WO2004074920A1 - Procede de production de corps composites electrochromes et corps composites electrochromes - Google Patents

Procede de production de corps composites electrochromes et corps composites electrochromes Download PDF

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Publication number
WO2004074920A1
WO2004074920A1 PCT/EP2004/001527 EP2004001527W WO2004074920A1 WO 2004074920 A1 WO2004074920 A1 WO 2004074920A1 EP 2004001527 W EP2004001527 W EP 2004001527W WO 2004074920 A1 WO2004074920 A1 WO 2004074920A1
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WIPO (PCT)
Prior art keywords
electrochromic
layer
electrolyte layer
sealant
interior
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PCT/EP2004/001527
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German (de)
English (en)
Inventor
Bernd Bronstert
Original Assignee
Basf Aktiengesellschaft
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Publication of WO2004074920A1 publication Critical patent/WO2004074920A1/fr

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    • 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
    • G02F1/153—Constructional details
    • G02F1/161—Gaskets; Spacers; Sealing of cells; Filling or closing of cells
    • 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
    • G02F2202/00—Materials and properties
    • G02F2202/02—Materials and properties organic material
    • G02F2202/022—Materials and properties organic material polymeric

Definitions

  • the present invention relates to the provision of air-bubble-free, robust and stable composite bodies, in particular for use in electrochromic systems, electrochromic glazing comprising such composite bodies, and a method for producing such composite bodies.
  • Electrochromic glazing typically has the following layer sequence:
  • Substrate e.g. glass or foil
  • transparent electrically conductive layer electrode
  • electrochromic functional layer solid
  • electrolyte transparent electrically conductive layer
  • counter electrode substrate
  • Such electrochromic composite bodies are typically produced by covering a glass substrate with a transparent, electron-conducting layer and with an electrochromic layer.
  • a second carrier is also provided with a transparent electron-conducting layer, which serves as a counter electrode.
  • An electrolyte layer is then either on the counter electrode or on the electrochromic Layer applied and the two carriers, with the uncoated sides facing away from each other, pressed together and laminated.
  • the composite body is then usually heated using temperature until the electrolyte layer (mostly a conductive polymer) becomes adhesive. Typical conditions are 85 ° C and pressures of 5 x 10 5 Pa and 6 l0 5 Pa.
  • the composite body is then typically sealed at its periphery to prevent entry of air and moisture and to increase the durability of the composite body.
  • the sealing is typically done by applying sealing tapes or by injecting sealants.
  • a disadvantage of this method is that the subsequent sealing does not fully guarantee that air and moisture are excluded and that the formation of air bubbles or air microbubbles cannot be prevented.
  • Another disadvantage of such conventional methods is that contact points or wires are attached after the sealing, which is usually done by drilling corresponding holes in the composite body. This in turn can lead to air and moisture ingress and, due to the drilling process, undesirable discolouration.
  • No. 5,244,557 describes a method for the production of air-bubble-free electrochromic composite bodies, in which the coated supports are placed parallel to one another at a distance of approximately 10 mm.
  • One of the carriers contains a thermoplastic sealant on the periphery, the carriers being heated under vacuum, as a result of which the solid electrolyte adheres, the sealant deforms and seals the composite body.
  • the object of the present invention is to provide a cost-effective method for producing air-free, durable and unbreakable, electrochromic composite bodies.
  • the present invention also relates to a method for
  • Another object of the invention is to provide a method for producing the above composite body, in that contact points and / or electron conductors, for example wires, can be attached before the sealing.
  • this object is achieved by a method in which
  • At least one electrochromic functional layer is applied to an optically transparent, electron-conductive surface of a first and a second substrate;
  • a deformable, optically transparent, electrolyte layer ES is applied to at least one of the electrochromic functional layers;
  • the substrates with the coated surfaces are directed towards one another, under largely air and moisture-excluding conditions,
  • a deformable sealant D is applied so that at least the layer ES is surrounded and sealed by the sealant when pressed together in iii), and a composite body produced by this method.
  • Another object of the present invention was to provide an electrochromic composite body that is shatterproof, durable, and free of air bubbles.
  • this object is achieved by a composite body containing at least two substrates, each with at least one optically transparent, electron-conductive surface, forming an interior I and an area B between said surfaces, area B surrounding the interior peripherally, said interior containing at least one layer sequence comprising an electrochromic Layer, an electrolyte layer ES, another electrochromic layer and said area B containing a sealant D plastic at room temperature, sealing the interior I.
  • the composite bodies according to the invention are particularly suitable for use in electrochromic windows, displays and glazing for automobiles or buildings.
  • the present invention therefore also relates to the use of an inventive
  • Displays, glazing and windows encompass the composite body.
  • glazing comprising a composite body according to the invention to be heated by applying an alternating current.
