EP1649320A1 - Electrically-controllable film having variable optical and/or energy properties - Google Patents

Electrically-controllable film having variable optical and/or energy properties

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Publication number
EP1649320A1
EP1649320A1 EP04767671A EP04767671A EP1649320A1 EP 1649320 A1 EP1649320 A1 EP 1649320A1 EP 04767671 A EP04767671 A EP 04767671A EP 04767671 A EP04767671 A EP 04767671A EP 1649320 A1 EP1649320 A1 EP 1649320A1
Authority
EP
European Patent Office
Prior art keywords
mixture
film
polymerization
derivatives
elements
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04767671A
Other languages
German (de)
French (fr)
Inventor
Grégoire MATHEY
Fabien Beteille
Claude Chevrot
Dominique Teyssie
François TRAN-VAN
Frédéric Bât PAV VIDAL
Layla Beouch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
Original Assignee
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saint Gobain Glass France SAS, Compagnie de Saint Gobain SA filed Critical Saint Gobain Glass France SAS
Publication of EP1649320A1 publication Critical patent/EP1649320A1/en
Withdrawn legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
    • G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
    • G02F1/15165—Polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F2001/15145—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material the electrochromic layer comprises a mixture of anodic and cathodic compounds

Definitions

  • the invention relates to electrocontrollable devices with variable optical and / or energetic properties. It is more particularly interested in devices using electrochromic systems, operating in transmission or in reflection. Examples of electrochromic systems are described in US Patents 5,239,406 and EP-612,826.
  • the electrochromic systems have been widely studied. They generally comprise, in known manner, two layers of electrochromic materials separated by an electrolyte and surrounded by two electrodes. Each of the electrochromic layers, under the effect of an electrical supply, can reversibly insert charges, the modification of their degree of oxidation following these insertions / disinsertions leading to a modification in their optical and / or thermal properties (for example , for tungsten oxide, a change from a blue color to a colorless appearance).
  • electrochromic systems into three categories: - that in which the electrolyte is in the form of a polymer or a gel; for example a proton-conducting polymer like those described in patents EP-253,713 or EP-670,346, or a lithium ion-conducting polymer like those described in patents EP-382,623, EP-518,754 and EP- 532,408; the other layers of the system generally being of mineral nature,
  • the electrochromic system comprises a stack of functional layers which essentially comprises two layers of electrochromic material separated by a layer of electrolyte and framed by two conductive layers.
  • the various layers forming this functional stack are deposited on glass substrates or integrated within these substrates by various techniques known to those skilled in the art (CVD, sol / gel technique, magnetron, spin-coating, etc.) , which however all need to be implemented according to very strict operating methods in order to preserve the optimal properties of the stack.
  • the present invention therefore aims to overcome these drawbacks by proposing an electrocontrollable device with optical / energetic properties of transmission or variable reflection which facilitates its integration within substrates.
  • the subject of the invention is therefore an electrocontrollable device with variable optical / energy properties of transmission or reflection, characterized in that it is shaped into a self-supporting film, said film being formed from a mixture of at least a first element adapted to provide an electrochromic functionality to the mixture, and at least a second element adapted to provide an electrolyte functionality for transporting ionic charges within said mixture.
  • the mixture constitutes a single matrix which is obtained by successive polymerization of the first and second elements initially included in the mixture, the mixture constitutes a single matrix which is obtained by simultaneous polymerization of the first and second elements initially included in the mixture, - the mixture constitutes a single matrix which is obtained by polymerization of the first and second elements successively included,
  • the first element is a conductive polymer, the first element is a polymer based on 3, 4 alkylene dioxy - thiophene or - pyrrole or one of its derivatives, the first element is a polymer based on carbazole or one of its derivatives, the first element is a polyaniline-based polymer or one of its derivatives, - the first element is a mixture of at least two electrochromic materials, at least one having an anodic coloring, the other having a cathodic coloring, the cathodic coloring material is a bipyr
  • the third element is based on diallyl carbonate of diethylene glycol or one of its derivatives or po! y (ethylene glycol) methyl ether methacrylate ...
  • the film constitutes an interpenetrated network of polymers with at least two components
  • the film constitutes a semi-interpenetrated network of polymers with at least two components
  • it has a composition gradient of the first element located according to a characteristic dimension of the film, - it also comprises at least one carrier substrate, said device being disposed between two current leads, respectively lower and upper ("lower” corresponding to the current supply closest to the subst carrier rat, as opposed to the “upper” current supply which is the farthest from said substrate)
  • it relates to an electrochromic system developed from at least one electrochromic device or viologene as previously described.
  • the second element is mixed with possibly the third element in the presence of at at least one polymerization initiating agent, - the second element is polymerized by thermal activation of the mixture and the thermal activation of the mixture is continued in order to obtain the polymerization of the third element - the second and the third element are polymerized or copolymerized in one step by thermal activation of the mixture - the first element is added to the mixture of second and third elements, the first element is polymerized by soaking the mixture with the aid of a polymerization initiating agent, the mixture is rinsed .
  • the first element is incorporated initially into the monomer mixture of the second and third element.
  • the first element is polymerized by soaking the mixture using a polymerization initiating agent, the mixture is rinsed, L the invention will be described in more detail with reference to the attached drawing in which: the single figure is a schematic view of an electrically controllable device according to the invention, produced according to a first embodiment,
  • certain elements can be represented at larger or smaller dimensions than in reality, and this in order to facilitate the understanding of the figures.
  • the single figure represents a glass 1 provided with a lower conductive layer 2, an active stack 3, surmounted by an upper conductive layer 4, a first network of conductive wires 5 or an equivalent device making it possible to bringing electric current above the upper conductive layer, a second network of conductive wires 6 or an equivalent device making it possible to bring electric current below the lower conductive layer 2.
  • the current leads are either conductive wires if the electrochromic active layer is sufficiently conductive, either a network of wires running over or within a layer forming the electrode, this electrode being metallic or of the TCO type (Transparent
  • the conducting wires 5, 6 are metallic wires, for example made of tungsten, optionally covered with carbon or a metallic oxide, with a diameter between 10 and 100 ⁇ m and preferably between 20 and
  • the lower conductive layer 2 is a bilayer consisting of a first SiOC layer of 50 nm surmounted by a second layer of SnO 2 : F of 400 nm (two layers preferably deposited successively by CVD on the float glass before cutting).
  • it may be a bilayer consisting of a first layer based on SiO 2 doped or not (in particular doped with aluminum or boron) of about 20 nm surmounted by a second layer of ITO of around 100 at 350 nm (two layers preferably deposited successively, under vacuum, by cathode sputtering assisted by magnetic field and reactive in the presence of oxygen, optionally hot).
  • the upper conductive layer is produced in a similar manner to the lower conductive layer 2.
  • the active stack 3 shown in the single figure is generally formed into a self-supporting film.
  • a film is said to be “self-supporting” when, by its mechanical properties, it acquires a cohesion which makes it manipulable and retains its shape and dimensions, which makes it easily manipulable, transportable, assemblable. These properties are obtained without the presence of reinforcing substrate.
  • This film is obtained from the mixture of at least two elements: a first suitable for providing an electrochromic functionality and a second suitable for providing a functionality for transporting ionic charges. According to a first embodiment, the mixture is obtained by successive polymerization of the first and second elements successively included, the first element being polymerized after the second.
  • the mixture is obtained by successive polymerization of a mixture of the first and second elements initially included, the first element being polymerized after the second
  • the first element is chosen from conductive polymers , and more particularly among those based on 3, 4-alkylene-dioxythiophene or one of its derivatives such as for example poly (3,
  • PEDT 4-ethylene-dioxythiophene
  • PEGDM poly (ethylene glycol) dimethacrylate
  • AIBN azo-bis-isobutyronitrile
  • a heat treatment at 50 ° C followed by post curing at 80 ° C allows the polymerization / crosslinking of the methacrylate functions.
  • the film is then immersed in a solution of pure ethylene dioxy-thiophene (EDT) or an organic solution containing EDT to allow the incorporation of the monomer into the film.
  • EDT ethylene dioxy-thiophene
  • variable immersion time will control the amount of EDT incorporated.
  • the film is then immersed in a solution containing an oxidant (FeCI 3 for example).
  • the amount of PEDT in the network is adapted as a function of the time of immersion of the film in the oxidizing solution.
  • the EDT monomer (sold by the company STARK of the Bayer Group) is incorporated into the mixture of PEGDM and AIBN. During crosslinking of the matrix, the EDT monomer is trapped in the three-dimensional material. Its subsequent polymerization takes place as in the previous case by immersion in an oxidizing solution.
  • this polymer is based on carbazole or one of its derivatives formed by chemical polymerization.
  • polycarbazoles N-substituted by alkyl or oligo (oxyethylene) chains obtained by chemical oxidative synthesis can be used.
  • a macromer with oxyethylene groups containing pendant carbazoles or thiophenes allowing chemical crosslinking is also possible.
  • the conductive polymer constituting the first element it is particularly stable, in particular to UV, and functions by insertion-disinsertion of cations (Na + , Li + , Ca 2+ , Ba 2+ ...), or alternatively d 'H + ions or anions (CF 3 SO 3 " , BF 4 “ , PF 6 “ , CIO 4 “ , Cl “ , TFSI, SCN “ ”), these ions being optionally incorporated in the form of molten salts.
  • the first element is not based on conductive polymer, but based on a mixture of organic molecules, namely a mixture of at least two electrochromic materials, at least one having an anodic coloring (based on 5, 10-phenazine or one of its derivatives, the other at least having a cathodic coloring (a bipyridine salt).
  • the phenazine derivatives used as organic molecules with anodic coloring can be 5,10 dialkyl 5,10 dihydrophenazine or 5,10-bis (2-hydroxypropyl) -5,10-dihydrophenazine or 5,10-dimethoxymethy!
  • the second element which is associated in the matrix of the film with the first element and which plays the role of electrolyte is also a polymer. It is chosen among polyoxyalkylenes, and more particularly still, it is based on polyoxyethylene (POE) or one of its derivatives.
  • POE polyoxyethylene
  • An example of such a polymer can be produced from poly (ethylene glycol) dimethacrylate or (PEGDM) or poly (ethylene glycol) diacrylate or from a poly (urethane) or poly (ester) network based on poly (oxyethylene). .
