FR2957159A1 - Electrocontrollable device useful in simple/multiple glazing, comprises a first substrate having glass function, first electronically conductive layer, electroactive system, second electronically conductive layer, and second substrate - Google Patents

Abstract

The electrocontrollable device having variable optical/energetic properties, comprises a first substrate (V1) having glass function, a first electronically conductive layer (TCC1) with an associated current supply, an electroactive system (EA), a second electronically conductive layer (TCC2) with an associated current supply, and a second substrate (V2) having glass function. The electronically conductive layers are formed by a continuous layer that is divided, by etching, into two independently addressable areas. The electroactive system comprises a medium. The electrocontrollable device having variable optical/energetic properties, comprises a first substrate (V1) having glass function, a first electronically conductive layer (TCC1) with an associated current supply, an electroactive system (EA), a second electronically conductive layer (TCC2) with an associated current supply, and a second substrate (V2) having glass function. The electronically conductive layers are formed by a continuous layer that is divided, by etching, into two independently addressable areas. The electroactive system comprises a medium containing an electroactive organic compound (ea 1+>) capable of reducing and/or accepting electrons and cations acting as compensation charges and electroactive organic compound (ea 2+>) capable of oxidizing and/or ejecting electrons and cations acting as compensation charges. The electroactive organic compounds is electrochrome to obtain a color contrast, and ionic charges allow, under the action of an electric current, oxidation and reduction reactions of the electroactive organic compounds, which are necessary to obtain the color contrast. The ionic charges are placed in a percolation path. Two electronically conductive layers are etched with one another. The etched electronically conductive layer has resistivity of 20-1 omega /square. The conductive layers comprise organic and/or inorganic sublayer and plastic substrates. The ionic charges are carried by electroactive organic compounds, ionic salt and/or an acid dissolved in the liquid. The electroactive system is present in the form of a self-supporting layer including a matrix with the self-supporting layer. The ionic liquid or molten salt forms a solubilizing liquid carrying ionic charges, which have all or part of the ionic charges of the electroactive material. The solubilization liquid is constituted of a solvent or a mixture of solvents. The electroactive system is a gel system formed by the solubilization liquid. The electroactive compounds, the ionic charges and a thickening agent dissolve in the liquid formed by the solvents and ionic liquids and/or molten salts. The matrix is translucent or transparent, when impregnated by the liquid with the solubilized electroactive compounds and ionic charges, and is able to preserve a portion of its integrity once impregnated by the liquid so that the electroactive system is ensured. The matrix is formed by a sheet or a stack of layers, where each layer is a textile or non-textile sheet and the textile sheet has a non-woven veil or mat form, woven or knitted form optionally coated with a binder, which is partially soluble in the liquid to form a gel. The polymer film comprises a non-textile sheet including a homopolymer or copolymer. The porous film is optionally capable of swelling in the liquid comprising ionic charges. The device is operated by transmission or reflection. The substrates are transparent, flat or curved, clear or mass colored or opaque, polygonal or partially curved, and incorporate another functionality such as solar control, anti-glare or self-cleaning functionality.

Description

ELECTROCOMMANDABLE DEVICE WITH VARIABLE OPTICAL / ENERGY PROPERTIES AND PREFERENTIAL COLORING AREAS, METHOD FOR MANUFACTURING THE SAME, AND GLAZING COMPRISING SUCH A DEVICE

The present invention therefore firstly relates to an electrically controllable device with variable optical / energy properties, comprising the following stack: a first glass-function substrate (V1); a first electronically conductive layer (TCC1) with an associated current supply; an electroactive system (EA); a second electronically conductive layer (TCC2) with an associated current supply; and a second glass-function substrate (V2). The present invention relates to a method of manufacturing this electrically controllable device and to a glazing unit comprising it. The object of the present invention is to provide an electrically controllable device of the aforementioned type with preferential coloration areas. The electrochromic technology based on electrochromic organic compounds solubilized in an active medium does not allow to have an electrochromic effect on only a part of the electrically controllable device or to control which parts of the pane must be colored or discolored. It is possible to obtain glazing with preferential areas of coloration by using an "all solid" technology with an electrochromic stack consisting of inorganic thin layers as described in the patent application WO2005 / 076061. In this case, to form independently addressable areas to obtain a preferential coloring, it is necessary to successfully burn the entire stack. Such etching is a delicate operation during which the stack can be degraded due to the manipulations performed for etching. The international application PCT WO 03/012541 A2, describes an EC glazing with preferential areas of coloration using a technology based on electrochromic organic compounds (also called "viologen" technology and used for example in mirrors). For this, the peripheral busbar of each substrate + TCC is replaced by several bus-bars and a coloring potential is applied only to bus-bars located in the area that the user wishes to be colored first. In this case, since the TCCs of each substrate are continuous, after a certain time, and as long as the glazing is fed, the coloring will gain all the glazing and there will be no preferential color zone.

A significant improvement of this invention would be to preserve the coloring by zones as a function of time when the glazing remains energized (the electrochromic glazings using organic electrochromic compounds have no memory effect and the coloration disappears when the glass is no longer electrically powered). The Applicant Company has now discovered that, in order to be able to produce, using "viologen" technology, electrochromic glazings with preferential zones of staining, which are stable over time, it is possible to etch only the TCCs of the substrates of the glazing in a manner that to be able to independently address several areas of the engraved TCCs. The Applicant Company has even shown that etching the TCC of only one of the two substrates, and then using conventional electrochromic assembly techniques with organic electrochromic compounds (for which the electroactive medium is continuous), is sufficient to obtain the desired effect. This etching of the two TCCs of an electrically controllable device and even better of a single TCC provides a simplicity advantage of the manufacturing process, several optical effects that can be obtained according to the power supply mode of the glazing. The present invention therefore firstly relates to an electrically controllable device with variable optical / energy properties, comprising the following stack: a first glass-function substrate (V1); a first electronically conductive layer (TCC1) with an associated current supply; an electroactive system (EA); a second electronically conductive layer (TCC2) with an associated current supply; and a second glass-function substrate (V2), characterized in that at least one of the electronically conductive layers (TCC1; TCC2) is formed by a continuous layer which has been etched into at least two independently addressable areas and that the electroactive system (EA) comprises a medium comprising: at least one electroactive organic compound (eal +) capable of being reduced and / or of accepting electrons and cations acting as compensation charges; at least one electroactive organic compound (ea2) capable of oxidizing and / or ejecting electrons and cations acting as compensation charges; at least one of said electroactive organic compounds (eal + and ea2) being electrochromic to obtain a color contrast; and ionic charges capable of allowing, under the action of an electric current, oxidation and reduction reactions of said electroactive organic compounds (eal + 10 and ea2), which are necessary to obtain the color contrast, said ionic charges having a percolation path; said electroactive compounds (eal + & ea2) and said ionic charges being solubilized by a solubilizing liquid (L), which is also capable of solubilizing the reduced and oxidized species (eal + ea2 +) respectively associated with said electroactive compounds ( eal + & ea2). By "compensating charge cations" is meant Li +, H +, etc. ions which can be inserted or disin- ferred into the electroactive compounds together with the electrons. An electroactive organic compound capable of being reduced and / or of accepting electrons and cations acting as compensation charges means a compound with negative redox activity, which may be a cathodic electrochrome or a non-electrochromic compound. , playing then only the role of reservoir ionic charges or against electrode. An electroactive organic compound capable of oxidizing and / or ejecting electrons and cations acting as compensation charges means a compound having a positive redox activity, which may be an anodic electrochromic or a non-anodic compound. electrochromic, playing only the role of tank ionic charges or against electrode. Assuming that the compound (eal +) is electrochromic (e.g., 1,1'-diethyl-4,4'-bipyridinium diperchlorate) and that the compound (ea2) is electrochromic (e.g. 10-dihydro-5,10-dimethylphenazine) or non-electrochromic acid being, for example, a ferrocene), the redox reactions which are established under the action of the electric current are as follows: eal + + e- = eal Ery2 = ea2 + + e Colorless if electrochromic Colorless if not electrochromed More preferably, only one of the electronically conductive layers has been etched. It is possible, however, that the two electronically conductive layers have been etched. In this case, the etchings of the two electronically conductive layers may have been arranged correspondingly. An etched electronically conductive layer advantageously has a resistivity of 100 to 0.5 S2 / square, especially 20 to 1 S2 / square. An etching on an electronically conductive layer has in particular been carried out along a line from 10 μm to 10 mm in width and preferably from 20 μm to 100 μm in width.