  • This additional function in addition to the DC circuit for electrochromic glazing is particularly advantageous for glazing for automobiles.
  • the present invention therefore also relates to electrochromic glazing, comprising the composite body mentioned above.
  • Substrates in the sense of the invention can be metals, glasses, polymer films (e.g. PET, PC), mirrors or components of a display, at least one of the substrates being optically transparent.
  • the composite body preferably has at least one substrate which comprises glass, polymer or film.
  • optically transparent is understood to mean that the light absorption of the corresponding substance in the visible range is ⁇ 20%.
  • a transparent electrode is applied to at least one surface of the substrate, preferably in a thickness of 0.001 to 0.2 ⁇ m.
  • the transparent electrode on the surface of the substrate is generally brought about by vapor deposition or sputtering with thin transparent electron-conducting metal oxide layers or by wet-chemical coating with metal salt or gel layers, possibly with subsequent precipitation, for example hydroxide precipitation on the glass surfaces.
  • electrochemical deposition of analog layers is also possible. All of these layers are often stabilized, fixed or their effectiveness optimized by subsequent heat, pyrolysis or oxidation treatment.
  • coatings based on ITO, FTO, ATO, ie doped tin oxide layers are mostly used.
  • electrochromic properties mean that a composite body according to the invention shows a change in the light absorption, in particular in the visible range, when a voltage is applied.
  • the transparent, electron-conductive surfaces of the first and second substrates are each brought into contact with at least one electrochromic functional layer, which is typically done by applying the electrochromic functional layers.
  • the application can take place, for example, by vapor deposition or wet-chemical, for example by means of immersion or sol-gel processes.
  • the electrochromic layers according to the invention are applied in a thickness of 0.0001 to 2.0 ⁇ m, preferably in a thickness of 0.001 to 0.2 ⁇ m, or are present in the composite body in such a thickness.
  • An electrochromic functional layer according to the invention contains at least one component which imparts electrochromic properties to the functional layer.
  • all compounds known to the person skilled in the art which impart electrochromic properties to the composite body i.e. lead in particular to a color change in the visible range when voltage is applied.
  • Such components are, for example, compounds which have different light absorption, in particular in the visible range, in different oxidation states and can be reversibly transferred from one to the other oxidation state.
  • compounds are suitable which are colorless in one oxidation state and colored in a second.
  • Such compounds are, for example, dihydrophenazines or similar compounds as described in US Pat. No. 6,249,369 or US Pat. No. 5,278,693.
  • Preferred components are CeTiO 2 , V 2 O 5 , TiV 2 O 5 , CrV 2 0 5 , NbV 2 O 5 , Ni (OH) 2 , b 2 ⁇ 5 , WO 3 , Ir 2 ⁇ 2 or a mixture of two or more of these compounds, which may also contain other metal atoms intercalated in their lattice.
  • WO 3 is particularly preferred.
  • the electrochromic layers according to the invention can contain further additives and auxiliaries known to the person skilled in the art.
  • additives and auxiliaries are, for example, binders, precipitants or leveling agents.
  • An electrolyte layer, ES is applied to at least one of the electrochromic functional layers.
  • All methods known to those skilled in the art for applying electrolyte layers can be used for this purpose (examples are wet-chemical methods for coating with the electrolyte, for example casting, painting, spraying, immersion, spincoat, reverse coat, sol-gel coating methods, direct methods) or indirect application of a viscous melt or solution, hot, cold, as well as pressure or wet laminate processes, combine under a certain contact pressure of a preformed solid, thermoplastic or plastic electrolyte layer with at least one of the EC functional layers or simply by placing the layers on top of each other).
  • the electrolyte layer according to the invention is optically transparent, deformable and is preferably applied in a thickness of 0.001 to 50 mm, preferably of 0.01 to 5 mm.
  • a particularly preferred electrolyte layer is a solid electrolyte layer.
  • the electrolyte layer is in the form of a film.
  • the .thickness of the film is selected depending on the desired application.
  • the foils can have thicknesses between 5 ⁇ m and 5 mm.
  • the films preferably have a thickness of 10 ⁇ m to 2 mm, in particular 100 ⁇ m to 1.5 mm, particularly preferably 0.5 to 1 mm.
  • the electrolyte layer has at least one of the properties (1) to (3):
  • glass transition temperature T g ⁇ -30 ° C is to be understood here in such a way that in a standard DSC device between -30 ° C and 120 ° C, i.e. in the temperature range in which glazing for buildings and in the vehicle sector is usually used , no clear turning point can be seen in the DSC curve.
  • the electrolyte layer fulfills all of the properties (1) to (3).
  • the conductivity at 20 ° C. of the electrolyte layer is preferably greater than 10 S / cm, in particular greater than 10 " S / cm.