  • PEGDM poly (ethylene glycol) dimethacrylate
  • PEGM poly (ethylene glycol) methacrylate
  • EDOT ethylenedioxythiophene
  • AIBN azo-bis-isobutyronitrile
  • a heat treatment at 50 ° C followed by a postcuring at 80 ° C allows the polymerization / crosslinking of the methacrylate functions.
  • a three-dimensional material is formed in which the EDOT monomer is trapped.
  • the film is then immersed in a solution containing the oxidant (FeCI 3 for example, sold by the company Acros).
  • the amount of PEDOT in the network depends on the time of immersion of the film in the oxidizing solution.
  • mixtures of PEGDM and PEGM ranging from 90/10 to 10/90 by mass can be produced to modulate the mechanical and ionic conduction properties.
  • DMA Dynamic Mechanical Analysis
  • the tangent temperature ⁇ of the various PEGDM / PEGM matrices is given below as a function of the molar mass of PEGDM (M ⁇ 875 and 550 g / mol) and the mass proportion of PEGDM and PEGM (x / y) initially introduced is shown in the following table.
  • this third element is a polymer chosen from polycarbonates, or more particularly still those based on diallyl carbonate of diethylene glycol (CR39) or one of its derivatives or else monomers based on methacrylate such than poly (ethylene glycol) methy! ether methacrylate or methyl methacrylate.
  • PEGDM poly (ethylene glycol) dimethacrylate
  • PEGM poly (ethylene glycol) methacrylate
  • EDOT ethylenedioxythiophene
  • AIBN azo-bis-isobutyronitrile
  • Aldrich a polymerization initiating agent
  • 1, 1'-azobis cyclohexanecarbonile
  • a heat treatment at 55 ° C, then at 80 ° C, and finally at 100 ° C followed by a postcuring at 120 ° C allows the polymerization / crosslinking of the allyl and methacrylate functions.
  • the subsequent polymerization is carried out as in the previous case, by immersion in an oxidizing solution.
  • the amount of PEDOT in the network is adapted as a function of the time of immersion of the film in this oxidizing solution.
  • the mixture of the first, second, and possibly third elements, shaped into a self-supporting film, is then positioned between at least two substrates, each of their faces facing the self-supported film being covered with the lower and upper conductive layers 2, 4, and possibly incorporating the current leads, this assembly then conforming an electrically controllable device with variable optical and / or energy properties.
  • said film Prior to assembly of the film within the two substrates, said film was impregnated with Li + salt or other cations among those already listed and possibly with a plasticizing agent. This impregnation can be carried out during the stages of preparation of the film, by incorporating into the mixture of monomers of the three elements the Li + salt in the case where it is insoluble in the solvents for washing and polymerizing the monomer.
  • the matrix forms either a network or an interpenetrating network of polymers.
  • the principle is to polymerize and / or crosslink mixtures (of monomers or prepolymers) of the second and third elements containing functions whose modes or conditions of polymerization or crosslinking are either identical or different.
  • the matrix is a network
  • the matrix is an interpenetrating network.
  • the presence of the third element is not essential.
  • the matrix is also a network.
  • the first element providing the electrochromic functionality is introduced either directly into the initial mixture of the second and third elements, or by impregnation of the network consisting of the second and third elements.
  • the presence of the third element is not essential.
  • the chemical polymerization of the first element within the interpenetrated networks thus formed is obtained by soaking in a solution containing at least one agent for polymerizing the first element (FeCI 3 for example). Depending on the polymerization solvent, the soaking time, the initial concentrations of the conjugated monomer and the thickness of the film, homogeneous or gradient networks can be obtained.
  • the three monomers forming the first, second and third elements are mixed initially as follows:
  • a first network is formed from a mixture of the monomers of the second and third element (in our case, poly ( ethylene glycol) dimethacrylate (PEGDM) with diallyl carbonate of diethylene glycol (CR39) in the presence of a mixture of polymerization initiating agents (AIBN and POB).
  • the polymerization of POE is carried out at 40 ° C.
  • the polymerization of the (PC) from (CR39) is carried out at 80 ° C.
  • the film formed then undergoes baking at 100 ° C. At this stage, the first interpenetrated network is obtained.
  • the polymerization of the first element (that which provides electrochromic functionality) within the first network is obtained by soaking the previous first network in an oxidizing solution (FeCI 3 ...,) the excess of the monomers of the first element which have not reacted t removed by washing said network obtained after soaking in a methanol solution.
  • a functional system of two homogeneous self-supporting films, as previously described (POE / PC / PEDT) framing a self-supported film based on the second and third element (POE / PC) framing a self-supported film based on the second and third element (POE / PC)
  • This assembly is represented in the table below and has optical characteristics (Tl for example) comparable to those obtained for electrochromic systems known from the prior art (namely obtained by electrodeposition techniques.
  • obtaining the network takes up the main steps of the method for obtaining the previous network.
  • the first network formed of the second and third elements is obtained in a similar manner except as regards the presence of the first element. This is not present initially in the mixture with the other two.
  • the first network (POE / PC) in a polymerized form is dipped in a monomer solution based on the first pure element (in our example, it is recalled that the first element is in particular based on EDT). After swelling of the POE / PC network matrix by EDT, the polymerization is obtained by soaking the first swollen network in an oxidizing solution (FeCI3, Iron Tosylate, etc.).
  • the network obtained is gradient.
  • the amount of PEDT is greater on the surface than in the center of the film.
  • the formation of the conductive polymer gradient in the insulating matrix can be followed by the change in ratio of the ohmic resistance at the surface of the film with respect to the thickness resistance. By following the evolution of this ratio as a function of the immersion time for different solvents, one can observe the influence of the nature of the solvent and of the matrix on the polymerization kinetics.
  • the electrically controllable device integrating a self-supporting gradient film between two glass substrates provided at their respective faces opposite the film with the active layers (and any current leads) makes it possible to obtain contrasts greater than 3 between an oxidized and reduced state.
  • said film prior to assembly of the film within the two substrates, said film was impregnated with Li + salt or another cation and optionally with a plasticizing agent. This impregnation can be carried out during the stages of preparation of the film, by incorporating into the mixture of monomers of the three elements the salt of Li + or another cation.
  • a single film can be used industrially to insert the electrochromic functions in the envisaged applications (described below) - interpenetration of the two species of polymers (the electrochromic polymer and the electrolyte polymer) with a conductive polymer gradient in the matrix generates external layers creating de facto contact surfaces with the electrodes (anode and cathode) without presenting the disadvantages (delamination) - the electrochromic material is partially protected from the outside thereby increasing the life of the electrically controllable device
  • the two glasses forming the substrates of the electrically controllable device described above are made of clear glass flat, standard, silica-soda-lime about 2 mm thick each.
  • the invention applies in the same way to curved and / or toughened glasses.
  • at least one of the glasses can be tinted in the mass, in particular tinted blue or green, gray, bronze or brown.
  • the substrates used in the invention can also be based on polymer (PMMA, PET, PC ).
  • the substrates can have very varied geometric shapes: they can be squares or rectangles, but also any polygon or profile at least partially curved, defined by rounded or wavy contours (round, oval, "waves", etc.).
  • At least one of the two glasses can be covered with a coating comprising another functionality (this other functionality being able for example to be an anti-solar stack, an anti-fouling stack or the like).
  • a coating comprising another functionality (this other functionality being able for example to be an anti-solar stack, an anti-fouling stack or the like).
  • an anti-solar stack it can be a stack of thin layers deposited by sputtering and comprising at least one silver layer. It is thus possible to have combinations of the type -glass / electrochromic system / anti-solar layers / glass.
  • thermoplastic can be chosen from PVB, PU.EVA
  • the sunscreen coating can also be deposited not on one of the glasses, but on a sheet of flexible polymer of the PET type (polyethylene terephthalate) .
  • PET polyethylene terephthalate
  • EP 826 641, EP 844 219, EP 847 965, WO99 / 45415, EP 1 010 677 can also be integrated within a tri-glass "substrate", the latter being advantageously used during the development of glazings which comply with safety requirements.

Abstract

The invention relates to an electrically-controllable device with variable optical/energy reflection or transmission properties. The invention is characterised in that the device is shaped in the form of a self-supporting film, said film being formed from a mixture comprising at least one first element which provides the mixture with an electrochrome functionality and at least one second element which produces an electrolyte functionality for ionic charge transfer within said mixture.