In the context of the present invention, the electronically conductive layers are preferably "TCC", an abbreviation of the term "Transparent Conductive Coating", an example of which is a transparent conductive oxide (TCO). The electronically conductive layers are in particular metal-type layers, such as layers of silver, gold, platinum and copper; or transparent conductive oxide (TCO) type layers, such as tin-doped indium oxide (In2O3: Sn or ITO), antimony-doped indium oxide (In2O3: Sb) layers. ), fluorine-doped tin oxide (SnO2: F) and zinc oxide doped with aluminum (ZnO: Al); or TCO / metal / TCO multilayers, the TCO and the metal being in particular chosen from those enumerated above; or NiCr / metal / NiCr type multilayers, the metal being in particular chosen from those enumerated above. The electronically conductive layers can also comprise a grid or a microgrid or be in the form of a grid or a microgrid; they may also comprise an organic and / or inorganic sub-layer, especially in the case of plastic substrates. When the electrochromic system is intended to work in transmission, the electroconductive materials are generally transparent oxides whose electronic conduction has been amplified by doping such as In2O3: Sn, In2O3: Sb, ZnO: Al or SnO2: F. Tin doped indium oxide (In2O3: Sn or ITO) is frequently selected for its high electronic conductivity and low light absorption properties.

Alternatively or in a complementary manner, when the system is intended to work in reflection, one of the electroconductive materials may be metallic in nature.

The substrates with a glass function are chosen in particular from glass (float glass, etc.) and transparent polymers, such as poly (methyl methacrylate) (PMMA), polycarbonate (PC), poly (ethylene terephthalate) ( PET), poly (ethylene naphthoate) (PEN) and cycloolefin copolymers (COC). The electroactive organic compound (s) (eal +) may or may be chosen from bipyridiniums or viologenes such as 1,1'-diethyl-4,4'-bipyridinium diperchlorate, pyraziniums, pyrimidiniums, quinoxaliniums, pyryliums, pyridiniums, tetrazoliums, verdazyls, quinones, quinodimethanes, tricyanovinylbenzenes, tetracyanoethylene, polysulfides and disulfides, as well as all the electroactive polymeric derivatives, such as polyviologenes, of the electroactive compounds which have just been mentioned. The electroactive organic compound (s) (ea2) may or may be chosen from metallocenes, such as cobaltocenes, ferrocenes, N, N, N ', N'-tetramethylphenylenediamine (TMPD), phenothiazines such as phenothiazine, dihydrophenazines such as 5,10-dihydro-5,10-dimethylphenazine, reduced methylphenothiazone (MPT), methylene violet bernthsen (MVB), verdazyls, and all the electroactive polymeric derivatives of the electroactive compounds that have just been mentioned. The ionic charges may be borne by at least one of said electroactive organic compounds and / or by at least one ionic salt and / or at least one acid solubilized in said liquid (L) and / or, in the case where the electroactive system is in the form of a self-supporting layer, by a matrix constituting or composing the self-supporting layer and capable of ensuring the mechanical strength. The solubilization liquid (L) may be constituted by a solvent or a mixture of solvents and / or by at least one ionic liquid or molten salt at ambient temperature, the said ionic liquid or molten salt or the said ionic liquids or molten salts then constituting a solubilizing liquid carrying ionic charges, which represent all or part of the ionic charges of said electroactive system. The ionic salt (s) may be chosen from lithium perchlorate, trifluoromethanesulfonate or triflate salts, trifluoromethanesulfonylimide salts and ammonium salts.

The acid (s) may be chosen from sulfuric acid (H2SO4), triflic acid (CF3SO3H), phosphoric acid (H3PO4) and polyphosphoric acid (Hn + 2 PnO3n + 1). be chosen from sulfolane, dimethylsulfoxide, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidinone, carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate, ethylene glycols such as tetraglyme, alcohols such as ethanol, ethoxyethanol, ketones such as cyclopentanone, benzylacetone, lactones such as gamma-butyrolactone, acetylbutyrolactone, nitriles such as acetonitile, glutaronitrile, 3-hydroxypropionitrile, anhydrides such as acetic anhydride, ethers such as 2-methoxyethyl ether, water, phthalates and adipates, citrates, sebacates, maleates, benzoates and succinates.

The ionic liquid or liquids may be chosen from imidazolium salts, such as 1-ethyl-3-methylimidazolium tetrafluoroborate (emim-BF4), 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (emim-CF3SO3), 1 3-methyl-3-methylimidazolium bis (trifluoromethylsulphonyl) imide (emim-N (CF3SO2) 2 or emim-TSFI) and 1-butyl-3-methylimidazolium bis (trifluoromethylsulphonyl) imide (bmim-N (CF3SO2) 2 or bimim- TFSI). The concentration of the ionic salt (s) and / or acid (s) in the solvent or solvent mixture is in particular less than or equal to 5 moles / liter, preferably less than or equal to 2 moles / liter, more or less more preferred, less than or equal to 1 mole / liter.

The or each solvent may be chosen from those having a boiling point of at least 70 ° C., preferably at least 150 ° C. According to a first embodiment of the electrically controllable device according to the present invention, the electroactive system is a liquid system formed by the solubilizing liquid (L), the electroactive compounds and the ionic charges, the liquid (L) consisting of a solvent or a mixture of solvents and / or at least one ionic liquid or molten salt at room temperature, said ionic liquid or molten salt or said ionic liquids or molten salts then constituting a solubilization liquid carrying ionic charges, which represent all or part of the ionic charges of said electroactive material. According to a second embodiment of the electrically controllable device according to the present invention, the electroactive system is a gelled system formed by the solubilization liquid (L), the electroactive compounds, the ionic charges and at least one thickening agent which will solubilize only in the liquid formed by the one or more solvents and the one or more ionic liquids and / or molten salts or only be inflated by this liquid, a gel being obtained in both cases, the liquid (L) being constituted by a solvent or a mixture of solvents and / or by at least one ionic liquid or molten salt at ambient temperature, said ionic liquid or molten salt or said ionic liquids or molten salts then constituting a solubilization liquid carrying ionic charges, which represent all or part of the ionic charges of said electroactive material.