  • the electrolyte layer according to the invention preferably contains a filler with a primary particle size of 1 nm to 20 ⁇ m, for example from 1 nm to 1000 nm, in particular from 1 nm to 500 nm, preferably from 1 nm to 300 nm, particularly preferably from 1 nm to 100 nm or also 5 to 10 nm.
  • this information relates to the diameter, in the case of irregularly shaped particles, such as, for example, in the case of needle-shaped particles, to the longest axis.
  • a very finely divided solid is preferably used, the primary particle size being in the range of the wavelength of visible light, so that an optically transparent solid electrolyte is obtained.
  • Suitable fillers are, for example, polymer particles which can also be crosslinked, such as those made of polystyrene, polycarbonate, or polymethyl methacrylate (eg Agfaperl ®).
  • inorganic fillers are Glass powder, nano glass particles, such as Monospher ® (Fa. Merck), glass microparticles, for example Spheriglass ® (FA. Potters-Ballotini).
  • Inorganic oxides and mixed oxides, in particular of the elements silicon, aluminum, magnesium, titanium or calcium, are also suitable.
  • fillers are silicon dioxide, in particular pyrogenic oxides, for example Aerosil ® (Messrs. Degussa), silicates, such as talc, pyrophyllite, wollastonite, aluminosilicates, for example feldspar or zeolites.
  • the fillers can also be coated with suitable dispersing aids, adhesion promoters or water repellents. Mixtures of two or more fillers can also be used. Particularly preferred are hydrophobic fumed Kieselgel Textren such as Aerosil ® R812, Aerosil ® R8200, Aerosil ® R974. Further fillers which can be used in the context of the invention are described in US Pat. No. 6,361,709.
  • the electrolyte layer or foil contains a high proportion, preferably greater than 10% by weight, of pyrogenic silica as a filler.
  • the filler is usually present in an amount of 1 to 80% by weight, based on the sum of all components of the electrolyte layer.
  • the electrolyte layer preferably contains 8 to 78% by weight of the filler, particularly preferably 10 to 67% by weight, in particular 20 to 50% by weight.
  • the electrolyte layer can also contain one or more binders.
  • binders In principle, all thermoplastically processable polymers with sufficient transparency are suitable as binders. Thermoplastics which have a light absorption of less than 20% in the UV / VIS range are particularly suitable.
  • binders which can be used in the context of the present invention are described in US Pat. No. 6,361,709.
  • the R 2 radicals can also carry one or more substituents, in particular chlorine or fluorine.
  • substituents include 2,2,2-trifluroethyl, 2,2,3,3-tetrafluoropropyl or 1,1,1,3,3,3, - hexafluoroisopropyl groups. Mixtures of two or more acrylates can also be used.
  • optically transparent polymers such as ethylene vinyl acetate (EVA), modified and unmodified polyvinyl alcohols, polyvinyl chloride (PVC) or polystyrene are also suitable.
  • Copolymers of acrylates with one or more comonomers can also be used as the polymeric binder.
  • the following are particularly suitable as comonomers:
  • acrylic or methacrylamide can be considered in the groups mentioned above under R 2 .
  • Suitable imides for example maleimide, can also be used.
  • the radical R 1 preferably represents hydrogen or methyl
  • the radicals R 2 and R 3 preferably denote hydrogen or hydrocarbon radicals.
  • Styrene is preferred as the comonomer.
  • Decene, cyclohexene and norbornene Preferred comonomers are ethylene, propylene and 1-butylene.
  • binders which can be processed thermoplastically are those polymers which are usually used for producing optical components from plastics. Such polymers and their properties are, for example, in "Optical Plastics”(Ullmann's Encyclopedia of Industrial Chemistry, 6 ⁇ Edition, 1998, Electronic Release).
  • polymers examples include polymethylmemacrylate, polycyclohexyl methacrylate, copolymers of cyclohexyl methacrylate and methyl methacrylate, copolymers of cyclohexyl methacrylate and / or methyl methacrylate and styrene, polystyrene, styrene / acrylonitrile copolymers, copolymers of styrene and maleic anhydride and polyphenols such as, for example, polycarbonates such as polycarbonates, Polyvinyl butyral, partially or fully hydrolyzed polyvinyl acetate / polyvinyl alcohol or their copolymers such as, for example, ethylene / polyvinyl acetate copolymers, diphenyl sulfide carbonate, polytrifluoromethylstyrene, polymethylpentene or cellulose esters such as, for example, cellulose acetate, cellulose propionate or cellulose
  • Mixtures of two or more different polymeric binders can also be used in the context of the present invention, provided that the polymers are compatible with one another.
  • the molecular weight of the polymers can be selected depending on the desired properties of the solid electrolyte.
  • the glass transition temperature of the polymer used should preferably be less than -30 ° C.