Description

FILM ELECTROCOMMANDABLE A PROPRIETES OPTIQUES ET/OU ENERGETIQUES VARIABLES ELECTRICALLY CONTROLLED FILM WITH VARIABLE OPTICAL AND / OR ENERGY PROPERTIES
L'invention concerne les dispositifs électrocommandables à propriétés optiques et/ou énergétiques variables. Elle s'intéresse plus particulièrement aux dispositifs utilisant des systèmes électrochromes, fonctionnant en transmission ou en réflexion. Des exemples de systèmes électrochromes sont décrits dans les brevets US-5 239 406 et EP-612 826. Les systèmes électrochromes ont été très étudiés. Ils comportent de façon connue généralement deux couches de matériaux électrochromes séparées par un électrolyte et encadrées par deux électrodes. Chacune des couches électrochromes, sous l'effet d'une alimentation électrique, peut insérer réversibiement des charges, la modification de leur degré d'oxydation suite à ces insertions/désinsertions conduisant à une modification dans leurs propriétés optiques et/ou thermiques (par exemple, pour l'oxyde de tungstène, un passage d'une coloration bleue à un aspect incolore). Il est d'usage de ranger les systèmes électrochromes en trois catégories : - celle où l'électrolyte est sous forme d'un polymère ou d'un gel ; par exemple un polymère à conduction protonique comme ceux décrits dans les brevets EP- 253 713 ou EP-670 346, ou un polymère à conduction d'ions lithium comme ceux décrits dans les brevets EP-382 623, EP-518 754 et EP-532 408 ; les autres couches du système étant généralement de nature minérale,The invention relates to electrocontrollable devices with variable optical and / or energetic properties. It is more particularly interested in devices using electrochromic systems, operating in transmission or in reflection. Examples of electrochromic systems are described in US Patents 5,239,406 and EP-612,826. The electrochromic systems have been widely studied. They generally comprise, in known manner, two layers of electrochromic materials separated by an electrolyte and surrounded by two electrodes. Each of the electrochromic layers, under the effect of an electrical supply, can reversibly insert charges, the modification of their degree of oxidation following these insertions / disinsertions leading to a modification in their optical and / or thermal properties (for example , for tungsten oxide, a change from a blue color to a colorless appearance). It is customary to classify electrochromic systems into three categories: - that in which the electrolyte is in the form of a polymer or a gel; for example a proton-conducting polymer like those described in patents EP-253,713 or EP-670,346, or a lithium ion-conducting polymer like those described in patents EP-382,623, EP-518,754 and EP- 532,408; the other layers of the system generally being of mineral nature,
>~ celle où l'électrolyte est une couche essentiellement minérale. On désigne souvent cette catégorie sous le terme de système « tout-solide », on pourra en trouver des exemples dans le brevet EP-867 752, EP-831 360, la demande de brevet français FR-2 791 147, la demande de brevet français FR-2 781 084, >- celle où l'ensemble des couches est à base de polymères, catégorie que l'on désigne souvent sous le terme de système « tout-polymère ». Beaucoup d'applications ont déjà été envisagées pour ces systèmes. Il s'est agit, le plus généralement, de les employer comme vitrages pour le bâtiment ou comme vitrages pour véhicule, notamment en tant que toits auto, ou encore, fonctionnant alors en réflexion et non plus en transmission, en tant que rétroviseurs anti-éblouissement. Quelle que soit la catégorie du système électrochrome, celui-ci comporte un empilement de couches fonctionnelles qui comprend essentiellement deux couches de matériau électrochrome séparées par une couche d'électrolyte et encadrées par deux couches conductrices. Classiquement les diverses couches formant cet empilement fonctionnel sont déposées sur des substrats verriers ou intégrés au sein de ces substrats par diverses techniques connues de l'homme de l'art (CVD, technique sol/gel, magnétron, spin-coating...), qui nécessitent toutes cependant d'être mises en œuvre selon des modes opératoires très stricts afin de conserver les propriétés optimales de l'empilement. La présente invention vise donc à pallier ces inconvénients en proposant un dispositif electrocommandable à propriétés optiques/énergétiques de transmission ou de réflexion variable qui facilite son intégration au sein de substrats. L'invention a alors pour objet un dispositif electrocommandable à propriétés optiques/énergétiques de transmission ou de réflexion variables, caractérisé en ce qu'il est conformé en un film auto supporté, ledit film étant formé à partir d'un mélange d'au moins un premier élément adapté pour apporter une fonctionnalité électrochrome au mélange, et d'au moins un second élément adapté pour apporter une fonctionnalité d'électrolyte de transport de charges ioniques au sein dudit mélange. Grâce à l'utilisation d'un film auto-supporté incorporant tous les matériaux nécessaires à la réalisation d'une fonction electrocommandable, il devient possible de dissocier l'élaboration de l'empilement de couches fonctionnelles de celle des substrats permettant ainsi de conserver des procédés d'assemblage standard (feuilletage, calandrage, étuvage, pressage). Dans des modes de réalisation préférés de l'invention, on peut éventuellement avoir recours en outre à l'une et/ou à l'autre des dispositions suivantes : le mélange constitue une matrice unique qui est obtenue par polymérisation successive des premier et second éléments inclus initialement dans le mélange, le mélange constitue une matrice unique qui est obtenue par polymérisation simultanée des premier et second éléments inclus initialement dans le mélange, - le mélange constitue une matrice unique qui est obtenue par polymérisation des premier et second éléments inclus successivement, le premier élément est un polymère conducteur, le premier élément est un polymère à base de 3, 4 alkylène dioxy - thiophène ou - pyrrole ou l'un de ses dérivés, le premier élément est un polymère à base de carbazole ou l'un de ses dérivés, le premier élément est un polymère à base de polyaniline ou l'un de ses dérivés, - le premier élément est un mélange d'au moins deux matériaux électrochromes, l'un au moins ayant une coloration anodique, l'autre ayant une coloration cathodique, le matériau à coloration cathodique est un sel de bipyridine, le matériau à coloration anodique est à base de 5, 10-phénazine ou l'un de ses dérivés, le second élément est un polymère choisi parmi les polyoxyalkylènes, le second élément est choisi parmi les poiyoxyéthylènes ou l'un de ses dérivés, - le second élément est à base de poly(éthylène glycol) difonctionnel (acrylate, méthacrylate, alcool, allylique,... ), le film auto supporté comporte éventuellement un troisième élément adapté pour améliorer sa tenue mécanique ou pour améliorer la conductivité ionique, le troisième élément est mélangé avec le second élément et leur polymérisation est simultanée ou successive, le troisième élément est un polymère choisi notamment parmi les polyacrylates, poly(méthacrylates), poly(carbonates), polyacétate, polyuréthanes, cellulosiques, ... le troisième élément est à base de diallyl carbonate de diéthylène glycol ou un de ses dérivés ou encore de po!y(éthylène glycol) méthyl éther méthacrylate ... , le film constitue un réseau interpénétré de polymères à au moins deux composants, le film constitue un réseau semi-interpénétré de polymères à au moins deux composants, il présente un gradient de composition du premier élément situé selon une dimension caractéristique du film, - il comporte en outre au moins un substrat porteur, ledit dispositif étant disposé entre deux amenées de courant, respectivement inférieure et supérieure (« inférieure » correspondant à l'amenée de courant la plus proche du substrat porteur, par opposition à l'amenée de courant « supérieure » qui est la plus éloignée dudit substrat), Selon un autre aspect de l'invention, celle-ci vise un système électrochrome élaboré à partir d'au moins un dispositif électrochrome ou viologène tel que précédemment décrit. Dans des modes de réalisation préférés de l'invention, on peut éventuellement avoir recours en outre à l'une et/ou à l'autre des dispositions suivantes : - il s'agit d'un toit auto pour véhicule, activable de façon autonome, ou d'une vitre latérale ou d'une lunette arrière pour véhicule, ou d'un rétroviseur, - il s'agit d'un pare-brise ou d'une portion de pare-brise, il s'agit d'un panneau d'affichage d'informations graphiques et/ou alphanumériques, d'un vitrage pour le bâtiment, d'un rétroviseur, d'un hublot ou d'un pare-brise d'avion, ou d'une fenêtre de toit, - il s'agit d'un vitrage intérieur ou extérieur pour le bâtiment, d'un présentoir, d'un comptoir de magasin pouvant être bombé, d'un vitrage de protection d'objet du type tableau, d'un écran anti- éblouissement d'ordinateur, d'un mobilier verrier, d'une paroi de séparation de deux pièces à l'intérieur d'un bâtiment ou d'une automobile il fonctionne en transmission ou en réflexion, le substrat est transparent, plan ou bombé, clair ou teinté dans la masse, de forme polygonale ou au moins partiellement courbe, le substrat est opaque ou opacifié, - il incorpore une autre fonctionnalité. Selon encore un autre aspect de l'invention, celle-ci vise un procédé d'obtention d'un dispositif tel que précédemment décrit qui se caractérise en ce que : - on mélange le second élément avec éventuellement le troisième élément en présence d'au moins un agent initiateur de polymérisation, - on procède à la polymérisation du second élément par activation thermique du mélange et on poursuit l'activation thermique du mélange afin d'obtenir la polymérisation du troisième élément - le deuxième et le troisième élément sont polymérisés ou copolymérisés en une étape par activation thermique du mélange - on ajoute au mélange des second et troisième éléments, le premier élément, on polymérise le premier élément par trempage du mélange à l'aide d'un agent initiateur de polymérisation, on effectue un rinçage du mélange. Selon une autre variante du procédé, le premier élément est incorporé initialement dans le mélange de monomère du deuxième et troisième élément. Après polymérisation des second et troisième éléments à l'aide d'au moins un agent initiateur de polymérisation, on polymérise le premier élément par trempage du mélange à l'aide d'un agent initiateur de polymérisation, on effectue un rinçage du mélange, L'invention sera décrite plus en détail au regard du dessin annexé sur lesquel : - la figure unique est une vue schématique d'un dispositif electrocommandable selon l'invention, réalisé selon un premier mode de réalisation, Sur les dessins annexés, certains éléments peuvent être représentés à des dimensions plus grandes ou plus petites que dans la réalité, et ce afin de faciliter la compréhension des figures. La figure unique représente un verre 1 muni d'une couche conductrice inférieure 2, d'un empilement actif 3, surmonté d'une couche conductrice supérieure 4, d'un premier réseau de fils conducteurs 5 ou d'un dispositif équivalent permettant d'amener du courant électrique au-dessus de la couche conductrice supérieure, d'un second réseau de fils conducteurs 6 ou d'un dispositif équivalent permettant d'amener du courant électrique en dessous de la couche conductrice inférieure 2. Les amenées de courant sont soit des fils conducteurs si la couche active électrochrome est suffisamment conductrice, soit un réseau de fils cheminant sur ou au sein d'une couche formant l'électrode, cette électrode