The thickening agent (s) is (are) chosen especially from. the homo- or copolymers having no ionic charges, in which case they are borne by at least one aforementioned electroactive organic compound and / or by at least one ionic salt or solubilized acid and / or by at least one ionic liquid or molten salt; the homo- or copolymers comprising ionic charges, in which case additional charges making it possible to increase the rate of percolation can be borne by at least one aforementioned electroactive organic compound and / or by at least one solubilized ionic or acidic salt and / or by at least one ionic liquid or molten salt; and mixtures of at least one homo- or copolymer not carrying ionic charges and at least one homo- or copolymer comprising ionic charges, in which case additional charges making it possible to reinforce the percolation rate may be carried by at least one aforementioned electroactive organic compound and / or with at least one solubilized ionic salt or acid and / or with at least one ionic liquid or molten salt. The thickening agent (s) may also be chosen from copolymers of ethylene, vinyl acetate, ethylene-vinyl acetate (EVA), polyurethanes (PU), polyvinyl butyral (PVB), polyimides (PI ), polyamides (PA), polystyrene (PS), polyvinylidene fluoride (PVDF), polyetherketones (PEK), polyether ether ketones (PEEK), epichlorohydrin copolymers, polyolefins, poly (ethylene oxide) (POE), polyacrylates, poly (methyl methacrylate) (PMMA), silicones or their derivatives or their monomers or their prepolymers. The thickening agent (s) may also be chosen from polyelectrolytes and especially sulphonated polymers which have been exchanged for H + ions of SO 3 H groups by the ions of the desired ionic charges. The sulphonated polymers are especially chosen from sulphonated tetrafluoroethylene copolymers, sulphonated polystyrenes (PSS), sulphonated polystyrene copolymers, poly (2-acrylamido-2-methyl-1-propanesulphonic acid) (PAMPS), polyetheretherketones (PEEK ) sulphonated and sulphonated polyimides. According to a third embodiment of the electrically controllable device according to the present invention, the electroactive system is in the form of a self-supporting layer comprising or being constituted by a matrix which is capable of ensuring the mechanical strength of said self-supporting layer as well as to ensure the percolation path to the ionic charges and in which are inserted the electroactive organic compounds and the ionic charges which are within the matrix in the solubilized state by the solubilizing liquid (L), which is constituted by a solvent or a mixture of solvents and / or at least one ionic liquid or molten salt at room temperature, said ionic liquid or molten salt or said ionic liquids or molten salts then constituting a solubilization liquid carrying ionic charges, which represent all or part ionic charges of said electroactive material, said matrix being translucent or transparent once impregnated with the liquid (L) having solubilized said electroactive compounds (eal + & ea2) and the ionic charges, and being able to retain at least part of its integrity once impregnated with the liquid (L) so that the holding of said electroactive system is ensured. The matrix may be formed by a web or a stack of webs, the or each web being a textile web, or non-textile, a non-textile web being defined as being a polymer web without a fibrous matrix or as being based on a film polymer. The textile web or textile web may have a non-woven (or matt) web, woven or knit fabric architecture, optionally coated with a binder, which may be at least partially soluble in the liquid (L) to form a gel. The terms "nonwoven web" and "mat" are each defined as a film structure with non-woven fibers, not knitted together.

The terms "woven" and "knitted" are defined as a matrix made of fibers and / or threads respectively woven and knitted. Fabrics and knits have the advantage of good yarn cohesion between themselves in the absence of a binder. Each textile web may be composed of one or more types of fibers or yarns, the yarns being defined as assemblies of several fibers. The textile ply or a textile ply is in particular based on synthetic fibers and / or yarns (artificial), chosen in particular from polyolefin fibers and / or yarns (such as polypropylene (PP)), polyester, fluorinated polymer (such as polytetrafluoroethylene (PTFE) or fluorinated polyvinylidene (PVDF), polyamide or polyimide) and / or mineral fibers such as glass fibers, and / or natural fibers and / or yarns, such as fibers and / or or cotton or woolen thread. According to a first variant, the textile ply or a textile ply is based on fibers and / or single-component or multicomponent yarns, the fibers and / or multi-component yarns being in particular fibers and / or hybrid yarns or fibers and or son having a core of a chemical resistance material, able to maintain its integrity during impregnation with the solubilizing liquid (L) to ensure the mechanical strength of the electroactive material, and at least one sheath of a soluble material in the solubilizing liquid (L) or able to give a gel during the impregnation of the textile web or the stack of webs by the impregnating liquid (L).

Examples of hybrid yarns include Twintex ® (Owens Corning) fibers which combine glass and polypropylene. According to a second variant, the textile web or a textile web is based on fibers and / or son insoluble in the impregnating liquid and fibers and / or son soluble in the solubilization liquid (L), the fibers and / or son thus solubilized having led to the formation of a gel. The amount of fibers and / or insoluble son relative to the amount of fibers and / or soluble son will be chosen so that the mechanical strength of the electroactive material is ensured. Systems combining fibers and gel will be mechanically more resistant than a system based on fibers and liquids. According to a third variant, the textile web or a textile web of the stack is a textile web coated with a material soluble in the solubilizing liquid (L) or capable of giving a gel during the impregnation of the web. textile or stack of webs by the solubilizing liquid (L); mention may be made of the use of veils or fabrics coated with a polymer such as silicone-coated glass fabrics marketed by the company "Saint-Gobain Performance Plastique" under the trademark COHRlastic®, the liquid (L) swelling or solubilizing the polymer coating. The polymer film constituting at least one non-textile web may be a homo- or copolymer in the form of a non-porous film capable of swelling in said liquid (L), or in the form of a film porous, said porous film optionally being able to swell in the liquid having ionic charges and whose porosity after swelling is chosen to allow the percolation of the ionic charges in the thickness of the film impregnated with liquid. The polymer film constituting at least one non-textile web may be a homo- or copolymer in the form of a porous film having a porosity sufficient to allow percolation of the ionic charges in the thickness of the film impregnated with liquid or being capable of swelling in the liquid having ionic charges and whose porosity after swelling is chosen to allow percolation of the ionic charges in the thickness of the liquid-impregnated film. The stack of webs may further comprise at least one textile web soluble in the liquid (L).