  • the polymeric binder is usually present in an amount of 5 to 97% by weight, preferably in an amount of 10 to 80% by weight, particularly preferably 20 to 50% by weight, in each case based on the sum of all constituents of the electrolyte layer contain.
  • the electrolyte layer according to the invention can also contain at least one conductive salt.
  • Examples of suitable cations for the conductive salt are H " , Li + , Na + , K + , Cs, Mg 2+ or Ag + . Preferred cations in the context of the present invention are H + or Li + .
  • Examples of suitable conductive salts III are LiCl, LiPF 6 , LiBF 4 , LiAsF 6 , LiCF 3 SO 3 , LiC (CF 3 SO 2 ) 3 , LiN (CF 3 SO 2 ) 2 , Li (C n F 2n + 1 ) SO 3 , LiC [(C n F 2n + 1 ) SO 2 ] 3 , LiNtCJ ⁇ SOJ ,, with n each 2 to 20, LiClO 4 , LiN (SO 2 F) 2 , LiSbF 6 , LiAlCl 4 , LiSiF 6 , NaPF 6 , NaBF 4 , NaCF 3 SO 3 , NaClO 4 , KPF 6 , KBF 4 , KCF
  • Organic salts such as sodium octyl sulfate, lithium dodecylbenzenesulfate can also be used.
  • LiClO 4 , LiN (CF 3 SO 2 ) is preferred as the conductive salt. 2 or LiCF 3 SO 3.
  • mixtures of two or more conductive salts can also be used.
  • the electrolyte layer can also have polymer-bound ionic groups.
  • polymer-bound acid anions are preferred according to the invention which have H + or Li + counterions.
  • the conductive salt is usually present in an amount of 0.5 to 40% by weight, based on the sum of all components of the electrolyte layer.
  • the electrolyte layer preferably contains 1 to 20% by weight of the conductive salt, particularly preferably 2 to 8% by weight.
  • the sum of the ionic groups preferably corresponds to 0.05 to 4 mol / 1, in particular 0.1 to 2 mol / 1, particularly preferably 0.2 to 0.8 mol / 1.
  • the electrolyte layer according to the invention can moreover. also contain plasticizers.
  • plasticizers Usual, high-boiling plasticizers or solvents are suitable as plasticizers. It is advantageous to use plasticizers which can solvate clays, especially Li ions. On the one hand, the plasticizers act as solvents for the conductive salts and continue to influence the mechanical properties of the solid electrolyte, for example by lowering its glass transition temperature. Suitable plasticizers compatible with the binder and filler used in each case are selected by the person skilled in the art. It should be noted that the plasticizer must not significantly impair the transparency of the solid electrolyte. Both protic and aprotic plasticizers can be used.
  • protic plasticizers examples include glycol and oligomeric polyethylene glycols or polypropylene glycols which have terminal OH groups. Such plasticizers are for example available under the trade name Pluriol ®. Primary alcohols such as 2-ethylhexanol can also be used.
  • aprotic plasticizers are linear or cyclic organic carbonates of the general formula R 4 O (CO) OR 5 , where R 4 and R 5 each represent straight-chain or branched alkyl radicals or aryl radicals which also carry inert substituents, such as chlorine or bromine can. Those carbonates with 1 to 6 carbon atoms are particularly suitable. R 4 and R 5 can also be connected to one another to form a 5- or 6-membered ring, for example. C atoms can also be substituted by O atoms.
  • Examples of such carbonates are ethylene carbonate, propylene carbonate, butylene carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, di (2-methoxyethyl) carbonate or di (2-butoxyethyl) carbonate.
  • Organic phosphates R'R “R '” P ⁇ 4 are also suitable, where R', R “and R '" each represent straight-chain or branched alkyl radicals having 1 to 8 carbon atoms or aryl radicals, which can also be further substituted. In particular, carbon atoms can also be substituted by O.
  • R ', R "and R m can also be connected in pairs to form a ring.
  • Suitable phosphates are trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triisobutyl phosphate, tripentyl phosphate, trihexyl phosphate, toctyl phosphate, tris (2-ethylhexyl) phosphate, tris Diethyl-n-butyl phosphate, tris (butoxyethyl) phosphate, tris (2-methoxyethyl) phosphate, tris (tetrahydrofuryl) phosphate, tris (lH, lH, 5H-octafluoropentyl) phosphate, tris (lH, lH-trifluoroethyl) phosphate, tris ( 2- (the ylamino) ethyl) phosphate, tris (methoxyethoxyethyl) phosphate, tris (ethoxycarbonyloxy
  • esters of organic acids for example esters of adipic acid or phthalic acid such as 2-ethylhexyl adipate or 2-ethylhexyl phthalate.