étant métallique ou du type TCO (Transparent> ~ that where the electrolyte is an essentially mineral layer. This category is often designated by the term “all-solid” system, examples of which can be found in patent EP-867,752, EP-831,360, French patent application FR-2,791,147, patent application. French FR-2 781 084, > - the one where all the layers are based on polymers, a category that is often referred to as the “all-polymer” system. Many applications have already been envisaged for these systems. It was, most generally, to use them as glazing for the building or as glazing for vehicle, in particular as car roofs, or else, then functioning in reflection and no longer in transmission, as rear-view mirrors glare. Whatever the category of the electrochromic system, it comprises a stack of functional layers which essentially comprises two layers of electrochromic material separated by a layer of electrolyte and framed by two conductive layers. Conventionally, the various layers forming this functional stack are deposited on glass substrates or integrated within these substrates by various techniques known to those skilled in the art (CVD, sol / gel technique, magnetron, spin-coating, etc.) , which however all need to be implemented according to very strict operating methods in order to preserve the optimal properties of the stack. The present invention therefore aims to overcome these drawbacks by proposing an electrocontrollable device with optical / energetic properties of transmission or variable reflection which facilitates its integration within substrates. The subject of the invention is therefore an electrocontrollable device with variable optical / energy properties of transmission or reflection, characterized in that it is shaped into a self-supporting film, said film being formed from a mixture of at least a first element adapted to provide an electrochromic functionality to the mixture, and at least a second element adapted to provide an electrolyte functionality for transporting ionic charges within said mixture. Thanks to the use of a self-supporting film incorporating all the materials necessary for achieving an electrocontrollable function, it becomes possible to dissociate the development of the stack of functional layers from that of the substrates, thus making it possible to conserve standard assembly processes (laminating, calendering, steaming, pressing). In preferred embodiments of the invention, it is optionally possible to have recourse to one and / or the other of the following arrangements: the mixture constitutes a single matrix which is obtained by successive polymerization of the first and second elements initially included in the mixture, the mixture constitutes a single matrix which is obtained by simultaneous polymerization of the first and second elements initially included in the mixture, - the mixture constitutes a single matrix which is obtained by polymerization of the first and second elements successively included, the first element is a conductive polymer, the first element is a polymer based on 3, 4 alkylene dioxy - thiophene or - pyrrole or one of its derivatives, the first element is a polymer based on carbazole or one of its derivatives, the first element is a polyaniline-based polymer or one of its derivatives, - the first element is a mixture of at least two electrochromic materials, at least one having an anodic coloring, the other having a cathodic coloring, the cathodic coloring material is a bipyridine salt, the anodic coloring material is based on 5, 10-phenazine or one of its derivatives, the second element is a polymer chosen from polyoxyalkylenes, the second element is chosen from polyoxyethylenes or one of its derivatives, - the second element is based on difunctional poly (ethylene glycol) (acrylate , methacrylate, alcohol, allyl, etc.), the self-supporting film optionally includes a third element adapted to improve its mechanical strength or to improve the ionic conductivity, the third element is mixed with the second element and their polymerization is simultaneous or successive, the third element is a polymer chosen in particular from polyacrylates, poly (methacrylates), poly (carbonates), polyacetate, polyurethanes, cellulosics, ... the third element is based on diallyl carbonate of diethylene glycol or one of its derivatives or po! y (ethylene glycol) methyl ether methacrylate ..., the film constitutes an interpenetrated network of polymers with at least two components, the film constitutes a semi-interpenetrated network of polymers with at least two components, it has a composition gradient of the first element located according to a characteristic dimension of the film, - it also comprises at least one carrier substrate, said device being disposed between two current leads, respectively lower and upper ("lower" corresponding to the current supply closest to the subst carrier rat, as opposed to the “upper” current supply which is the farthest from said substrate), According to another aspect of the invention, it relates to an electrochromic system developed from at least one electrochromic device or viologene as previously described. In preferred embodiments of the invention, one can optionally have recourse to one and / or the other of the following provisions: - it is a car roof for a vehicle, activatable independently , or a side window or a rear window for a vehicle, or a rear view mirror, - it is a windshield or a portion of the windshield, it is a display panel for graphical and / or alphanumeric information, glazing for the building, rear-view mirror, porthole or windshield of an aircraft, or a roof window, - it is an interior or exterior glazing for the building, a display stand, a store counter that can be curved, a glass for protecting an object such as a painting, a computer anti-glare screen, glass furniture, a partition wall of two parts inside a building or an automobile it works in transmission or in reflection, the substrate is transparent, flat or curved, clear or tinted in the mass, of polygonal shape or at least partially curved, the substrate is opaque or opacified, - it incorporates another functionality. According to yet another aspect of the invention, it relates to a process for obtaining a device as previously described which is characterized in that: - the second element is mixed with possibly the third element in the presence of at at least one polymerization initiating agent, - the second element is polymerized by thermal activation of the mixture and the thermal activation of the mixture is continued in order to obtain the polymerization of the third element - the second and the third element are polymerized or copolymerized in one step by thermal activation of the mixture - the first element is added to the mixture of second and third elements, the first element is polymerized by soaking the mixture with the aid of a polymerization initiating agent, the mixture is rinsed . According to another variant of the process, the first element is incorporated initially into the monomer mixture of the second and third element. After polymerization of the second and third elements using at least one polymerization initiating agent, the first element is polymerized by soaking the mixture using a polymerization initiating agent, the mixture is rinsed, L the invention will be described in more detail with reference to the attached drawing in which: the single figure is a schematic view of an electrically controllable device according to the invention, produced according to a first embodiment, In the appended drawings, certain elements can be represented at larger or smaller dimensions than in reality, and this in order to facilitate the understanding of the figures. The single figure represents a glass 1 provided with a lower conductive layer 2, an active stack 3, surmounted by an upper conductive layer 4, a first network of conductive wires 5 or an equivalent device making it possible to bringing electric current above the upper conductive layer, a second network of conductive wires 6 or an equivalent device making it possible to bring electric current below the lower conductive layer 2. The current leads are either conductive wires if the electrochromic active layer is sufficiently conductive, either a network of wires running over or within a layer forming the electrode, this electrode being metallic or of the TCO type (Transparent
Conductive Oxide) en ITO, SnO2:F, ZnO :AI, soit une couche conductrice seule. Les fils conducteurs 5, 6 sont des fils métalliques par exemple en tungstène, éventuellement recouvert de carbone ou d'un oxyde métallique, d'un diamètre compris entre 10 et 100 μm et preferentiellement compris entre 20 etConductive Oxide) in ITO, SnO 2 : F, ZnO: AI, i.e. a conductive layer alone. The conducting wires 5, 6 are metallic wires, for example made of tungsten, optionally covered with carbon or a metallic oxide, with a diameter between 10 and 100 μm and preferably between 20 and
50 μm, rectilignes ou ondulés, déposés sur une feuille de PU par une technique connue dans le domaine de pare-brise chauffants à fils, par exemple décrite dans les brevets EP-785 700, EP-553 025, EP-506 521 , EP-496 669. Une de ces techniques connues consiste dans l'utilisation d'un galet de pression chauffé qui vient presser le fil à la surface de la feuille de polymère, ce galet de pression étant alimenté en fil à partir d'une bobine d'alimentation grâce à un dispositif guide-fil. La couche conductrice inférieure 2 est un bicouche constitué d'une première couche SiOC de 50 nm surmontée d'une seconde couche en Sn02 :F de 400 nm (deux couches de préférence déposées successivement par CVD sur le verre float avant découpe). Alternativement, il peut s'agir d'un bicouche constitué d'une première couche à base de SiO2 dopée ou non (notamment dopé avec de l'aluminium ou du bore) d'environ 20 nm surmontée d'une seconde couche d'ITO d'environ 100 à 350 nm (deux couches de préférence déposées successivement, sous vide, par pulvérisation cathodique assistée par champ magnétique et réactive en présence d'oxygène éventuellement à chaud). La couche conductrice supérieure est réalisée de manière analogue à la couche conductrice inférieure 2. L'empilement actif 3 représenté en figure unique est globalement conformé en un film autosupporté. Au sens de la présente invention, un film est dit « autosupporté » lorsque de par ses propriétés mécaniques, il acquiert une cohésion qui le rend manipulable et conserve sa forme et ses dimensions, ce qui le rend aisément manipulable, transportable, assemblable. Ces propriétés sont obtenues sans la présence de substrat de renfort. Ce film est obtenu à partir du mélange d'au moins deux éléments : un premier adapté pour apporter une fonctionnalité électrochrome et un second adapté pour apporter une fonctionnalité de transport de charges ioniques. Selon un premier mode de réalisation, le mélange est obtenu par polymérisation successive des premiers et second éléments inclus successivement, le premier élément étant polymérise après le second. Selon un deuxième mode de réalisation, le mélange est obtenu par polymérisation successive d'un mélange des premiers et second éléments inclus initialement, le premier élément étant polymérise après le second Dans ces deux modes de réalisation, le premier élément est choisi parmi les polymères conducteurs, et plus particulièrement parmi ceux à base de 3, 4- alkylène-dioxythiophène ou l'un de ses dérivés comme par exemple le poly(3,50 μm, straight or wavy, deposited on a PU sheet by a technique known in the field of heated windshields with wires, for example described