The porous polymeric films may be selected from the transfer, filtration or microfiltration membranes available under the trade names Durapore®, Millipore ImmobilonTM, Osmonics MagnaTM, Versapor®, RepelTM, Metrical®, Fluorodyne®n Verical®, VividTM® Pall Corporation, GoreTM, Tenara® of Gore, etc. The polymer constituting at least one non-textile web may be chosen from homo or copolymers that do not comprise ionic charges, in which case they are borne by at least one aforementioned electroactive organic compound and / or by at least one ionic salt. or solubilized acid and / or at least one ionic liquid or molten salt; the homo- or copolymers comprising ionic charges, in which case additional charges for increasing the rate of percolation may be borne by at least one aforementioned electroactive organic compound and / or by at least one solubilized ionic or acidic salt and / or by at least one ionic liquid or molten salt; and mixtures of at least one homo- or copolymer not carrying ionic charges and at least one homo- or copolymer comprising ionic charges, in which case additional charges making it possible to reinforce the percolation rate may be carried by at least one aforementioned electroactive organic compound and / or with at least one solubilized ionic salt or acid and / or with at least one ionic liquid or molten salt. The non-textile web may consist of a film based on a homo- or copolymer comprising ionic charges, capable of giving itself a film essentially capable of ensuring the desired percolation rate for the electroactive system or a speed higher percolation than the latter and a homo or copolymer with or without ionic charges, able to give by itself a film that does not necessarily ensure the desired percolation rate but essentially able to ensure the holding mechanically, the contents of each of these two homo- or copolymers being adjusted so that both the desired percolation rate and the mechanical strength of the resulting self-supporting organic active medium are ensured. The polymer or polymers of a non-textile web having no ionic fillers can be chosen from copolymers of ethylene, vinyl acetate, ethylene-vinyl acetate (EVA) and polyurethanes (PU). , polyvinyl butyral (PVB), polyimides (PI), polyamides (PA), polystyrene (PS), polyvinylidene fluoride (PVDF), polyetherketones (PEK), polyether-ether- ketones (PEEK), epichlorohydrin copolymers, polyolefins, polyethylene oxide (POE), polyacrylates, poly (methyl methacrylate) (PMMA), silicones or their derivatives or their monomers or still their pre-polymers. The polymer (s) of the non-textile web carrying ionic charges may or may be chosen in particular from polyelectrolytes and in particular the sulfonated polymers which have been subjected to an exchange of H + ions of SO 3 H groups by the ions of the desired ionic charges, this exchange of ions having taken place before and / or simultaneously with the swelling of the matrix in the liquid comprising ionic charges, the sulphonated polymers being chosen in particular from sulphonated tetrafluoroethylene copolymers, sulphonated polystyrenes (PSS), sulphonated polystyrene copolymers, poly (2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS), sulfonated polyetheretherketones (PEEK) and sulfonated polyimides. The matrix, before impregnation in said liquid (L), has in particular a thickness of less than 2000 μm, preferably of 500 to 1000 μm. Moreover, the matrix and the liquid (L) are advantageously chosen so that the active medium withstands a temperature corresponding to the temperature required for a subsequent lamination or calendering step, namely a temperature of at least 80 ° C. in particular at least 100 ° C.

The materials constituting the matrix and the solubilizing liquid (L) may have different or substantially equal indices. It is preferable that the indices are substantially equal, with a difference of at most 0.10, or even at most 0.05, so as to reduce the blurriness of the device. By way of example, the matrix consists of a sheet of glass fibers, for example glass E (with a theoretical index of about 1.55), and the solubilization liquid (L) consists of dimethyl phthalate. (theoretical index of about 1.515). According to another example, the matrix is constituted by a porous polyvinylidene fluoride (PVDF) membrane with a theoretical index of approximately 1.42, and the solubilization liquid (L) is constituted by propylene carbonate. Theoretical index 1.422. In order to manufacture an electroactive material as defined above, impregnation of the matrix is carried out by the solubilization liquid of the electroactive system, and then, if appropriate, draining is carried out. The immersion can be carried out for a period of 2 minutes to 3 hours. The immersion may be carried out under heating, for example at a temperature of 40 to 80 ° C. Immersion can also be performed with the application of ultrasound to aid in the penetration of the solubilizing liquid into the matrix.

The electrically controllable device of the present invention may be configured to form a motor vehicle roof, autonomously activatable, or a side window or a rear window for a motor vehicle or a rearview mirror; a windshield or a portion of a windshield of a motor vehicle, an airplane or a ship; an automobile roof; an airplane porthole; glazing for cranes, construction machinery, tractors; a display panel of graphical and / or alphanumeric information; indoor or outdoor glazing for the building; a roof window; a display stand, a shop counter; a protective glazing of an object of the table type; an anti-glare computer screen; glass furniture; a partition wall of two rooms inside a building; a bottle. The electrically controllable device according to the invention can operate in transmission or in reflection.

The substrates may be transparent, flat or curved, clear or tinted in the mass, opaque or opacified, polygonal in shape or at least partially curved. At least one of the substrates may incorporate other functionality such as solar control, anti-reflective or self-cleaning functionality. The present invention also relates to a method of manufacturing the electrically controllable device as defined above, characterized in that at least one etching of at least one electronically conductive layer (TCCl; TCC2) is carried out on its substrate with associated glass function (V1; V2) in order to form at least two independently addressable areas and that the various layers of which it is composed are combined by calendering or lamination if necessary under heating with registering of the engravings when they have performed in both TCC1 and TCC2 layers. Alternatively or in a complementary manner, when the system is intended to work in reflection, one of the electroconductive materials may be metallic in nature. Etching can be carried out by any chemical or mechanical means, in particular cutting, or advantageously by laser irradiation. Other means can be used to perform the abrasive etching. Thus, it is possible to use an emitter of gas or liquid under pressure (nitrogen, air), or an emitter of abrasive particles (glass beads, corundum, shot, solid CO2 beads), etc. The present invention finally relates to a single or multiple glazing, characterized in that it comprises an electrically controllable device as defined above.

It is therefore possible to assemble the different layers composing said system in single or multiple glazing. To further illustrate the object of the present invention, will be described hereinafter, by way of indication and not limitation, several particular embodiments with reference to the accompanying drawing.

On this drawing :

Figure 1 is a schematic front view of an electrochromic device according to the prior art;

- Figures 2 and 3 are schematic sectional views respectively II-II and III-III of Figure 1; - Figures 4 to 8 each show an example of etching performed on at least one of the substrates of an electrochromic device of the invention;

Figure 9 is a schematic front view of an electrochromic device according to the invention, with its two substrates coated with TCC which have been etched; - Figures 10 and 11 are schematic sectional views respectively X-X and XI-XI of Figure 9;

Fig. 12 shows a photograph of the electrochromic device of Example 3, zone-stained;

FIG. 13 is a diagram of the wafer of the electrochromic device of Example 3 explaining the mechanism of the zone coloration, only the electroactive system 10 and the TCCs having been represented;

14 is a diagrammatic front view of an electrochromic device according to the invention, with only one of its two substrates coated with TCC which has been etched;

- Figures 15 and 16 are schematic sectional views respectively XV-XV and XVI-XVI of Figure 14;

FIGS. 17 and 18 each show a photograph of the electrochromic device of Example 4, respectively, zoned in the case where the etched TCC is used as a cathode and in the case where the etched TCC is used as the anode; Figures 19 and 20 are each a schematic diagram of the wafer of the electrochromic device of Example 4 explaining the mechanism of the zonal dyeing, only the electroactive system and the TCCs being shown, these diagrams being shown respectively in FIG. case where the engraved TCC is used as a cathode and in the case where the engraved TCC is used as anode; Fig. 21 shows a photograph of the electrochromic device of Example 5 stained by zones;

22 and 23 each show a photograph of the device of Example 4 colored in zones, respectively in the case where the engraved TCC is used as cathode and in the case where the engraved TCC is used as anode; Fig. 24 shows a photograph of the electrochromic device of Example 8 colored by zones;

FIGS. 25 to 29 show photographs of the electrochromic device of Example 9 as a function of the power supply mode and, when a zone is powered, the use of the TCC1 of this zone as a cathode or as anode; and

Figure 30 is a photograph of the electrochromic device of Example 10, stained by zones. Referring to FIGS. 1 to 3, it can be seen that the glazing shown therein schematically comprises two glass plates V1, V2 arranged facing each other, one being offset with respect to the other to meet for mounting purposes. The internal faces of each of these plates V1, V2 are coated with an electronically conductive layer, respectively TCC1 and TCC2, consisting in particular of a TCO. Between the two regions facing the thus-coated plates V1, V2 is a "reservoir" zone filled with an electroactive medium EA, in solution, gelled or self-supporting, this reservoir being closed over its entire periphery by a gasket. encapsulation J or frame, electrical insulation, formed in particular of a double-sided adhesive whose two adhesive faces are applied to the layers respectively TCC1 and TCC2. The current leads to the layers respectively TCC1, TCC2 are made by foils each consisting of a metal strip M applying against the TCC1 layer portion, TCC2 protruding from the "reservoir" respectively along the upper edge and along the bottom edge of the glazing.

