JP4782283B2

Glazing with optical and/or energetic properties capable of being electrically controlled

Abstract

This record has no abstract on file.

Term

Term ended

Expired 8 July 2019, 7.2 years ago.

13 claims: 10 independent, 3 dependent

1
少なくとも1つのエレクトロクロミック系(3) 及び基材(2) を具備しているグレイジングであって、前記グレイジングが、前記エレクトロクロミック系(3)によって前記グレイジングに与えられる光学的な外観を調節する少なくとも1つの手段も有し、且つ前記手段が、可視光領域において反射防止性の少なくとも1つの反射防止コーティング(12)、及び反射における前記グレイジングの色を弱める/変える少なくとも1つのコーティング(11)を含むこと、前記反射防止コーティング(12)が、前記グレイジングの外側面の少なくとも1つに堆積しており、且つ屈折率が大きい薄層と屈折率が小さい薄層とを交互に有する積層体、又は屈折率の勾配を持つ層を有すること、並びに反射における前記グレイジングの色を弱める/変える前記コーティング(11)が、このコーティング(11)のそれぞれの面に接触している材料の屈折率の中間の屈折率を持つ薄層の形であり、屈折率1.6~1.9の薄層、又は平均屈折率1.6~1.9の重ねられた少なくとも2つの薄層を有し、且つ前記基材(2)と前記エレクトロクロミック系(3)との間に配置されていること、を特徴とする、少なくとも1つのエレクトロクロミック系(3) 及び基材(2) を具備しているグレイジング。
2
反射における前記グレイジングの色を弱める/変える前記コーティング(11)が、反射における前記グレイジングの(L、a * 、b * )表色系におけるC * 飽和値を低下させる、請求項1に記載のグレイジング。
3
屈折率1.6~1.9の前記薄層が、酸化アルミニウムAl 2 O 3 、酸化イットリウムY 2 O 3 、酸炭化ケイ素SiOC、及は酸窒化ケイ素SiONののうちの少なくとも1つに基づくものである、請求項1又は2に記載のグレイジング。
4
前記反射防止コーティング(12)が、ドープした金属酸化物又は伝導性ポリマータイプの導電性材料から少なくとも1つの薄層が作られている積層体を有することによって、静電気防止性も有することを特徴とする、請求項1~3のいずれかに記載のグレイジング。
5
前記エレクトロクロミック系(3)のためのキャリアー基材(2)に関して、前記エレクトロクロミック系(3)のためのプライマーコーティングを有することを特徴とする、請求項1~4のいずれかに記載のグレイジング。
6
親水性/曇り防止性のコーティング、又は疎水性/防滴性のコーティングを、前記グレイジングの外側面の少なくとも1つに有する、請求項1~5のいずれかに記載のグレイジング。
7
前記疎水性のコーティングが、アルコキシ官能基がケイ素原子に直接に結合している少なくとも1種類のフルオロアルコキシシラン、1種類又は複数種類の水性溶媒の系、及び酸及び/又はブレンステッド塩基から選択される少なくとも1種類の触媒を含む組成物からなる少なくとも1つの層を有することを特徴とする、請求項6 に記載のグレイジング。
8
光触媒性/汚れ防止性のコーティングを更に有することを特徴とする、請求項1~7のいずれかに記載のグレイジング。
9
電磁スクリーン性を持つ少なくとも1つのコーティングを更に有することを特徴とする、請求項1~8のいずれかに記載のグレイジング。
10
前記エレクトロクロミック系(3)が、2つのキャリアー基材(1,2)の間に配置された機能層の積層であり、且つ前記2つのキャリアー基材のそれぞれが、硬質、半硬質又は可撓性であってよいことを特徴とする、請求項1~9のいずれかに記載のグレイジング。
11
前記エレクトロクロミック系(3)が、キャリアー基材として、グレイジングを構成している硬質基材のうちの少なくとも1つ(2)、及び/又はグレイジングを構成している硬質基材のうちの1つ(1)に積層によって結合されている少なくとも1つの可撓性キャリアー基材(13)を使用する、請求項10 に記載のグレイジング。
12
前記エレクトロクロミック系(3)が、キャリアー基材(2)上に配置された機能層の積層であり、且つ無機層又はポリマー層タイプの保護フィルムを具備していることを特徴とする、請求項1~9のいずれかに記載のグレイジング。
13
建築物のグレイジングとして;列車、航空機、自動車若しくは船舶タイプの移動手段の窓又は内側のパーティションに備え付けられるグレイジングとして;コンピューター又はテレビのスクリーンのタイプのディスプレイスクリーンのグレイジングとして;眼鏡若しくはカメラレンズのグレイジングとして;又はソーラーパネルの保護材としての、請求項1~12のいずれかに記載のグレイジングの使用。