  • Cyclic esters such as omega - (+/-) - butyrolactone, dimethyl-omega-butyrolactone, diethyl-omega-butyrolactone, omega-valerolactone, 4,5-dimethyl-1,3-dioxolan-2-one, 4,4 can be advantageous -Dimethyl-l, 3-dioxolan-2-one, 4-ethyl-l, 3-dioxolan-2-one, 4-methyl-5-ethyl-1, 3-dioxolan-2-one, 4,5-diethyl - 1,3-dioxolan-2-one, 4,4-diethyl-1,3-dioxolan-2-one, 1,3-dioxan-2-one, 4-
  • Esters of inorganic acids which have - (CH 2 -CH 2 0) n CH 3 groups in particular esters of boric acid, carbonic acid, sulfuric acid and phosphoric acid, can also advantageously be used. Esters of the type mentioned are disclosed by WO 98/44576, pages 27 to 31.
  • ethers such as, for example, dibutyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, didodecyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, 1,2-dimethoxypropane, diethylene glycol dibutyl ether, triethylene glycol ethylene glycol, 1,4-methyl ether, tetra-ethylene glycol -Dioxane, 1,3-dioxane, 2,5-diethoxy-tetrahydrofuran or 2,5-dime oxytetrahydrofuran.
  • plasticizers that can be used in the context of the invention are mentioned in US Pat. No. 6,361,709.
  • the plasticizer is usually contained in an amount of 0 to 90% by weight, based on the sum of all constituents of the electrolyte layer.
  • the electrolyte layer preferably contains 1 to 70% by weight, in particular 10 to 50% by weight, of the plasticizer, particularly preferably 20 to 40% by weight.
  • the electrolyte layer according to the invention can also contain further additives and auxiliaries.
  • antioxidants such as Irganox ® , Ultranox ® or Sicostab ®
  • UV stabilizers such as Uvinul ® or ⁇ rgastab ®
  • dispersion aids such as Lutensol ® or Sokalan ® be used for the filler or adhesion promoters.
  • the amount of additives and auxiliaries can be selected by the person skilled in the art as required. According to the invention, the proportion of additives and auxiliaries, based on the sum of the constituents of the electrolyte layer, is not greater than 30% by weight, preferably not greater than 20% by weight, in particular not greater than 10% by weight.
  • the electrolyte layer according to the invention can be uncrosslinked, but can also be crosslinked. In the latter case, it also contains the reaction products of compounds added for crosslinking, for example the polymers resulting from the photopolymerization of ethylenically unsaturated compounds with suitable photoinitiators.
  • All components of the electrolyte layer according to the invention form a homogeneous, preferably a colorless and crystal-clear mass.
  • the filler is preferably evenly dispersed in the binder and the conductive salt is preferably completely dissolved.
  • the light absorption of the electrolyte layer is preferably less than 20%, particularly preferably less than 15%.
  • the electrolyte layer according to the invention can also be milky, that is to say having higher scattering components, or colored if this is necessary for a specific application.
  • the electrolyte layer can be produced, for example, by melt extrusion.
  • the invention also encompasses other procedures, such as dissolving all of the constituents except the filler in a suitable solvent, uniformly dispersing the filler therein, pouring a layer onto a suitable substrate and evaporating the solvent again.
  • Another variant of the process is to first produce a solid electrolyte without the conductive salt, and to introduce the conductive salt only at a later point in time by soaking the solid electrolyte with a solution of the conductive salt in a suitable solvent.
  • the electrolyte layer according to the invention can also be crosslinked.
  • the crosslinking can take place thermally by adding thermal crosslinkers to the starting materials which do not yet crosslink at the melt extrusion process temperature. After the molding, the crosslinking is triggered by heating the molded body or the film to higher temperatures. However, radiation crosslinking is preferably carried out. Crosslinkers or auxiliaries required for this, such as photoinitiators, are added to the starting materials and compounded with them and melt-extruded.
  • Radiation crosslinking can take place, for example, by irradiation with high-energy radiation, such as ionic radiation, ionizing radiation, electron beams, X-rays or gamma rays, if appropriate using additional initiators.
  • Crosslinking is advantageously carried out with actinic light, in particular with UV light.
  • polymerizable compounds or monomers are used in a known manner.
  • the monomers have at least one polymerizable ethylenic double bond.
  • the choice of type and amount depends on the desired properties of the electrolyte layer and the compatibility with the other components, in particular with the binder.
  • Polar monomers that bind or solvate ions and thus contribute to conductivity are particularly suitable.
  • Examples of preferred compounds are those having hydroxyl groups, amide groups or polyethylene glycol structural units.
  • Mono- and polyacrylates and / or methacrylates of mono- and polyhydric alcohols are also very suitable.
  • (meth) acrylic acid esters of alkanols having 1 to 20 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, cyclohexyl (meth) acrylate
  • (Meth) acrylic esters of polyhydric alcohols with 2 to 20 carbon atoms e.g.