The conditions of assembly are the conditions used in a standard way which lead to the formation of a continuous electroactive medium throughout the glazing. The size of the cells is 12 x 14 cm 2 with an active area of 8 x 8 cm 2.

FIG. 4 represents a schematic front view of a rectangular TCO layer comprising two vertical etching lines G (shown in dotted lines) which are parallel to the long side of the rectangle and which delimit three independently addressable zones A, B, C in accordance with FIG. the invention. In the example shown in this figure, the rectangular TCO layer is 14 cm long and 12 cm wide, the etching lines being each made 5.5 cm from the corresponding large side of the rectangular layer.

The electrochromic cell shown in Figure 4 has a 75% light transmission in the unstained area and a 14% light transmission in the stained area. FIG. 5 represents a diagrammatic front view of a rectangular TCO layer comprising the same etching lines as the TCO layer of FIG. 4, namely GP vertical engraving vertical lines represented in large dashed lines and, in addition, four secondary etching lines GS, represented in small dotted lines, each of which is formed in the vicinity of one side of the rectangular TCO layer being parallel to this side. GS secondary engravings are used to avoid short-circuits at the edge of the glass where the main engraving GP may have defects. In the example shown in this figure, the rectangular TCO layer is that of Figure 4, with GS engravings consisting of four etching lines each located 0.5 cm from each of the edges of the plate. Figures 6 and 7 show rectangular TCO layers with GP main engraving lines that draw the acronyms "SG" and "SGR" as well as the same GS secondary etching lines as the layers in Figure 5. Two addressable areas Z1 and Z2 are thus formed in each case. The layer of Figure 7 further comprises two non-addressable areas ZNA - which will always be discolored - formed by the two lines closed on themselves which are necessary to form the letter "R". Figure 8 is a view similar to Figure 7 showing a rectangular layer with the drawing of the initials "SGR" in the form of an image in a mirror of the previous one, the two layers of Figures 7 and 8 being able to be the layers Vl + TCC1 and V2 + TCC2 of the same device whose layered glasses would both be etched. The TCO etchings can be done at the diamond point on a layered glass (Vl + TCC1 or V2 + TCC2) or both. However, to improve the sharpness of the etching and realize complex shapes, we used a laser ROFIN RSM 30D mounted on a digital table.

Figures 9 to 11 are diagrams of the same type as Figures 1 to 3, respectively, except that the two substrates or L1 + TCC1 and V2 + TCC2 layers were etched as shown in Figure 4. The same letters were used of reference that those used to designate the same elements in Figures 1 to 3, areas A, B and C and engraving lines G in addition and the three metal strips MA, MB and MC associated with each of the zones A, B and C of each layer glass Vl + TCC1 and V2 + TCC2. The diagrams of FIGS. 14 to 16 are identical to those of FIGS. 9 to 11, respectively, except that only a layered glass has been etched (Vl + TCC1), so that a single metal strip M is arranged on TCC2 and three strips. MA, MB and MC are arranged on TCC1 to make the current leads. The following Examples illustrate the present invention without however limiting its scope. In these examples, the following abbreviations have been used. - PVDF: poly (vinylidene fluoride) - POE: poly (ethylene oxide) - ITO: tin doped indium oxide (In2O3: Sn) - LiTFSI: lithium bis (trifluoromethylsulfonyl) imide - eminTFSI: bis (1-ethyl-3-methylimidazolium-ddp trifluoromethylsulfonyl) imide: potential difference applied across the electrochromic device - TL: light transmission in the visible of the device - Ru: surface resistance of the conductive layers The "K-glassTM" glass used in these examples is a glass coated with an electroconductive layer of SnO 2: F with a surface resistance R 0 equal to 20.5% (glass sold under this name by the company "Pilkington"). PVDF films were made with the polyvinylidene fluoride powder manufactured by the company "Arkema" under the name "Kynar® LBG1". Other PVDF films used are filtration membranes sold by the company Millipore under the name Durapore® HVHP 29325. The gelled electroactive medium was manufactured using a POE resin marketed by the Dai-Ichi-Kogyo Seiyaku Company under the name denomination Elexcel® TA-140. EXAMPLE 1 Preparation of an electrochromic device according to the prior art Vl + TCC1: "K-glass" glass - the SnO2: F layer is continuous (not etched) EA: gelled electroactive medium: POE resin + 1,1'-diethyl-4,4'-bipyridinium diperchlorate (colorless electroactive compound eal + capable of being stained when it is reduced to eal) + ferrocene (colorless electroactive compound ea2 and which remains colorless when oxidized to ea2 +) + lithium salt (which plays the role of electrolyte) V2 + TCC2: "K-glass" glass - the SnO2 layer: F is continuous (not etched) 30 - M: strip metallic (optional) on the glasses e.

A gel was prepared by mixing 23.71 g of POE resin, 12.43 g of emimTFSI, 1.38 g of LiTFSI, 0.016 g of ferrocene and 0.36 g of 1,1-diethyl-4 diperchlorate. 4'-bipyridinium. The gel was stirred for 1 hour at 80 ° C and another hour at room temperature. 100 μl of gel was deposited on a 12 × 14 cm 2 "K-glass ™" glass plate. Thanks to a paper mask deposited on the glass plate "K-glassTM", the deposit was made on a surface of 8x8cm2. After removal of the mask, a frame J 2 cm wide, double-sided adhesive 100p.m thick, was used as a spacer around the electroactive medium. The second "K-glassTM" plate was deposited on the film impregnated with electroactive solution and the frame, in double-sided adhesive, and clamps were used to ensure a good contact between the glass and the film. The electrochromic device thus manufactured, which has an active surface area of 8 × 8 cm 2, is that schematized in FIGS. 1 to 3.

When no ddp is applied to the device, or a null dp is applied, the device is in the faded state and its light transmission is about 77%. When a 1.5V ddp is applied to the terminals of the device, it dyes and the light transmission increases to approximately 27%. The coloration is homogeneous over the entire active surface. EXAMPLE 2 Preparation of an electrochromic device according to the prior state of the art - Vl + TCC1: "K-glassTM" glass - the SnO2: F layer is continuous (not etched) EA: electroactive system: Durapore® HVHP membrane 29325 + 1,1'-diethyl-4,4'-bipyridinium diperchlorate (colorless electroactive compound eal + capable of coloring when reduced to eal) + ferrocene (colorless electroactive compound ea2 and remaining colorless when oxidized in ea2 +) + lithium perchlorate (which plays the role of electrolyte) + propylene carbonate - V2 + TCC2: "K-glassTM" glass - the SnO2: F layer is continuous (not etched) M: metal strip ( optional) on coated glasses. An electroactive solution was prepared at 0.06 mol / L ferrocene, 0.06 mol / L 1,1'-diethyl-4,4'-bipyridinium diperchlorate and 0.15 mol / L lithium triflate in propylene carbonate. The solution was stirred for 1 hour. Three membranes about 100 microns thick, with a surface area of 8 × 8 cm 2, were immersed for 5 minutes in the electroactive solution thus prepared before being deposited on each other on a "K-glass ™" glass plate. The second plate of "K-glassTM" was deposited on the stack of films impregnated with electroactive solution, a frame, 2 cm wide, double-sided adhesive about 300 μm thick, was used as a spacer around electroactive medium, and clamps were used to ensure good contact between the glass and the film stack. The electrochromic device thus manufactured, which has an active area of 8x8 cm 2, can be schematized in the same manner as the device of Example 1 in Figures 1 to 3.