in patents EP-785,700, EP-553,025, EP-506,521, EP One of these known techniques consists in the use of a heated pressure roller which presses the wire on the surface of the polymer sheet, this pressure roller being supplied with wire from a reel d 'feed through a wire guide device. The lower conductive layer 2 is a bilayer consisting of a first SiOC layer of 50 nm surmounted by a second layer of SnO 2 : F of 400 nm (two layers preferably deposited successively by CVD on the float glass before cutting). Alternatively, it may be a bilayer consisting of a first layer based on SiO 2 doped or not (in particular doped with aluminum or boron) of about 20 nm surmounted by a second layer of ITO of around 100 at 350 nm (two layers preferably deposited successively, under vacuum, by cathode sputtering assisted by magnetic field and reactive in the presence of oxygen, optionally hot). The upper conductive layer is produced in a similar manner to the lower conductive layer 2. The active stack 3 shown in the single figure is generally formed into a self-supporting film. For the purposes of the present invention, a film is said to be “self-supporting” when, by its mechanical properties, it acquires a cohesion which makes it manipulable and retains its shape and dimensions, which makes it easily manipulable, transportable, assemblable. These properties are obtained without the presence of reinforcing substrate. This film is obtained from the mixture of at least two elements: a first suitable for providing an electrochromic functionality and a second suitable for providing a functionality for transporting ionic charges. According to a first embodiment, the mixture is obtained by successive polymerization of the first and second elements successively included, the first element being polymerized after the second. According to a second embodiment, the mixture is obtained by successive polymerization of a mixture of the first and second elements initially included, the first element being polymerized after the second In these two embodiments, the first element is chosen from conductive polymers , and more particularly among those based on 3, 4-alkylene-dioxythiophene or one of its derivatives such as for example poly (3,
4-éthylène-dioxythiophène) dénommé PEDT formé par polymérisation chimique. Par exemple un mélange de poly(éthylèneglycol)diméthacrylate (PEGDM) de masse molaire variable (550 et 875 g/mol) et d'azo-bis- isobutyronitrile (AIBN) est coulé entre deux plaques de verre séparées par un joint en « Téflon ». Un traitement thermique à 50°C suivi d'une post cuisson à 80°C permet la polymérisation / réticulation des fonctions méthacrylate. Le film est ensuite immergé dans une solution d'éthylène dioxy-thiophène (EDT) pur ou d'une solution organique contenant de l'EDT pour permettre l'incorporation du monomère dans le film. Le temps d'immersion variable permettra de contrôler la quantité d'EDT incorporée. Le film est alors immergé dans une solution contenant un oxydant (FeCI3 par exemple). La quantité de PEDT dans le réseau est adaptée en fonction du temps d'immersion du film dans la solution oxydante. Selon un deuxième mode de réalisation, le monomère EDT (commercialisé par la société STARK du Groupe Bayer) est incorporé dans le mélange de PEGDM et d'AIBN. Lors de la réticulation de la matrice, le monomère EDT est piégé dans le matériau tridimensionnel. Sa polymérisation ultérieure se fait comme dans le cas précédent par immersion dans une solution oxydante. Selon un autre exemple de polymère conducteur utilisé en tant que premier élément, ce polymère est à base de carbazole ou l'un de ses dérivés formé par polymérisation chimique. Par exemple des polycarbazoles N-substitués par des chaînes alkyles ou oligo (oxyéthylenes) obtenus par synthèse oxidative chimique peuvent être utilisés. Un macromère à groupements oxyéthylenes contenant des carbazoles ou thiophènes pendants permettant une réticulation chimique est également possible. Quel que soit le polymère conducteur constituant le premier élément, il est particulièrement stable, notamment aux UV, et fonctionne par insertion- désinsertion de cations (Na+, Li+, Ca2+, Ba2+...), ou alternativement d'ions H+ ou encore d'anions (CF3SO3 ", BF4 ", PF6 ", CIO4 ", Cl", TFSI, SCN"...), ces ions étant éventuellement incorporés sous forme de sels fondus. Selon encore un autre exemple de réalisation, le premier élément n'est pas à base de polymère conducteur, mais à base d'un mélange de molécules organiques, à savoir un mélange d'au moins deux matériaux électrochromes, l'un au moins ayant une coloration anodique (à base de 5, 10-phénazine ou un ses dérivés, l'autre au moins ayant une coloration cathodique (un sel de bipyridine). Les dérivés de phénazines utilisés comme molécules organiques à coloration anodique peuvent être des 5,10 dialkyl 5,10 dihydrophénazine ou des 5,10-bis(2-hydroxypropyl)-5,10-dihydrophénazine ou des 5,10- diméthoxyméthy!-5,10-dihydrophénazine par exemple. Le second élément qui est associé dans la matrice du film au premier élément et qui joue le rôle d'électrolyte est également un polymère. Il est choisi parmi les polyoxyalkylènes, et plus particulièrement encore il est à base de polyoxyéthylène (POE) ou l'un de ses dérivés. Un exemple d'un tel polymère peut être réalisé à partir de poly(éthylène glycol)diméthacrylate ou (PEGDM) ou de poly(éthylène glycol)diacrylate ou de réseau poly(uréthane) ou poly(ester) à base de poly(oxyéthylene). Par exemple, un mélange de 2g de poly(éthylèneglycol)diméthacrylate (PEGDM) (commercialisé par la société Aldrich, M=550 ou 875 g/mol), 2g de poly(éthylèneglycol)méthacrylate (PEGM) (commercialisé par la société Aldrich, M=475 g/mol), d'éthylènedioxythiophène (EDOT) (1 ou 2 ou 10% en masse par rapport au PEGDM et PEGM) et d'azo-bis-isobutyronitrile (AIBN) (commercialisé par la société Aldrich, 1% en masse par rapport au PEGDM et PEGM) est coulé entre deux plaques de verre séparées par un joint de « téflon » (marque déposée). Un traitement thermique à 50°C suivi d'une postcuisson à 80°C permet la polymérisation / réticulation des fonctions méthacrylates. Un matériau tridimensionnel est formé dans lequel est piégé le monomère EDOT. Le film est ensuite immergé dans une solution contenant l'oxydant (FeCI3 par exemple, commercialisé par la société Acros). La quantité de PEDOT dans le réseau dépend du temps d'immersion du film dans la solution oxydante. A partir des mêmes conditions opératoires, des mélanges de PEGDM et de PEGM allant de 90/10 à 10/90 en masse peuvent être réalisés pour moduler les propriétés mécaniques et de conduction ionique. Une des méthodes permettant de quantifier les propriétés mécaniques du film consiste à utiliser la DMA (Dynamic Mechanical Analysis). A l'aide de cette méthode, on donne ci-après la température de tangente δ des différentes matrices PEGDM/PEGM en fonction de la masse molaire en PEGDM (M≈875 et 550 g/mol) et la proportion massique de PEGDM et PEGM (x/y) introduit initialement est représentée dans le tableau qui suit. 4-ethylene-dioxythiophene) called PEDT formed by chemical polymerization. For example, a mixture of poly (ethylene glycol) dimethacrylate (PEGDM) of variable molar mass (550 and 875 g / mol) and of azo-bis-isobutyronitrile (AIBN) is poured between two glass plates separated by a "Teflon" seal. ". A heat treatment at 50 ° C followed by post curing at 80 ° C allows the polymerization / crosslinking of the methacrylate functions. The film is then immersed in a solution of pure ethylene dioxy-thiophene (EDT) or an organic solution containing EDT to allow the incorporation of the monomer into the film. The variable immersion time will control the amount of EDT incorporated. The film is then immersed in a solution containing an oxidant (FeCI 3 for example). The amount of PEDT in the network is adapted as a function of the time of immersion of the film in the oxidizing solution. According to a second embodiment, the EDT monomer (sold by the company STARK of the Bayer Group) is incorporated into the mixture of PEGDM and AIBN. During crosslinking of the matrix, the EDT monomer is trapped in the three-dimensional material. Its subsequent polymerization takes place as in the previous case by immersion in an oxidizing solution. According to another example of conductive polymer used as the first element, this polymer is based on carbazole or one of its derivatives formed by chemical polymerization. For example, polycarbazoles N-substituted by alkyl or oligo (oxyethylene) chains obtained by chemical oxidative synthesis can be used. A macromer with oxyethylene groups containing pendant carbazoles or thiophenes allowing chemical crosslinking is also possible. Whatever the conductive polymer constituting the first element, it is particularly stable, in particular to UV, and functions by insertion-disinsertion of cations (Na + , Li + , Ca 2+ , Ba 2+ ...), or alternatively d 'H + ions or anions (CF 3 SO 3 " , BF 4 " , PF 6 " , CIO 4 " , Cl " , TFSI, SCN " ...), these ions being optionally incorporated in the form of molten salts. According to yet another exemplary embodiment, the first element is not based on conductive polymer, but based on a mixture of organic molecules, namely a mixture of at least two electrochromic materials, at least one having an anodic coloring (based on 5, 10-phenazine or one of its derivatives, the other at least having a cathodic coloring (a bipyridine salt). The phenazine derivatives used as organic molecules with anodic coloring can be 5,10 dialkyl 5,10 dihydrophenazine or 5,10-bis (2-hydroxypropyl) -5,10-dihydrophenazine or 5,10-dimethoxymethy! -5,10-dihydrophenazine for example The second element which is associated in the matrix of the film with the first element and which plays the role of electrolyte is also a polymer. It is chosen among polyoxyalkylenes, and more particularly still, it is based on polyoxyethylene (POE) or one of its derivatives. An example of such a polymer can be produced from poly (ethylene glycol) dimethacrylate or (PEGDM) or poly (ethylene glycol) diacrylate or from a poly (urethane) or poly (ester) network based on poly (oxyethylene). . For example, a mixture of 2 g of poly (ethylene glycol) dimethacrylate (PEGDM) (sold by the company Aldrich, M = 550 or 875 g / mol), 2 g of poly (ethylene glycol) methacrylate (PEGM) (sold by the company Aldrich, M = 475 g / mol), ethylenedioxythiophene (EDOT) (1 or 2 or 10% by mass relative to PEGDM and PEGM) and azo-bis-isobutyronitrile (AIBN) (sold by the company Aldrich, 1% in mass compared to PEGDM and PEGM) is poured between two glass plates separated by a "Teflon" seal (registered trademark). A heat treatment at 50 ° C followed by a postcuring at 80 ° C allows the polymerization / crosslinking of the methacrylate functions. A three-dimensional material is formed in which the EDOT monomer is trapped. The film is then immersed in a solution containing the oxidant (FeCI 3 for example, sold by the company Acros). The amount of PEDOT in the network depends on the time of immersion of the film in the oxidizing solution. Starting from the same operating conditions, mixtures of PEGDM and PEGM ranging from 90/10 to 10/90 by mass can be produced to modulate the mechanical and ionic conduction properties. One of the methods for quantifying the mechanical properties of the film consists in using DMA (Dynamic Mechanical Analysis). Using this method, the tangent temperature δ of the various PEGDM / PEGM matrices is given below as a function of the molar mass of PEGDM (M≈875 and 550 g / mol) and the mass proportion of PEGDM and PEGM (x / y) initially introduced is shown in the following table.