Independent claims13

1 paragraph, as filed

[0001] The present invention,lightWith respect to glazing capable of electrically controlling physical and / or energetic properties. [0002]That is,The present invention relates to glazing in which some of the features can be altered by a suitable electrical source. Here, these features are particularly the transmittance and absorption of electromagnetic waves of specific wavelengths, especially visible and / or infrared light.RateAnd reflectance, or light scattering. [0003] In fact, there is an increasing demand for so-called "smart" glazing that can change its nature. [0004]heatPerspectiveRegarding, At least part of the solar spectrumaboutGlazing that can change the transmittance / absorption rate is as glazing on the outside of the building.、Alternatively, when installed as a window of a type of mobile medium including automobiles, trains, aircraft, etc., it is possible to control the solar heat flowing into the interior or cabin area / compartment. So this is in the presence of strong sunlightEvenExcessive heating of indoor or guest room areas / compartments can be prevented. [0005] Also opticalRegarding the viewpointThis glazing allows you to control the degree of vision, which when attached as an outer glazing, in the presence of strong sunlightEvenGlare can be prevented. It is also used as an outer glazingTo doeven when、Used as inner glazingand when, For example, the room between each room (office in the building)ForUsed for articulationand when,Or used, for example, for independent compartments of trains or aircraftand whenAlso has a beneficial shutter effect. [0006] There are many other uses, for example, glazing with variable light transmission / reflectance.、It can be used for the manufacture of rearview mirrors, which can be darkened as needed to prevent blinding the driver. They can also be used for display panels on the road or for any display panel, for example thereby displaying a message / display only temporarily to attract further attention. [0007] One particularly advantageous application of this system with variable absorbance relates to display screens, especially any display screens installed in television and computer hardware. This is because this type of glazing can improve the contrast of the image, especially taking into account the ambient brightness. [0008] In fact, many systems have already been studied because of the benefits that such glazing can provide. [0009] Here, known systems capable of altering the light transmittance or absorptivity of glazing are particularly so-called biologene-based systems, as described, for example, in US Pat. No. 5,239,406 or European Patent No. 0,612,826. It's like. These are essentially capable of varying absorptivity in the visible light region. [0010] So-called electrochromic systems also exist for the same purpose. The operating principle of this systemBelowBriefly explain.. The electrochromic system isReversible ions and electronsandIt had a layer of electrochromic material that could be inserted at the same time in a known manner and was inserted.StatusAnd the oxidized state of this electrochromic material corresponding to the extracted stateAre each otherIt has a different color and one of these oxidized states has a higher light transmittance than the other. The insertion or extraction reaction is controlled by an appropriate electrical supply using a current generator or voltage generator. Therefore, electrochromic materials, which are usually based on tungsten oxide, must be in contact with an electron source, such as a transparent conductive layer, and an ion (cation) source, such as an ionic conductive electrolyte. [0011] Furthermore, in order to guarantee at least 100 switching operations, DSymmetrical with layers of rectrochromic materialandReversiblyCationCan be insertedversusThe electrodes are bonded to a layer of electrochromic material, therebyGiantIt is known to make the electrolyte visually considered as one ionic medium. [0012]versusThe electrode may consist of a neutral colored layer, or at least a transparent or barely colored layer when the electrochromic layer is uncolored. Tungsten trioxide、Cathode electrochromic materialFee,In other words, the colored state corresponds to the most reduced state.As a material, it is generally for counter electrodesAnode electrochromic material based on nickel oxide or iridium oxideuseTo use.TargetIt has also been proposed to use an optically neutral material, such as cerium oxide, or an organic material such as a conductive polymer (such as polyaniline), or Prussian blue in the oxidized state. [0013] Such systems are described, for example, in European Patents 0,338,876, 0,408,427, 0,575,207, and 0,628,849. [0014] These systems may recently be classified into the following two types, depending on the type of electrolyte used. Electrolytes in the form of polymers or gels. For example, a proton conductive polymer as described in European Patents 0,253,713 and 0,670,346, or lithium ion conduction as described in European Patents 0,382,623, 0,518,754, or 0,532,408. Examples include sex polymers. An ionic conductive but electrically insulating inorganic layer electrolyte. These are called "tout-solide" electrochromic systems. For a description of this "all-solid" electrochromic system, European Patent Application No. 97/400702.3 (submitted March 27, 1997) and European Patent No. 0,831,360 can be referred to. [0015] Other systems, PossibleIons can be inserted in reverseSlightly differentUse electrochromic type