When no ddp is applied to the device, or a zero dp is applied, the device is in the faded state and its light transmission is about 73%. When a 1.5V ddp is applied to the terminals of the device, it dyes and the light transmission increases to about 0.03%. The coloration is homogeneous over the entire active surface. EXAMPLE 3 Preparation of an Electrochromic Device with Preferential Coloring Zones - VI + TCC1: "K-glass" Glass with R = 20.552 / - The SnO2: F layer is etched as shown schematically in FIG. 5 - EA: electroactive system: PVDF + 1,1'-diethyl-4,4'-bipyridinium diperchlorate (colorless electroactive compound eal + capable of staining when reduced to eal) + 5,10-dihydro-5,10-dimethylphenazine ( colorless electroactive compound ea2 capable of coloring when oxidized to ea2 +) + lithium triflate + propylene carbonate - V2 + TCC2: "K-glass" glass with Rc = 20.552 / ^ - the SnO2: F layer is etched as shown schematically in Figure 5 - MB, MB, MC: (optional) metal strips on the layered glasses. A self-supporting PVDF film was made by mixing 6.5 g of PVDF powder, 13.0 g of dibutyl phthalate, 0.5 g of nanoporous silica and 25 g of acetone. The formulation was stirred for two hours and cast on a glass plate. After evaporation of the acetone, the PVDF film was removed from the glass plate under a trickle of water. The film thus obtained has a thickness of about 300 μm. An electroactive solution at 0.06 mol / L of 5,10-dihydro-5,10-dimethylphenazine, 0.06 mol / L of 1,1'-diethyl-4,4'-bipyridinium diperchlorate and 0 15 mol / L of lithium triflate in propylene carbonate. The solution was stirred for 1 hour. The PVDF film, about 300 microns thick, with a surface area of 8 × 8 cm 2, was immersed for 5 minutes in diethyl ether (for solubilizing dibutyl phthalate) and then for 5 minutes in the electroactive solution before being deposited on a surface. "K-glassTM" glass plate engraved. A second plate of "K-glassTM" engraved was deposited on the film impregnated with electroactive solution, a frame, 2cm wide, double-sided adhesive about 300pm thick, was used as a spacer around the electroactive medium and pliers were used to ensure good contact between the glass and the film. The two engraved "K-glassTM" glass plates were positioned to superimpose the etching lines located 5.5 cm from the edges. The electrochromic device thus manufactured, which has an active surface of 8 × 8 cm 2 with three zones, denoted "Zone A", "Zone B" and "Zone C", independently addressable, is as shown diagrammatically in FIGS. 9 to 11. no dpd is applied to the device, or a null dp is applied, the device is in the faded state and the light transmission is the same in each zone and is about 43%.

When the same ddp is applied to each zone of the device, it dyes homogeneously. When a 1.5V ddp is applied to each zone, the light transmission on each zone is less than 0.05%. Different ddp values were then applied to each area of the device. In zone A, 1.5V was applied on zone A, OV on zone B and 0.8V on zone C. The three zones of the device are colored differently, as shown in the photograph of the device shown in FIG. and the light transmittance values that were measured and presented in Table 1. To aid in the understanding of the zonal staining, the staining mechanism then occurring is shown schematically in FIG. 13. After holding the powered device for 2 hours, the appearance remained unchanged and the values of light transmission in each zone have changed little.

Table 1: Light transmission values of the electrochromic device of Example 3 as a function of the ddp value applied to each zone Zone of measurement Zone A Zone B Zone C ddp applied per zone 1.5 V 0 0.8V TL <0 , 05% 42.8% 0.54% EXAMPLE 4 Preparation of an Electrochromic Device with Preferential Coloring Zones V1 + TCC1: Glass "K-glassTM" with R 1 = 20.5 S 2/2 - the SnO 2 layer : F is etched as schematized in FIG. 5 - EA: electroactive system of Example 3 - V2 + TCC2: "K-glassTM" glass - the SnO2: F layer is continuous (not etched) - M: metal strip ( optional) on V2 + TCC2 - MA, MB, MC glass: metal strips (optional) on V1 + TCC1 coated glass A second electrochromic device was made using a "K-glass" plate engraved like this is shown schematically in Figure 5 and a plate of "K-glass" not engraved, the SnO2 layer: F being continuous. With the exception of the use of a non-etched K-glass plate, this second device was manufactured as described in Example 3. The electrochromic device thus manufactured has an active surface area of 8 × 8 cm 2 with three zones, denoted "Zone A", "Zone B" and "Zone C", addressable independently, and is shown schematically in Figures 14 to 16.

When no power is applied to the device, or a null dp is applied, the device is in the faded state and the light transmission is the same in each zone and is about 42.5.

As a "K-glass" glass plate is etched and the other is continuous, it is possible to feed the device using either the TCC1, etched, cathode and TCC2, not etched, anode, or the TCC1, engraved, anode and TCC2, not engraved, cathode. Applying different device ddp values. 1.5V was applied on zone B and 0.8V on zone C. The three zones of the device These two modes of supply were tested on each zone zone A, OV on different colors photographs of the device 10 when the TCC1, etched, is FIG. 18, when the TCC2, as shown in FIG. 17, used as the cathode, and the non-etched, is used as the cathode, and the light transmission values that have been measured and presented in Table 2. To aid in the understanding of zone staining, the staining mechanism occurring then is shown schematically in FIG. 19, when the etched TCC1 is used as a cathode, and FIG. TCC2, not engraved, is used as a cathode. After keeping the device powered for 2 hours, Zone B was slightly colored either when the cathode is on the TCC1, etched, or on the TCC2, not etched. When the same ddp is applied to each area of the device, and the unetched TCC1, etched, or TCC2, is used as a cathode, the device will stain evenly. When a 1.5V ddp is applied to each zone, the light transmission on each zone is less than 0.05%. Table 2: Light transmission values of the electrochromic device of Example 4 as a function of the value of ddp applied to each zone Measuring zone Zone A Zone B Zone C ddp applied per zone 1.5 V 0 0.8V TL when cathode is <0.05% 42.4% 0.5% placed on the TCC1, engraved TL when cathode is <0.05% 42.7% 0.5% put on TCC2, not etched EXAMPLE 5: Preparation of an electrochromic device with preferential color zones - V1 + TCC1: "K-glassTM" glass with R ## STR2 ## The SnO2: F layer is etched as schematized in Figure 5 - EA: Electroactive system of Example 2 - V2 + TCC2: K-glass ™ glass with R = 20, 5S2 / ^ - SnO2: F layer is etched as schematized in Figure 5 - MA, MB, MC: metal strips (optional) on each coated glass. An electrochromic device was manufactured following the protocol described in Example 2 but using two engraved "K-glass" glass plates. When no dpd is applied to the device, or a null dp is applied, the device is in the faded state and the light transmission is the same in each zone and is about 72%. When the same ddp is applied to each zone of the device, it dyes homogeneously.