Lorsque l'on désire améliorer les propriétés de tenue mécanique du film auto supporté formé par le mélange des premier et second éléments, on prévoit d'incorporer audit mélange précédent un troisième élément, pouvant être lui- même constitué d'un mélange ou de plusieurs polymères. Selon un mode de réalisation, ce troisième élément est un polymère choisi parmi les polycarbonates, ou plus particulièrement encore ceux à base de diallyl carbonate de diéthylène glycol (le CR39) ou l'un de ses dérivés ou bien des monomères à base de méthacrylate tels que le poly(ethylène glycol) méthy! éther méthacrylate ou du méthacrylate de méthyle. Pour une matrice PEGDM/PEGM/PC (40/40/20), un mélange de 2g de poly(éthylèneglycol)diméthacrylate (PEGDM) (commercialisé par la société Aldrich, M=875 g/mol), 2g de poly(éthylèneglycol)méthacrylate (PEGM) (commercialisé par la société Aldrich, M=475 g/mol), 1g de bisallylcarbonate (CR39) (commercialisé par la société Aldrich, M=274,27 g/mol), d'éthylènedioxythiophène (EDOT) (commercialisé par la société Stark, 2% en masse par rapport au PEGDM, PEGM et CR39, M=142 g/mol) est préparée. A ce mélange, est additionné 3% en masse d'azo-bis-isobutyronitrile (AIBN) (commercialisé par la société Aldrich) (pourcentage en masse par rapport au PEGDM, PEGM et CR39 introduits initialement) et 4% en masse d'un autre agent initiateur de polymérisation, le 1 ,1'-azobis(cyclohexanecarbonile) (commercialisé par la société Acros) (pourcentage en masse par rapport au CR39 introduit initialement). Comme précédemment, le mélange est coulé entre deux plaques de verre séparées par un joint de « téflon » (marque déposée). Un traitement thermique à 55°C, puis à 80°C, et enfin à 100°C suivi d'une postcuisson à 120°C permet la polymérisation / réticulation des fonctions allyles et méthacrylates. La polymérisation ultérieure se fait comme dans le cas précédent, par immersion dans une solution oxydante. La quantité de PEDOT dans le réseau est adaptée en fonction du temps d'immersion du film dans cette solution oxydante. Le mélange des premier, second, et éventuellement troisième éléments, conformés en film autosupporté, est alors positionné entre au moins deux substrats, chacune de leurs faces en regard du film autosupporté étant recouverte des couches conductrices inférieure et supérieure 2, 4, et éventuellement incorporant les amenées de courant, cet assemblage conformant alors un dispositif electrocommandable à propriétés optiques et/ou énergétiques variables. Préalablement à l'assemblage du film au sein des deux substrats, ledit film a été imprégné de sel de Li+ ou d'autres cations parmi ceux déjà énumérés et éventuellement d'un agent plastifiant. Cette imprégnation peut être réalisée lors des étapes d'élaboration du film, en incorporant dans le mélange de monomères des trois éléments le sel de Li+ dans le cas ou celui ci est insoluble dans les solvants de lavage et de polymérisation du monomère. Selon un mode de réalisation de ce dispositif electrocommandable, la matrice forme soit un réseau, soit un réseau interpénétré de polymères. Le principe est de polymériser et/ou de réticuler des mélanges (de monomères ou de prépolymères) des deuxième, et troisième éléments contenant des fonctions dont les modes ou conditions de polymérisation ou de réticulation sont soit identiques, soit différents. Dans le premier cas, la matrice est un réseau, dans le second cas la matrice est un réseau interpénétré. La présence du troisième élément n'est pas indispensable. Dans ce dernier cas la matrice est aussi un réseau. Par exemple, des monomères ou des prépolymères du deuxième élément polymérisant par voie radicalaire et des monomères du troisième élément polymérisant par voie radicalaire, cationique ou anionique, des polymères ou des prépolymères des deuxième et troisième éléments polymérisant à des températures identiques ou différentes. Le premier élément apportant la fonctionnalité électrochrome est introduit soit directement dans le mélange initial des deuxième et troisième éléments, soit par imprégnation du réseau constitué des deuxième et troisième éléments. La présence du troisième élément n'est pas indispensable. Dans un mode de réalisation, la polymérisation chimique du premier élément au sein des réseaux interpénétrés ainsi constitués est obtenue par trempage dans une solution contenant au moins un agent de polymérisation du premier élément (FeCI3 par exemple). Selon le solvant de polymérisation, le temps de trempage, les concentrations initiales du monomère conjugué et l'épaisseur du film, des réseaux homogènes ou à gradient peuvent être obtenus. Ainsi par exemple, les trois monomères formant les premier, second et troisième éléments sont mélangés initialement de la manière suivante : Un premier réseau est formé à partir d'un mélange des monomères des deuxième et troisième élément (dans notre cas on mélange du poly(éthylène glycol)diméthacrylate (PEGDM) avec du diallyl carbonate de diéthylène glycol (CR39) en présence d'un mélange d'agents initiateurs de polymérisation (AIBN et POB). La polymérisation du POE (issu du PEGDM) est réalisée à 40°C. La polymérisation du (PC) issu du (CR39) est réalisée à 80°C. Le film formé subit alors une cuisson à 100°C. A ce stade, le premier réseau interpénétré est obtenu. La polymérisation du premier élément (celui qui apporte la fonctionnalité électrochrome) au sein du premier réseau est obtenue par trempage du premier réseau précédent dans une solution oxydante (FeCI3...,) l'excès des monomères du premier élément qui n'ont pas réagi est ôté par lavage dudit réseau obtenu après trempage dans une solution de méthanol. Par exemple, un système fonctionnel de deux films autosupportés homogènes, tels que précédemment décrits (POE/PC/PEDT) encadrant un film autosupporté à base des deuxième et troisième élément (POE/PC), l 'ensemble associé à des couches actives formant électrodes inférieure et supérieure est fonctionnel et permet d'obtenir des contrastes supérieurs à 3 entre un état oxydé et réduit. Cet ensemble est représenté dans le tableau ci-dessous et dispose de caractéristiques optiques (Tl par exemple) comparables à celles obtenues pour des systèmes électrochromes connus de l 'art antérieur (à savoir obtenus par des techniques de électrodépositions.When it is desired to improve the mechanical strength properties of the self-supporting film formed by the mixture of the first and second elements, provision is made to incorporate into said preceding mixture a third element, which may itself consist of a mixture or of several polymers. According to one embodiment, this third element is a polymer chosen from polycarbonates, or more particularly still those based on diallyl carbonate of diethylene glycol (CR39) or one of its derivatives or else monomers based on methacrylate such than poly (ethylene glycol) methy! ether methacrylate or methyl methacrylate. For a PEGDM / PEGM / PC matrix (40/40/20), a mixture of 2 g of poly (ethylene glycol) dimethacrylate (PEGDM) (sold by the company Aldrich, M = 875 g / mol), 2 g of poly (ethylene glycol) methacrylate (PEGM) (marketed by Aldrich, M = 475 g / mol), 1g of bisallylcarbonate (CR39) (marketed by Aldrich, M = 274.27 g / mol), ethylenedioxythiophene (EDOT) (marketed by the company Stark, 2% by mass relative to PEGDM, PEGM and CR39, M = 142 g / mol) is prepared. To this mixture is added 3% by mass of azo-bis-isobutyronitrile (AIBN) (sold by the company Aldrich) (percentage by mass relative to the PEGDM, PEGM and CR39 introduced initially) and 4% by mass of a another polymerization initiating agent, 1, 1'-azobis (cyclohexanecarbonile) (marketed by the company Acros) (percentage by mass relative to the CR39 introduced initially). As before, the mixture is poured between two glass plates separated by a "teflon" (registered trademark) seal. A heat treatment at 55 ° C, then at 80 ° C, and finally at 100 ° C followed by a postcuring at 120 ° C allows the polymerization / crosslinking of the allyl and methacrylate functions. The subsequent polymerization is carried out as in the previous case, by immersion in an oxidizing solution. The amount of PEDOT in the network is adapted as a function of the time of immersion of the film in this oxidizing solution. The mixture of the first, second, and possibly third elements, shaped into a self-supporting film, is then positioned between at least two substrates, each of their faces facing the self-supported film being covered with the lower and upper conductive layers 2, 4, and possibly incorporating the current leads, this assembly then conforming an electrically controllable device with variable optical and / or energy properties. Prior to assembly of the film within the two substrates, said film was impregnated with Li + salt or other cations among those already listed and possibly with a plasticizing agent. This impregnation can be carried out during the stages of preparation of the film, by incorporating into the mixture of monomers of the three elements the Li + salt in the case where it is insoluble in the solvents for washing and polymerizing the monomer. According to one embodiment of this electrocontrollable device, the matrix forms either a network or an interpenetrating network of polymers. The principle is to polymerize and / or crosslink mixtures (of monomers or prepolymers) of the second and third elements containing functions whose modes or conditions of polymerization or crosslinking are either identical or different. In the first case, the matrix is a network, in the second case the matrix is an interpenetrating network. The presence of the third element is not essential. In the latter case the matrix is also a network. For example, monomers or prepolymers of the second radical polymerizing element and monomers of the third radical polymerizing element, cationic or anionic, polymers or prepolymers of the second and third polymerizing elements at identical or different temperatures. The first element providing the electrochromic functionality is introduced either directly into the initial mixture of the second and third elements, or by impregnation of the network consisting of the second and third elements. The presence of the third element is not essential. In one embodiment, the chemical polymerization of the first element within the interpenetrated networks thus formed is obtained by soaking in a solution containing at least one agent for polymerizing the first element (FeCI 3 for example). Depending on the polymerization solvent, the soaking time, the initial concentrations of the conjugated monomer and the thickness of the film, homogeneous or gradient networks can be obtained. Thus, for example, the three monomers forming the first, second and third elements are mixed initially as follows: A first network is formed from a mixture of the monomers of the second and third element (in our case, poly ( ethylene glycol) dimethacrylate (PEGDM) with diallyl carbonate of diethylene glycol (CR39) in the presence of a mixture of polymerization initiating agents (AIBN and POB). The polymerization of POE (from PEGDM) is carried out at 40 ° C. The polymerization of the (PC) from (CR39) is carried out at 80 ° C. The film formed then undergoes baking at 100 ° C. At this stage, the first interpenetrated network is obtained. The polymerization of the first element (that which provides electrochromic functionality) within the first network is obtained by soaking the previous first network in an oxidizing solution (FeCI 3 ...,) the excess of the monomers of the first element which have not reacted t removed by washing said network obtained after soaking in a methanol solution. For example, a functional system of two homogeneous self-supporting films, as previously described (POE / PC / PEDT) framing a self-supported film based on the second and third element (POE / PC), the whole associated with active layers forming electrodes lower and upper is functional and allows to obtain contrasts higher than 3 between an oxidized and reduced state. This assembly is represented in the table below and has optical characteristics (Tl for example) comparable to those obtained for electrochromic systems known from the prior art (namely obtained by electrodeposition techniques.
