. Glazing according to one of the preceding claims, characterized in that that it constitutes a glazing of motor vehicles, aircraft or buildings.

14. Glazing according to any one of claims 1 to 12, characterized in that it constitutes a facade positioned in front of a vehicle dashboard.

15. Glazing according to claim 14 characterized in that it is used as a head-up display screen type "HUD".