When a 1.5V ddp is applied to each zone, the light transmission on each zone is approximately 0.3%. Different ddp values were then applied to each area of the device. In zone A, 1.5V was applied on zone A, OV on zone B and 0.8V on zone C.

The three zones of the device are colored differently as shown in the photograph of the device shown in Figure 21 and the light transmission values measured and presented in Table 3. After maintaining the device powered for 2 hours, the appearance remained unchanged and the light transmission values in each zone have changed little. Table 3: Light transmission values of the electrochromic device of Example 5 as a function of the value of 20 ddp applied to each zone Zone of measurement Zone A Zone B Zone C ddp 1, 5 V 0 0, 8V TL 0.3% 72.2 38.2 EXAMPLE 6 Preparation of an Electrochromic Device with 25 Preferential Coloring Zones - V1 + TCC1: "K-glass" Glass with R1 = 20.5 S2 / - The SnO2: F Coat is Engraved as shown diagrammatically in FIG. 5 - SE: electroactive system of Example 2 »36 V2 + TCC2: glass« K-glass continuous (not etched), - the SnO2: F layer is metal strip (optional) on the glasses layer.

The electroactive system of Example 2 was used to make an electrochromic device with an etched "K-glass" glass plate and an un-etched "K-glass" glass plate as described in Example 4. When no ddp is applied to the device, or a zero dp is applied, the device is in the faded state and the light transmission is the same in each zone and is about 73%. Different ddp values were applied to each zone of the device using TCC1, either etched or unetched TCC2, as the cathode, and zone staining was obtained. 1.5V was applied on area A, OV on area B and 0.8V on area C. The three areas of the device stain differently as shown in the photographs of the device shown in Figure 22, when TCC1, engraved, is used as the cathode, and Figure 23, when the TCC2, not engraved, is used as the cathode, and the light transmittance values measured and presented in Table 4. After keeping the device powered for 2 hours, when c 'is the TCC2, not engraved which is used as cathode, Zone B has slightly colored. When the engraved TCC1 is used as the cathode, the appearance of the device remains unchanged and the light transmission values in each zone have also remained unchanged. Table 4: Light transmission values of the electrochromic device of Example 6 as a function of the ddp value applied to each zone Measuring zone Zone A Zone B Zone C ddp per zone 1.5 V 0 0.8V TL when cathode is 0.3% 73.1% 38.0% put on the TCC1, engraved TL when cathode is 0.3% 72.5% 39.5% put on the TCC2, not engraved EXAMPLE 7: Preparation of a device electrochromic with preferential staining areas - V1 + TCC1: "K-glass" glass with R = 20, 5S2 / - the SnO2: F layer is etched as shown diagrammatically in FIG. 5 - EA: electroactive system: Voile no fiberglass weave + electroactive solution of Example 2 - V2 + TCC2: "K-glass" glass - the SnO2: F layer is continuous (not etched) - M: metal strip (optional) on the glass layer V2 + TCC2-MA, MB, MC: metal strips (optional) on the V1 + TCC1 layer glass A non-woven fiberglass fleece, obtained by the dry route, was immersed. 13pm thick fibers, and itself a thickness 500pm and a surface 8x8cm2, for 5 minutes in the electroactive solution of Example 2 before placing it on a plate of glass "K-glass" etched. The subsequent manufacture of the device was done as in Example 4, using a double-sided adhesive about 500p ~ m thick. When no ddp is applied to the device, or a null dp is applied, the device is in the faded state and the TL is the same in each zone and is about 67%. By choosing to use the TCC1, etched, as cathode, we applied a 1.5V ddp on zone A, OV on zone B and 0.8V on zone C. The three zones of the device are colored differently as shown by the light transmission values presented in Table 5.

Table 5: Light transmission values of the electrochromic device of Example 7 as a function of the ddp value applied to each zone Zone of measurement Zone A Zone B Zone C ddp applied per zone 1.5 V 0 0.8V TL when cathode is 3.9% 67.5 40.2 put on the TCC1, etched EXAMPLE 8: Preparation of a preferential coloring zone electrochromic device V1 + TCC1: ITO layer glass with R ^ = 4.852 / - The ITO layer is etched as shown schematically in FIG. 6 - EA: electroactive system: Durapore® membrane and electroactive solution of Example 3 ITO-coated glass with R 1 = 4.852 / 2 the ITO layer is continuous (not engraved) M: metal strip (optional) on V2 + TCC2 glass - MA, MB, MC: metal strips (optional) on V1 + TCC1 glass With a layered glass plate of non-etched ITO and a glass plate covered with an ITO layer etched as described in FIG. Electrochromic positive with three thicknesses of membranes Durapore® HVHP 29325 impregnated with the electroactive solution manufactured for Example 3 and following the protocol described in Example 2. On this new electrochromic device, it is possible to color the zones Z1 and / or Z2. If one chooses to use as cathode the layer TCC1, engraved, and to apply a ddp of 1.5V at the zone Z1, one will color only the interior of the Z1 pattern as shown in the photograph of the device presented to the Figure 24.

EXAMPLE 9 Preparation of an Electrochromic Device with Preferential Coloring Zone - V1 + TCC1: ITO-Coated Glass with Rt = 4.852 / - The ITO layer is etched as shown schematically in Figure 7 - EA: System electroactive agent of Example 1 - V 2 + TCC 2: ITO-coated glass with R 1 = 4.852 / 2 - the ITO layer is continuous (not etched) - M: metal strip (optional) on the glass layer V2 + TCC2 - MA, MB, MC: metal strips (optional) on V1 + TCC1 layer glass With a glass plate covered with a non-etched ITO layer and a glass plate covered with a layer of Etched as described in Figure 7, an electrochromic device was made with the electroactive system and following the protocol described in Example 1.

On this new electrochromic device, it is possible to color zones Z1 and / or Z2. When no ddp is applied to the device, it is completely discolored as shown in Figure 25.

If one chooses to use as cathode the layer TCC1, engraved, and to apply a ddp of 1,5V at the zone Z1 and a ddp null at the level of Z2, one will color only the interior of the Z1 pattern like the shows the photograph of the device in FIG. 26. The device was left in the vertical position for several days and powered with a ddp equal to 1.5V on the zone Z1, using the TCC1 etched as a cathode, and a null ddp on the zone Z2. The appearance of the device remained the same with a coloring only on zone Z1 as shown in FIG. 26. If one chooses to use as anode the TCC1 layer, etched, and to apply a 1.5V ddp. at Z1 and a zero ddp at Z2, the interior of the Z1 pattern will initially be stained, but the color will migrate at the periphery of the Z1 pattern after several minutes as shown in the photograph of the device of Figure 27. .

If one chooses to use as cathode the layer TCC1, engraved, and to apply a ddp of 1,5V at the level of the zone Z2 and to apply a ddp null at level Z1, only the zone Z2 will be colored as shows the photograph of the device in Figure 28. The appearance of the device remains unchanged if the feed mode described above is maintained for several hours. If one chooses to use as cathode the layer TCC1, engraved, and to apply a ddp of 1.5 at a time at the zones Z1 and Z2, these are colored simultaneously and only the two zones nonaddressable, ZNA , remain colorless as the photograph of the device in Figure 29.