  • epoxy and urethane (meth) acrylates such as, for example, by reacting bisphenol A diglycidyl ether with (meth) acrylic acid or by reacting mono- or diisocyanates with hydroxyalkyl (meth) acrylates and, if appropriate, with polyesters containing hydroxyl groups or Polyethers can be obtained.
  • Derivatives of the are also suitable Acrylamides and methacrylamides, for example ethers of their N-methylol derivatives with mono- and polyhydric alcohols, such as ethylene glycol, glycerol, 1,1,1-trimethylolpropane, oligomeric or polymeric ethylene oxide derivatives.
  • Suitable initiators for the photopolymerization include benzoin or berrzoin derivatives, such as alpha-methylbenzoin or benzoin ether, benzene derivatives, such as benzil ketals, acylarylphosphine oxides, acylarylphosphinic acid esters, Melrrkemchinone or benzophenones.
  • Crosslinking with actinic light can take place immediately after the production of the electrolyte layer, that is to say, for example, by irradiating and crosslinking the electrolyte film produced by extrusion with a suitable radiation device directly behind the extruder. However, it can also be networked at a later point in time, for example only after installation in an electrochromic glazing.
  • the method can also include a further step in which at least one adhesion-giving component is applied before step iv.
  • adhesion-promoting compounds known to the person skilled in the art can be used as adhesion-giving components in the context of the invention, provided that they are compatible with the other chemical components.
  • Modified polyvinyl alcohols are particularly advantageous components. According to the invention, mixtures of two or more different modified polyvinyl alcohols can also be used. In the context of the present invention, particular preference is given to acetals, semi-acetals or ketals of a polyvinyl alcohol, for example polyvinyl butyral.
  • the adhesion-giving component can also be applied together with an electrochromic functional layer, electrolyte layer or sealant or incorporated into these layers or the sealant.
  • At least one separate layer is applied which contains at least one adhesion-giving component.
  • This layer is preferably less than 1 ⁇ m in thickness, particularly preferably in a thickness applied smaller than 0.1 ⁇ m.
  • one or more of these layers can be applied, for example, to one or more electrochromic layers, to the electrolyte layer or to the sealant. It is also possible for one or more of these layers to be introduced into the electrolyte layer, for example by applying an electrolyte layer, followed by applying a layer containing an adhesion-promoting component, again followed by applying an electrolyte layer.
  • a sealant D is applied before the substrates are pressed together.
  • the sealant in the sense of the invention is deformable and is impermeable to air and moisture.
  • a sealant that is plastic at room temperature is preferred. Any such sealant known to those skilled in the art can be used within the scope of the invention.
  • the sealant should match those used in the ES layer
  • a sealant with adhesive properties can be selected, i.e. it can be sticky or that
  • Adhesive materials can be added to the sealant.
  • Suitable sealants for the purposes of the invention are, for example: PUB, PIB copolymers with other olefins, for example with styrene end blocks, polyolefins in general, PP, PE, PE-
  • Copolymers for example EVA or PE / AS copolymers, PS, thermoplastic rubbers based on isoprene-styrene, butadiene-styrene or PUR, acrylates, epoxy resins,
  • the sealant is applied in such a way that it encloses the layer ES airtight and moisture-tight at least during and / or after being pressed together. This can be achieved, for example, by only partially covering the surface and / or the electrochromic layer by the layer ES and by leaving a region surrounding the layer ES which can then be filled in by the sealant. Typically, this range is 1 to 100, preferably 2 to 20 mm.
  • the sealant has at least the thickness of the layer ES.
  • the sealant can also be applied to the substrate first and then, in the area that remains free, the layer ES.
  • the sealant can be applied both to the first and to the second substrate or in parts to both substrates.
  • At least the surface of the first substrate is only partially coated with the electrochromic functional layer and electrolyte layer, and an area surrounding the layers remains left out. This range is preferably 0.2 to 2 mm wide. This area contains sealant D either before or after application of the layers.
  • the individual are brought into contact by pressing the substrates together, and the composite body is produced.
  • the first and second substrates (with the previously coated surfaces facing each other) are pressed together with the exclusion of air, e.g. by reduced air pressure or by applying a vacuum or by applying an essentially oxygen and / or moisture-free atmosphere.
  • the substrates are pressed together under reduced air pressure at a pressure of less than 100 Pascal.
  • the compression is typically carried out with a pressure of at least 10,000 Pascal (N / m 2 ).
  • the compression is typically carried out at a temperature between 4 and 30 degrees Celsius, preferably at room temperature 25 degrees Celsius, but, if desired, can also be carried out at a temperature greater than 30 degrees Celsius.