Selon un deuxième mode de réalisation du film autosupporté, l'obtention du réseau reprend les principales étapes de la méthode d'obtention du réseau précédent. Le premier réseau formé des second et troisième éléments est obtenu d'une manière similaire sauf en ce qui concerne la présence du premier élément. Celui-ci n'est pas présent initialement dans le mélange avec les deux autres. Le premier réseau (POE/PC) sous une forme polymérisée est trempé dans une solution de monomère à base de premier élément pur (dans notre exemple, on rappelle que le premier élément est notamment à base de EDT). Après gonflement de la matrice du réseau POE/PC par l'EDT, la polymérisation est obtenue par trempage du premier réseau gonflé dans une solution oxydante (FeCI3, Tosylate de Fer,...). La pénétration du monomère puis de l'agent de polymérisation dans la matrice gonflée n'étant pas homogène dans l'épaisseur du film autosupporté, le réseau obtenu est à gradient. La quantité de PEDT est plus importante en surface qu'au centre du film. En faisant varier la nature du solvant de la solution de polymérisation, le gradient peut être ajusté. La formation du gradient de polymère conducteur dans la matrice isolante peut être suivi par l'évolution de rapport de la résistance ohmique à la surface du film par rapport à la résistance en épaisseur. En suivant l'évolution de ce rapport en fonction du temps d'immersion pour différents solvants, on peut observer l'influence de la nature du solvant et de la matrice sur la cinétique de polymérisation. Par un contrôle du temps d'immersion pour un solvant donné, il est possible de contrôler le gradient en polymère conducteur dans le film. L'exemple de réalisation montre que le dispositif electrocommandable intégrant un film autosupporté à gradient entre deux substrats verriers munies au niveau de leur face respective en regard du film des couches actives (et des éventuelles amenées de courant) permet d'obtenir des contrastes supérieurs à 3 entre un état oxydé et réduit. De même, préalablement à l'assemblage du film au sein des deux substrats, ledit film a été imprégné de sel de Li+ ou d'un autre cation et éventuellement d'un agent plastifiant. Cette imprégnation peut être réalisée lors des étapes d'élaboration du film, en incorporant dans le mélange de monomères des trois éléments le sel de Li+ ou un autre cation. Ces films autosupportés présentent un certain nombre d'avantages par rapport à une technique d'assemblage traditionnel (dépôt de couches) : - un seul film est utilisable industriellement pour insérer les fonctions électrochromes dans les applications envisagées (décrites ci-après) - l'interpénétration des deux espèces de polymères (le polymère électrochrome et le polymère de l'électrolyte) avec un gradient de polymère conducteur dans la matrice génère des couches extérieures créant de facto des surfaces de contact avec les électrodes (anode et cathode) sans en présenter les inconvénients (le délaminage) - le matériau électrochrome est partiellement protégé vis-à-vis de l'extérieur augmentant de ce fait la durée de vie du dispositif electrocommandable Par ailleurs, les deux verres formant les substrats du dispositif electrocommandable décrits précédemment sont en verre clair plan, standard, silico-sodo-calcique d'environ 2 mm d'épaisseur chacun. L'invention s'applique de la même manière à des verres bombés et/ou trempés. De même, au moins un des verres peut être teinté dans la masse, notamment teinté en bleu ou en vert, en gris, bronze ou brun. Les substrats utilisés dans l'invention peuvent aussi être à base de polymère (PMMA, PET, PC...). On note aussi que les substrats peuvent avoir des formes géométriques très variées : il peut s'agir de carrés ou de rectangles, mais aussi de tout polygone ou profil au moins partiellement courbe, défini par des contours arrondis ou ondulés (rond, ovale, « vagues », etc.). Par ailleurs, au moins un des deux verres (sur la face qui n'est pas munie du système électrochrome ou équivalent) peut être recouvert d'un revêtement comportant une autre fonctionnalité (cette autre fonctionnalité pouvant être par exemple un empilement anti-solaire, un empilement antisalissure ou autre). En tant qu'empilement anti-solaire, il peut s'agir d'un empilement de couches minces déposées par pulvérisation cathodique et comprenant au moins une couche d'argent. On peut ainsi avoir des combinaisons du type -verre/système électrochrome/couches anti-solaire/verre. -verre/système électrochrome/verre/thermoplastique/verre. -verre/système électrochrome/thermoplastique/verre Le thermoplastique peut être choisi parmi le PVB, PU.EVA On peut aussi déposer le revêtement anti-solaire non pas sur un des verres, mais sur une feuille de polymère souple du type PET (polyéthylènetéréphtalate). Pour des exemples de revêtements anti-solaires, on peut se reporter aux brevets EP 826 641 , EP844 219, EP 847 965, WO99/45415, EP 1 010 677. Le dispositif objet de l'invention précédemment décrit peut être aussi intégré au sein d'un « substrat » tri-verre, ce dernier étant avantageusement utilisé lors de l'élaboration de vitrages conformes aux exigences de sécurité. According to a second embodiment of the self-supporting film, obtaining the network takes up the main steps of the method for obtaining the previous network. The first network formed of the second and third elements is obtained in a similar manner except as regards the presence of the first element. This is not present initially in the mixture with the other two. The first network (POE / PC) in a polymerized form is dipped in a monomer solution based on the first pure element (in our example, it is recalled that the first element is in particular based on EDT). After swelling of the POE / PC network matrix by EDT, the polymerization is obtained by soaking the first swollen network in an oxidizing solution (FeCI3, Iron Tosylate, etc.). The penetration of the monomer and then of the polymerization agent into the swollen matrix not being homogeneous in the thickness of the self-supported film, the network obtained is gradient. The amount of PEDT is greater on the surface than in the center of the film. By varying the nature of the solvent in the polymerization solution, the gradient can be adjusted. The formation of the conductive polymer gradient in the insulating matrix can be followed by the change in ratio of the ohmic resistance at the surface of the film with respect to the thickness resistance. By following the evolution of this ratio as a function of the immersion time for different solvents, one can observe the influence of the nature of the solvent and of the matrix on the polymerization kinetics. By controlling the immersion time for a given solvent, it is possible to control the gradient of conductive polymer in the film. The exemplary embodiment shows that the electrically controllable device integrating a self-supporting gradient film between two glass substrates provided at their respective faces opposite the film with the active layers (and any current leads) makes it possible to obtain contrasts greater than 3 between an oxidized and reduced state. Likewise, prior to assembly of the film within the two substrates, said film was impregnated with Li + salt or another cation and optionally with a plasticizing agent. This impregnation can be carried out during the stages of preparation of the film, by incorporating into the mixture of monomers of the three elements the salt of Li + or another cation. These self-supporting films have a certain number of advantages compared to a traditional assembly technique (layer deposition): - a single film can be used industrially to insert the electrochromic functions in the envisaged applications (described below) - interpenetration of the two species of polymers (the electrochromic polymer and the electrolyte polymer) with a conductive polymer gradient in the matrix generates external layers creating de facto contact surfaces with the electrodes (anode and cathode) without presenting the disadvantages (delamination) - the electrochromic material is partially protected from the outside thereby increasing the life of the electrically controllable device Furthermore, the two glasses forming the substrates of the electrically controllable device described above are made of clear glass flat, standard, silica-soda-lime about 2 mm thick each. The invention applies in the same way to curved and / or toughened glasses. Likewise, at least one of the glasses can be tinted in the mass, in particular tinted blue or green, gray, bronze or brown. The substrates used in the invention can also be based on polymer (PMMA, PET, PC ...). We also note that the substrates can have very varied geometric shapes: they can be squares or rectangles, but also any polygon or profile at least partially curved, defined by rounded or wavy contours (round, oval, "waves", etc.). Furthermore, at least one of the two glasses (on the face which is not provided with the electrochromic system or equivalent) can be covered with a coating comprising another functionality (this other functionality being able for example to be an anti-solar stack, an anti-fouling stack or the like). As an anti-solar stack, it can be a stack of thin layers deposited by sputtering and comprising at least one silver layer. It is thus possible to have combinations of the type -glass / electrochromic system / anti-solar layers / glass. -glass / electrochromic system / glass / thermoplastic / glass. -glass / electrochromic system / thermoplastic / glass The thermoplastic can be chosen from PVB, PU.EVA The sunscreen coating can also be deposited not on one of the glasses, but on a sheet of flexible polymer of the PET type (polyethylene terephthalate) . For examples of anti-solar coatings, reference may be made to patents EP 826 641, EP 844 219, EP 847 965, WO99 / 45415, EP 1 010 677. The device which is the subject of the invention previously described can also be integrated within a tri-glass "substrate", the latter being advantageously used during the development of glazings which comply with safety requirements.

Claims

REVENDICATIONS
1. Dispositif electrocommandable à propriétés optiques/énergétiques de transmission ou de réflexion variables, caractérisé en ce qu'il est conformé en un seul film auto supporté, ledit film étant formé à partir d'un mélange polymérise d'au moins un premier élément adapté pour apporter une fonctionnalité électrochrome au mélange, et d'au moins un second élément adapté pour apporter une fonctionnalité d'électrolyte de transport de charges ioniques au sein dudit mélange. 1. Electrocontrollable device with variable optical / energy properties of transmission or reflection, characterized in that it is shaped as a single self-supporting film, said film being formed from a polymerized mixture of at least one first suitable element. to provide electrochromic functionality to the mixture, and at least one second element adapted to provide electrolyte functionality for transporting ionic charges within said mixture.
2. Dispositif selon la revendication 1 , caractérisé en ce que le mélange constitue une matrice unique qui est obtenue par polymérisation simultanée des premier et second éléments.2. Device according to claim 1, characterized in that the mixture constitutes a single matrix which is obtained by simultaneous polymerization of the first and second elements.
3. Dispositif selon la revendication 1 , caractérisé en ce que le mélange constitue une matrice unique qui est obtenue par polymérisation successive des premier et second éléments.3. Device according to claim 1, characterized in that the mixture constitutes a single matrix which is obtained by successive polymerization of the first and second elements.
4. Dispositif selon l'une des revendications 1 ou 2, caractérisé en ce que le premier élément est un polymère conducteur.4. Device according to one of claims 1 or 2, characterized in that the first element is a conductive polymer.
5. Dispositif selon la revendication 4, caractérisé en ce que le premier élément est un polymère à base de 3, 4 alkylène dioxythiophène ou l'un de ses dérivés.5. Device according to claim 4, characterized in that the first element is a polymer based on 3,4 alkylene dioxythiophene or one of its derivatives.
6. Dispositif selon la revendication 4, caractérisé en ce que le premier élément est un polymère à base de carbazole ou l'un de ses dérivés.6. Device according to claim 4, characterized in that the first element is a polymer based on carbazole or one of its derivatives.
7. Dispositif selon la revendication 1 , caractérisé en ce que le premier élément est un mélange d'au moins deux matériaux électrochromes, l'un au moins ayant une coloration anodique, l'autre ayant une coloration cathodique.7. Device according to claim 1, characterized in that the first element is a mixture of at least two electrochromic materials, at least one having an anodic coloring, the other having a cathodic coloring.
8. Dispositif selon la revendication 7, caractérisé en ce que le matériau à coloration cathodique est un sel de bipyridine.8. Device according to claim 7, characterized in that the cathodically colored material is a bipyridine salt.
9. Dispositif selon la revendication 7, caractérisé en ce que le matériau à coloration anodique est à base de 5, 10-phénazine ou l'un de ses dérivés.9. Device according to claim 7, characterized in that the material with anodic coloring is based on 5, 10-phenazine or one of its derivatives.