EXAMPLE 10 Preparation of an Electrochromic Device with Preferential Coloring Zone - V1 + TCC1: "K-glass" Glass with R = 20.552 / - The SnO2: F layer is etched as shown schematically in FIG. 7 - EA: electroactive system of Example 1 - V2 + TCC2: "K-glassTM" glass with R = 20, 552 / - the SnO2: F layer is etched as shown schematically in FIG. 8 - MA, MB, MC: strips Metallic (optional) on each of the V1 + TCC1 and V2 + TCC2 coated glasses With a "K-glassTM" glass plate covered with a layer of SnO2: F etched as described in Figure 7 and a glass plate " K-glass ™ coated with a layer of SnO 2: F etched as described in FIG. 8, an electrochromic device was manufactured with the electroactive system and following the protocol described in Example 1. By applying a ddp equal to 1.5V at the zone Z1 and a zero dp at the zone Z2, we only colored the zone Z1 as shown in FIG. Figure 30. After several tens of minutes, the appearance of the electrochromic device has changed and the Z2 zone has partially colored because the main etchings of the two substrates were not perfectly superimposed during assembly of the device.

Claims (16)

CLAIMS1 - Electrically controllable device with variable optical / energy properties, comprising the following stack: a first glass-function substrate (V1); a first electronically conductive layer (TCC1) with an associated current supply; An electroactive system (EA); a second electronically conductive layer (TCC2) with an associated current supply; and a second glass-function substrate (V2), characterized in that at least one of the electronically conductive layers (TCC1; TCC2) is formed by a continuous layer which has been etched into at least two addressable areas independently, and that the electroactive system (EA) comprises a medium comprising: at least one electroactive organic compound (eal +) capable of being reduced and / or of accepting electrons and cations acting as compensation charges; at least one electroactive organic compound (ea2) capable of oxidizing and / or ejecting electrons and cations acting as compensation charges; At least one of said electroactive organic compounds (eal + and ea2) being electrochromic to obtain a color contrast; and ionic charges capable of allowing, under the action of an electric current, oxidation and reduction reactions of said electroactive organic compounds (eal + and ea2), which are necessary to obtain the color contrast, said ionic charges having a percolation path, said electroactive compounds (eal + & ea2) and said ionic charges being in the solubilized state by a solubilizing liquid (L), which is also able to solubilize the reduced and oxidized species (eal + ea2 + ) respectively associated with said electroactive compounds (eal + & ea2). 2 - Electrically controllable device according to claim 1, characterized in that only one of the electronically conductive layers has been etched. 3 - Device according to claim 1, characterized in that the two electronically conductive layers have been etched. 4 - electrically controllable device according to claim 3, characterized in that the etchings of the two electronically conductive layers have been arranged correspondingly. 5 - Electrically controllable device according to one of claims 1 to 4, characterized in that an etched electronically conductive layer has a resistivity of 100 to 0.5 S2 / square, especially 20 to 1 S2 / square. 6 - Electrically controllable device according to any one of claims 1 to 5, characterized in that the layers 'CC' and TCC2 comprise an organic and / or inorganic sub-layer, especially in the case of plastic substrates. 7 - electrically controllable device according to one of claims 1 to 6, characterized in that the ionic charges are borne by at least one of said electroactive organic compounds and / or by at least one ionic salt and / or at least one acid solubilized in said liquid (L) and / or, in the case where the electroactive system is in the form of a self-supporting layer, a matrix constituting or composing the self-supporting layer and capable of ensuring mechanical strength. 8 - Electrically controllable device according to one of claims 1 to 7, characterized in that the solubilizing liquid (L) is constituted by a solvent or a mixture of solvents and / or by at least one ionic liquid or salt melted at temperature ambient, said ionic liquid or molten salt or said ionic liquids or molten salts then constituting a solubilization liquid carrying ionic charges, which represent all or part of the ionic charges of said electroactive material. 9 - electrically controllable device according to one of claims 1 to 8, characterized in that the electroactive system is a liquid system formed by the solubilization liquid (L), the electroactive compounds and the ionic charges, the liquid (L) being constituted by a solvent or a mixture of solvents and / or by at least one ionic liquid or salt melted at room temperature, said ionic liquid or molten salt or said ionic liquids or molten salts then constituting a solubilization liquid carrying ionic charges, which represent all or part of the ionic charges of said electroactive material. 10 - Electrically controllable device according to one of claims 1 to 8, characterized in that the electroactive system is a gelled system formed by the solubilization liquid (L), the electroactive compounds, the ionic charges and at least one thickening agent which will solubilize only in the liquid formed by the solvent (s) and the ionic liquid (s) and / or salts or will be only swollen by this liquid, a gel being obtained in both cases, the liquid (L) consisting of a solvent or a mixture of solvents and / or at least one ionic liquid or molten salt at room temperature, said ionic liquid or molten salt or said ionic liquids or molten salts then constituting a solubilization liquid carrying ionic charges, which represent all or part ionic charges of said electroactive material. 11 - Electrically controllable device according to one of claims 1 to 8, characterized in that the electroactive system is in the form of a self-supporting layer comprising or being constituted by a matrix which is adapted to ensure the mechanical strength of said layer self-supporting as well as to ensure the percolation path to the ionic charges and in which are inserted the electroactive organic compounds and the ionic charges which are within the matrix in the solubilized state by the solubilization liquid (L), which is constituted by a solvent or a mixture of solvents and / or by at least one ionic liquid or salt melted at room temperature, said ionic liquid or molten salt or said ionic liquids or molten salts then constituting a solubilization liquid carrying ionic charges, which represent all or part of the ionic charges of said electroactive material, said matrix being translucent or transparent once impregnated with the liquid (L) having solubilized said electroactive compounds (eal + & ea2) and the ionic charges, and being able to retain at least part of its integrity once impregnated with the liquid (L) so that the keeping said electroactive system is ensured, 12 - Electrically controllable device according to claim 11, characterized in that the matrix is formed by a web or a stack of webs, the or each web being a textile or non-textile web, the textile web or a textile web having in particular a web architecture. non-woven or mat veil, woven or knit, optionally coated with a binder, which may be at least partially soluble in the liquid (L) to form a gel; the polymer film constituting at least one non-textile web being in particular a homo- or copolymer in the form of a nonporous film but capable of swelling in said liquid (L), or in the form of a porous film said porous film possibly being able to swell in the liquid having ionic charges and whose porosity after swelling is chosen to allow percolation of the ionic charges in the thickness of the liquid-impregnated film, the stack of layers may further comprise at least one textile web soluble in the liquid (L). 13 - Electrically controllable device according to one of claims 1 to 12, characterized in that it operates in transmission or in reflection. 14 - Electrically controllable device according to one of claims 1 to 13, characterized in that the substrates are transparent, planar or curved, clear or tinted in the mass, opaque or opaque, polygonal or at least partially curved. 15 - Electrically controllable device according to one of claims 1 to 14, characterized in that at least one of the substrates incorporates another feature such as solar control functionality, antireflection or self-cleaning. 16 - Single or multiple glazing characterized in that it comprises an electrically controllable device as defined in one of claims 1 to 15.