  • the sealant By pressing the electrolyte layer into contact with the other electrochromic layers, the sealant is deformed and the solid electrolyte is sealed against the ingress of air and oxygen.
  • the invention relates to a composite body with electrochromic properties, which is durable, unbreakable and free of air bubbles.
  • the composite body contains at least two substrates, which are either optically transparent and electron-conductive or have at least one optically transparent, electron-conductive surface. The substrates form an interior I between them or between said surfaces.
  • the interior comprises an electrochromic layer which is in contact with the substrate or optionally with the electron-conducting and optically transparent surface of the first substrate and a further electrochromic layer which is in contact with the second substrate or its electron-conducting and optically transparent surface.
  • the interior further comprises at least one electrolyte layer ES in contact with the electrochromic layers.
  • Area B is filled with a sealant D which is plastic at room temperature and which is also impermeable to air and moisture.
  • the composite body according to the invention can also have further layers.
  • a composite body according to the invention can have further optically transparent carrier layers, for example made of glass or optically transparent polymers, as well as one or more conductivity layers S.
  • the conductivity layer can be, for example, an ITO (indium tin oxide) layer, an FTO (fluorine-doped tin oxide) layer or an ATO (antimony-doped tin oxide) layer.
  • An optically highly transparent polymer electrolyte layer is produced by compounding in a twin-screw extruder from 17 parts by weight of PMMA, 17 parts by weight of PVB, 32 parts by weight of tetraethylene glycol dimethyl ether, 2 parts by weight of lithium perchlorate and 32 parts by weight of Aerosil® (pyrogenic silica) according to the teaching of US Pat. No. 6,361,709.
  • Aerosil® R8200 from Degussa was used as the fumed silica.
  • the melt is discharged via a slot die and two 0.125 mm thick separating films made of PET film siliconized on one side are placed in a calender so that a polymer electrolyte layer thickness of 0.75 mm results.
  • the polymer electrolyte film, (hereinafter referred to as SPE) between the two protective films, is aligned on one of the glasses (functional layer of the glass facing upwards!) So that an 8 mm wide edge remains free for the edge seal.
  • One side is then fixed to the glass surface with a self-adhesive tape.
  • the SPE is folded down by 180 °.
  • One of the PETP protective films is peeled off from the edge that was fixed to the glass with the tape so that the SPE does not detach from the second protective film.
  • the SPE is then raised to approx. 90 ° (vertical) at the non-fixed edge.
  • a rubber roller e.g.
  • the SPE is placed on the glass pane free of air bubbles and pressed on.
  • This lamination step can be carried out in a temperature range from room temperature to 120 ° C. For reasons of simplicity, the room temperature is preferred.
  • tempering in a circulating air dryer can then take place at 100 to 120 ° C (0.5 to 1 hour). This creates a very good adhesion to the glass.
  • the composite is then allowed to cool to room temperature (for 30 minutes).
  • the cohesion of the SPE increases again to the initial value, so that the second protective film can be removed without damage.
  • Annealing may also be omitted - if the second one is removed Protective film is possible without partial delamination from the glass substrate. This is the preferred method.
  • the next step is to prepare the edge seal (e.g. by applying a plastic adhesive sealant in the form of a bead, all around the polymer electrolyte layer).
  • the second protective film is then removed from the polymer electrolyte layer.
  • the second electrochromically coated glass pane with an air gap is positioned in an evacuable chamber with a precise fit over the first glass pane with polymer electrolyte and edge seal.
  • the chamber is then evacuated to, for example, 100 Pascal air pressure.
  • the two glass panes are then pressed against one another with a pressure of, for example, 10,000 to 100,000 Pascals or even more, for example by means of a hydraulic pressing device which is positioned under the lower glass pane.
  • the glazing can be autoclaved in the usual way, like the pre-composite of a double-pane safety laminated glass, whereby a temperature of 100 to 140 ° C should be set to ensure good adhesion to the glass panes. If treatment in an autoclave is not necessary, the EC laminated glass pane must be heated to> 100 ° C for at least 30 minutes to ensure good adhesion of the polymer electrolyte layer to the carrier layer (EC glass).
  • Tin oxide layer polymer electrolyte layer as described a 30 x 30 cm and 4 mm thick float glass, sputtered with an FTO conductivity and a WO 3 electrochromic layer.
  • the two glass panes had already been provided with self-adhesive copper foil on the front side on two opposite sides before processing into a bond.
  • an additional solder strip was applied on the front using the ultrasonic soldering process.
  • the wiring can be easily soldered or pressed on, for example, after the finished electochromic glazing has been produced.
  • the glazing thus produced was applied by applying 2.7 volts for 30 minutes. Voltage was formed, ie lithium cations from the polymer electrolyte were embedded in the lithium storage layer (TiV 2 O 5 ) for the first time. Thereafter, the electrochromic glazing produced in this way with 2.7 volt voltage could be darkened in 120 seconds from 64% transmission to 7% transmission, measured at 620 nm, and lighted again within 100 seconds.