10. Dispositif selon l'une des revendications 1 à 3, caractérisé en ce que le second élément est un polymère choisi parmi les polyoxyalkylènes 10. Device according to one of claims 1 to 3, characterized in that the second element is a polymer chosen from polyoxyalkylenes
1 1. Dispositif selon la revendication 10, caractérisé en ce que le second élément est choisi parmi les polyoxyéthylènes ou l'un de ses dérivés.1 1. Device according to claim 10, characterized in that the second element is chosen from polyoxyethylenes or one of its derivatives.
12. Dispositif selon l'une des revendications 10 ou 1 1 , caractérisé en ce que le second élément est à base de poly(éthylène glycol) difonctionnel ou l'un de ses dérivés.12. Device according to one of claims 10 or 1 1, characterized in that the second element is based on poly (ethylene glycol) difunctional or one of its derivatives.
13. Dispositif selon l'une des revendications 1 à 12, caractérisé en ce que le film auto supporté comporte au moins un troisième élément adapté pour améliorer sa tenue mécanique ou pour améliorer la conductivité ionique. 13. Device according to one of claims 1 to 12, characterized in that the self-supporting film comprises at least a third element adapted to improve its mechanical strength or to improve the ionic conductivity.
14. Dispositif selon la revendication 13, caractérisé en ce que le troisième élément est un polymère choisi notamment parmi les polyacrylates, poly(méthacrylates), poly(carbonates), polyacétate, polyuréthanes, cellulosiques,...14. Device according to claim 13, characterized in that the third element is a polymer chosen in particular from polyacrylates, poly (methacrylates), poly (carbonates), polyacetate, polyurethanes, cellulosics, etc.
15. Dispositif selon l'une des revendications 13 ou 14, caractérisé en ce que le troisième élément est à base de diallyl carbonate de diéthylène glycol ou un de ses dérivés ou encore de poly(éthylène glycol)méthyl éther métacrylate.15. Device according to one of claims 13 or 14, characterized in that the third element is based on diallyl carbonate of diethylene glycol or one of its derivatives or also of poly (ethylene glycol) methyl ether metacrylate.
16. Dispositif selon l'une quelconque des revendications 1 à 15, caractérisé en ce que le film constitue un réseau interpénétré. 16. Device according to any one of claims 1 to 15, characterized in that the film constitutes an interpenetrating network.
17. Dispositif selon l'une quelconque des revendications 1 à 15, caractérisé en ce que le film constitue un réseau semi-interpénétré. 17. Device according to any one of claims 1 to 15, characterized in that the film constitutes a semi-interpenetrating network.
18. Dispositif selon l'une des revendications 1 à 16, caractérisé en ce qu'il présente un gradient de composition du premier élément situé selon une dimension caractéristique du film. 18. Device according to one of claims 1 to 16, characterized in that it has a composition gradient of the first element located along a characteristic dimension of the film.
19. Système incorporant au moins un dispositif selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il comporte en outre au moins un substrat porteur, ledit dispositif étant disposé entre deux amenées de courant, respectivement inférieure et supérieure (« inférieure » correspondant à l'amenée de courant la plus proche du substrat porteur, par opposition à l'amenée de courant « supérieure » qui est la plus éloignée dudit substrat)19. System incorporating at least one device according to any one of the preceding claims, characterized in that it further comprises at least one carrier substrate, said device being disposed between two current leads, respectively lower and upper ("lower" corresponding to the current supply closest to the carrier substrate, as opposed to the "upper" current supply which is the farthest from said substrate)
20. Système selon la revendication 19, caractérisé en ce qu'il s'agit d'un système électrochrome ou viologène.20. System according to claim 19, characterized in that it is an electrochromic or viologene system.
21 . Système selon l'une des revendications 19 ou 20, caractérisé en ce qu'il s'agit d'un toit auto pour véhicule, activable de façon autonome, ou d'une vitre latérale ou d'une lunette arrière pour véhicule, ou d'un rétroviseur.21. System according to either of Claims 19 or 20, characterized in that that it is a car roof for a vehicle, which can be activated independently, or a side window or a rear window for a vehicle, or a rear view mirror.
22. Système selon l'une des revendications 19 ou 20, caractérisé en ce qu'il s'agit d'un pare-brise ou d'une portion de pare-brise.22. System according to one of claims 19 or 20, characterized in that it is a windshield or a portion of the windshield.
23. Système selon l'une des revendications 19 ou 20, caractérisé en ce qu'il s'agit d'un panneau d'affichage d'informations graphiques et/ou alphanumériques, d'un vitrage pour le bâtiment, d'un rétroviseur, d'un hublot ou d'un pare-brise d'avion, ou d'une fenêtre de toit. 23. System according to one of claims 19 or 20, characterized in that it is a display panel for graphic and / or alphanumeric information, glazing for the building, a rear view mirror , an aircraft window or windshield, or a roof window.
24. Système selon l'une des revendications 19 ou 20, caractérisé en ce qu'il s'agit : - d'un vitrage intérieur ou extérieur pour le bâtiment, - d'un présentoir, comptoir de magasin pouvant être bombé, - d'un vitrage de protection d'objet du type tableau, - d'un écran anti-éblouissement d'ordinateur, - d'un mobilier verrier, - d'une paroi de séparation de deux pièces à l'intérieur d'un bâtiment ou d'une automobile24. System according to one of claims 19 or 20, characterized in that it is: - an interior or exterior glazing for the building, - a display, store counter that can be curved, - d '' protective glass for an object such as a painting, - a computer anti-glare screen, - glass furniture, - a partition wall of two rooms inside a building, or of an automobile
25. Système selon l'une quelconque des revendications 19 à 24, caractérisé en ce qu'il fonctionne en transmission ou en réflexion.25. System according to any one of claims 19 to 24, characterized in that it operates in transmission or in reflection.
26. Système selon l'une des revendications 19 à 25, caractérisé en ce que le substrat est transparent, plan ou bombé, clair ou teinté dans la masse, de forme polygonale ou au moins partiellement courbe.26. System according to one of claims 19 to 25, characterized in that the substrate is transparent, flat or curved, clear or tinted in the mass, of polygonal shape or at least partially curved.
27. Système selon l'une des revendications 19 à 26, caractérisé en ce que le substrat est opaque ou opacifié.27. System according to one of claims 19 to 26, characterized in that the substrate is opaque or opacified.
28. Système selon l'une des revendications 19 à 27, caractérisé en ce qu'il incorpore une autre fonctionnalité.28. System according to one of claims 19 to 27, characterized in that it incorporates another functionality.
29. Procédé d'obtention d'un dispositif selon l'une quelconque des revendications 1 à 18, caractérisé en ce que : - on mélange le second élément avec éventuellement le troisième élément en présence d'un agent initiateur de polymérisation, - on procède à la polymérisation du second élément par activation thermique du mélange et on poursuit l'activation thermique du mélange afin d'obtenir la polymérisation du troisième élément, - le deuxième et le troisième élément sont polymérisés ou copolymérisés en une étape par activation thermique du mélange29. Process for obtaining a device according to any one of claims 1 to 18, characterized in that: - the second element is mixed with optionally the third element in the presence of a polymerization initiating agent, - one proceeds to the polymerization of the second element by thermal activation of the mixture and the thermal activation of the mixture is continued in order to obtain the polymerization of the third element, - the second and the third element are polymerized or copolymerized in one step by thermal activation of the mixture
30. Procédé d'obtention selon la revendication 29, caractérisé en ce qu' - on ajoute au mélange des second et troisième éléments, le premier élément, - on polymérise le premier élément par trempage du mélange à l'aide d'un agent initiateur de polymérisation - on effectue un rinçage du mélange30. Obtaining method according to claim 29, characterized in that - the first element is added to the mixture of second and third elements, - the first element is polymerized by soaking the mixture using an initiating agent polymerization - the mixture is rinsed
31. Procédé selon la revendication 29, caractérisé en ce qu' - on effectue une mise en contact du mélange polymérise des second et troisième éléments dans un bain à base du premier élément, - on polymérise le premier élément par trempage du mélange à l'aide d'un agent initiateur de polymérisation - on effectue un rinçage du mélange. 31. Method according to claim 29, characterized in that - the polymerization mixture of the second and third elements is brought into contact in a bath based on the first element, - the first element is polymerized by soaking the mixture with using a polymerization initiating agent - the mixture is rinsed.
32. Procédé selon l'une des revendications 29 à 31 , caractérisé en ce que le film est imprégné de sel de Li+ , ou d'un autre cation, et éventuellement d'un agent plastifiant. 32. Method according to one of claims 29 to 31, characterized in that the film is impregnated with Li + salt, or another cation, and optionally with a plasticizing agent.
33. Procédé selon l'une des revendications 29 à 31 , caractérisé en ce que l'imprégnation du film est réalisée lors des étapes d'élaboration du film, en incorporant dans le mélange de monomères des trois éléments, un apporteur de charge- 33. Method according to one of claims 29 to 31, characterized in that the impregnation of the film is carried out during the stages of preparation of the film, by incorporating into the mixture of monomers of the three elements, a charge supplier.
EP04767671A 2003-07-16 2004-07-13 Electrically-controllable film having variable optical and/or energy properties Withdrawn EP1649320A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0308647A FR2857759B1 (en) 2003-07-16 2003-07-16 ELECTROCOMMANDABLE FILM WITH VARIABLE OPTICAL AND / OR ENERGY PROPERTIES
PCT/FR2004/001841 WO2005008326A1 (en) 2003-07-16 2004-07-13 Electrically-controllable film having variable optical and/or energy properties

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EP (1) EP1649320A1 (en)
JP (1) JP2007529025A (en)
KR (1) KR20060065630A (en)
CN (1) CN1823297A (en)
AR (1) AR047555A1 (en)
BR (1) BRPI0412642A (en)
FR (1) FR2857759B1 (en)
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WO (1) WO2005008326A1 (en)

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BRPI0412642A (en) 2006-09-26
JP2007529025A (en) 2007-10-18
CN1823297A (en) 2006-08-23
AR047555A1 (en) 2006-01-25
US20070041074A1 (en) 2007-02-22
FR2857759B1 (en) 2005-12-23
FR2857759A1 (en) 2005-01-21
MXPA06000602A (en) 2006-04-11
WO2005008326A1 (en) 2005-01-27

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