materials. These are, for example, so-called gaschromic systemsTo.Here, the electrochromic material is provided with a layer of catalyst capable of decomposing hydrogen.This electrochromic material,Installed on the gas space side inside the double glazing system. Tungsten oxide develops color by sending hydrogen to the gas space inside this double glazing system. By injecting oxygen into this inner space instead of hydrogen, it returns to its decolorized state. [0016] These systems with one or more materials capable of reversible insertion are particularly advantageous in that they allow absorption over a wide wavelength range compared to biologen-based systems. That is, they allow variable absorption not only in visible light, but especially in the infrared light region, which can provide an effective thermal / optical role. [0017] Viologen-based or electrochromic systems deposited on or in combination with a transparent substrate have absorptivity and light transmittance (and energy transmittance), especially the selection of electrochromic materials to be used and / or them. The choice of thickness results in glazing that can be varied within a predetermined range. [0018] Another type of "smart"MothThe lath can be made by what is called an "optical bulb". This "optical bulb" is a film having a generally crosslinked polymer matrix in which microdroplets are dispersed, and these microdroplets have the property of being oriented in a preferred direction by the action of an electric or magnetic field. Contains. These films are marked, especially at the ends of the conductive layers placed on both sides of the film.Be addedIt has variable optical properties depending on the potential and the properties and concentrations of the orientable particles. Here, WO 93/09460 is an optical valve based on a crosslinkable polyorganosilane matrix and a film having inorganic or organic orientable particles, particularly light-absorbing particles such as polyiodide particles. Is disclosed. Mark the voltage on this filmAdditionThen mark the voltageAdditionWhen notWhenIt hardly blocks light in comparison. [0019] Glazing, which can change light scattering by the same operating principle, is also known by the expression "liquid crystal glazing". is this、2Placed between two conductive layersPolymer material systemBased on the use of filmThere is. Here in this filmLiquid crystal droplets, especially positive dielectric anisotropy nematic liquid crystal dropletsButDistributedare doing.. Mark the voltage on the filmAdditionThen the liquidCrystalIn the preferred directionOriented, therebyThe outlook becomes clear. Mark the voltageAdditionOtherwise, the crystals will be orientedNot by thatThe film becomes scatterable、Obstruct your view. Examples of such films are described in European Patent Nos. 0,238,164 and US Pat. Nos. 4,435,047, 4,806,922, and 4,732,456. Assembled by laminating between two glass substratesRuThis type of film is sold by Saint-Gobain Vitrage under the trade name "Priva-lite". In fact, any liquid crystal device known by the terms "NCAP" (nematic curve alignment phase), or "PDLC" (polymer-dispersed liquid crystal), or "CLC" (costelic liquid crystal) can be used. .. They may further contain a dichroic dye, especially in the solution in the liquid crystal droplets. Moreover, it is possible to change the light scattering rate and the absorptive rate of the system in combination. [0020] Also, for example, a gel based on a costeric liquid crystal containing a small amount of crosslinked polymer can be used, as described in WO 92/19695. [0021] [0021] However, for all of these various systems / glazing assemblies、These have their own limitationsTo.This limitation is especially、It relates to their optical appearance. [0022] Here, in the case of electrochromic type glazing, for example, a material that can be reversibly inserted.To the feeLight transmittance (T) by adjusting the thickness of one or more layers based onL) Can be varied in the range of achievable values. However, in a given system, this TLThe value of can only be somewhat larger or smaller, and it is not easy to exceed this. The choice of material that allows for more reversible insertion affects the chromatic appearance of glazing in both transmission and reflection. [0023] Therefore, an object of the present invention is particularly described above by proposing a new electrically controllable glazing with variable optical / energetic properties that can also change the optical appearance. It is to alleviate the drawbacks. [0024] The subject of the present invention isVariable light and / or energy transmission / absorption and / or variable light scattering, etc.At least one electrically controllable system with variable optical / energetic propertiesEquippedGrazinInis there. Also this glazing, DenKi controllable systemButFor glazinggiveAdjust the optical appearancesectionFurther have at least one means of doing so. This means advantageously smells in the visible or near infrared range.Anti-reflectiveIt is in the form of at least one coating. [0025] For simplicity, the following refers to this coating as "Anti-reflective coating, And an electrically controllable system is called a "functional system". [0026] This featuresystemWhenAnti-reflective coating with precise feature adjustmentWhen combined with, GuActually changing the optical or thermal performance of the lasingButTo be possibleNaTo. Here thisAnti-reflective coatingIs, GuRagingBy a temporary supply of electricityIt can affect the range of light or solar transmittance