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.

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• Physics & Mathematics (AREA)
• Nonlinear Science (AREA)
• Chemical & Material Sciences (AREA)
• Optics & Photonics (AREA)
• General Physics & Mathematics (AREA)
• Inorganic Chemistry (AREA)
• Electrochemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Optical Elements Other Than Lenses (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Laminated Bodies (AREA)

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• 2003
  • 2003-07-16 FR FR0308647A patent/FR2857759B1/fr not_active Expired - Fee Related
• 2004
  • 2004-07-13 KR KR1020067000921A patent/KR20060065630A/ko not_active Application Discontinuation
  • 2004-07-13 US US10/564,195 patent/US20070041074A1/en not_active Abandoned
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  • 2004-07-13 EP EP04767671A patent/EP1649320A1/de not_active Withdrawn
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  • 2004-07-13 WO PCT/FR2004/001841 patent/WO2005008326A1/fr active Application Filing
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