  • the lens had a very good optical quality and was crystal clear with a light scatter of only 1.4%.
  • the boundary of the polymer electrolyte layer to the edge seal was completely sharp, in particular there were no air or residual gas inclusions left.
  • a 30-day storage showed no marginal effects even with repeated light / dark switching, which suggests a perfect seal against air humidity and oxygen.
  • the electrochromic glazing had safety glass properties, ie a 250 g steel ball from a height of 7 m did not break through the glazing and all the glass fragments were held in place by the polymer electrolyte film. Just some glass powder parted from the glazing. The so-called pummel test by security film processors (laminated glass manufacturers) was also passed.
  • Another disadvantage is that the sensitive glass edges are easily damaged or soiled with the electrical contact.
  • a further disadvantage is that the application of the sealant takes a long time in this way and moisture can diffuse for too long on the unsealed edges of the polymer electrolyte and then later side effects occur when switching on and off or a reduced service life of the electrochromic glazing.
  • electron-conductive dirt for example metal from the electrical contacting of the glass edges
  • a darkening or light coloring once set no longer remains constant for a few days after being disconnected from the voltage source, but the window is brightened or darkened after minutes or hours.
  • this filling process is much more expensive because the edge seal requires an additional step.
  • a faulty edge seal leads to the failure of the window's electrochromic function due to the penetration of moisture and / or oxygen. Discoloration, milky clouding or even delamination can also occur.

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un procédé de production de corps composites électrochromes, consistant à appliquer sur une surface conductrice d'électrons et optiquement transparente d'un premier et d'un second substrat au moins une couche fonctionnelle électrochrome, ainsi qu'une couche d'électrolyte et un produit d'étanchéité, puis à compacter les deux substrats. L'invention concerne également des corps composites produits par ce procédé, en particulier des vitrages composites.
PCT/EP2004/001527 2003-02-19 2004-02-18 Procede de production de corps composites electrochromes et corps composites electrochromes WO2004074920A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10306944A DE10306944A1 (de) 2003-02-19 2003-02-19 Verfahren zur Herstellung von elektrochromen Verbundkörpern
DE10306944.5 2003-02-19

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WO2004074920A1 true WO2004074920A1 (fr) 2004-09-02

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
US10975016B2 (en) 2017-10-02 2021-04-13 Tbf Environmental Technology Inc. Solvent compounds for use as glycol ether replacements
US11708500B2 (en) 2017-10-02 2023-07-25 Tbf Environmental Technology Inc. Solvent compounds for use as coalescents

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014209891B4 (de) * 2014-05-23 2016-07-28 Innovent E.V. Elektrochrome Zelle und Verfahren zu deren Herstellung
DE102016224420A1 (de) * 2016-12-08 2018-06-14 Robert Bosch Gmbh Verfahren zur Herstellung eines Festelektrolyten

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Publication number Priority date Publication date Assignee Title
US5244557A (en) * 1990-09-14 1993-09-14 Saint Gobain Vitrage International Method for forming electrochromic glazings
WO2000052523A1 (fr) * 1999-03-01 2000-09-08 Flabeg Gmbh& Co. Kg Element electrochrome
EP1056097A2 (fr) * 1999-05-26 2000-11-29 Basf Aktiengesellschaft Electrolyte solide polymère optiquement transparente
EP1253461A2 (fr) * 2001-04-24 2002-10-30 Schott-Donnelly LLC Verre électrochrome de sécurité
EP1283436A2 (fr) * 2001-08-01 2003-02-12 Basf Aktiengesellschaft Vitrage feuilleté et couches primaires pour des vitrages électrochromiques

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5244557A (en) * 1990-09-14 1993-09-14 Saint Gobain Vitrage International Method for forming electrochromic glazings
WO2000052523A1 (fr) * 1999-03-01 2000-09-08 Flabeg Gmbh& Co. Kg Element electrochrome
EP1056097A2 (fr) * 1999-05-26 2000-11-29 Basf Aktiengesellschaft Electrolyte solide polymère optiquement transparente
EP1253461A2 (fr) * 2001-04-24 2002-10-30 Schott-Donnelly LLC Verre électrochrome de sécurité
EP1283436A2 (fr) * 2001-08-01 2003-02-12 Basf Aktiengesellschaft Vitrage feuilleté et couches primaires pour des vitrages électrochromiques

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10975016B2 (en) 2017-10-02 2021-04-13 Tbf Environmental Technology Inc. Solvent compounds for use as glycol ether replacements
US11708500B2 (en) 2017-10-02 2023-07-25 Tbf Environmental Technology Inc. Solvent compounds for use as coalescents

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