that can be possessed. thisAnti-reflective coatingIn particular, in a controlled manner, these transmission ranges are relatively large TLOr TEIt can be transferred to the value of (energy transmittance). Especially this is a given functional systemregarding,Without changing the functional layer itselfBy adding an anti-reflective coatingTLOr TERange ofDepends on the intended useIt means that it can be changed. This allows for much more flexible and rational manufacturing of glazing compared to the case where many different functional systems have to be manufactured for the intended use. [0027] This depends on the application、Mark the voltageAdditionThe purpose is to provide a strong color / absorption effect when the voltage is marked.AdditionSome residual color when notButToleranceBe done(For example, when glazing with a shutter effect in the developed state is desirable). [0028] On the other hand, in other applications, mark the voltageAdditionWhen not、It is necessary that there is little or no residual glazing color. This is the case, for example, in the case of functional systems for display screens. In addition, it maintains a limited number of "standard" functional systems as much as possible, and is special, which is considerably simpler to manufacture than functional systems.Anti-reflective coatingBy, "Standard" functional systemAdapting is fairly simple. [0029] thisAnti-reflective coatingIs、Reachable TLOr TEIt is also possible to extend the range of values for. This is a very important advantage regardless of the intended use. This advantage is especially important when using glazing to promote display screen contrast. When manufacturing a new TV that uses flat screen plasma technology、This is the most important. Here, this new TV、Sometimes called the radial type, MarkIt is considerably less bright than a quasi-cathode ray tube TV. [0030]Anti-reflective coatingOne of the advantageous aspects of glazing is the outer surface of glazing, i.e. glazing, which is directly exposed to the environmental atmosphere.FaceConsists of depositing it on at least one of. Both of these faces can be processed, or in the case of display screen glazing、Only the outward facing surface of this device can be processed. Known styleso, This coating alternatesofHigh refractive indexlayerAnd low refractionWith the rate layerLaminates can be included. is this、The interference effect tends to reduce the light reflection of glazing and provide the benefit of increasing light transmission... AntiShootingPreventionExamples of laminates are known from European Patents No. 0,728,712, No. 0,712,815, and No. 0,791,562. [0031] These layers are generally、Oxide type, fluoride type, nitride tiePumataIs a dielectric material for silicon derivatives. Here, an example of an oxide typeRegardingSiO for layers with small dielectric constants less than 1.72Or Al2O3Can be mentioned,SnO for layers with a relatively large permittivity of 1.9 or higher2, TiO2, Or Nb2O5Can be mentionedTo.As an example of the fluoride type, MgF as a low dielectric constant layer2Can be mentioned, Si as an example of the nitride type3N4Can be mentionedOr, as an example of a silicon derivative, SiOxNzOr SiOxCyYou can list the types. [0032] However, as a layer of low or high index of refraction, at least a layer of slightly conductive materialAnti-reflective coatingThe coating may be provided with an antistatic function in combination with. A layer of doped metal oxide, eg F: SnO with a refractive index of at least 1.9-2.02Alternatively, a layer of ITO (tin-doped indium oxide) or a conductive polymer can be selected. [0033]Anti-reflective coatingMay consist of only a single layer having a refractive index gradient with respect to its thickness direction. Such layers are obtained, for example, using pyrolysis deposition techniques. Such thermal deposition techniques make it possible to obtain layers that are particularly durable in terms of machinery, which can be very important depending on the intended use of the system, and in particular thereby. It is possible to touch the coating, clean it repeatedly, and so on. This layer, in which the refractive index gradient is present, actually has a chemical composition that varies with respect to the thickness direction, for example, this chemical composition is SiOC or SiON type composition to SiO.2Gradually approach the composition of the type. [0034] The glazing of the present invention is a functional system.ButGive this glazingEruMeans for adjusting the optical appearance can also be included, which includes at least one coating that changes / weakens the glazing color in the reflection (this coating is previously described).Anti-reflective coatingInstead of or aheadAnti-reflective coatingExists in addition to). This is because, for some applications, for example, in the case of glazing of any type of display screen, the glazing color in the reflection is as neutral as possible, especially.CompleteThe glazing is not completely colored when it is completely decolorized, and thereforeTesuThis is because it is preferable not to change the color of the image that appears cleanly as much as possible.Anti-reflective coatingOther coatings allow you to reduce the intensity of glazing light reflections in general.、By weakening its color in reflection、It plays its optical role. This is actually the glazing in reflection, (L, a*, B*) Color system C*This is done by lowering the saturation value. [0035] The coating is advantageously in contact with the functional system and is in the form of a thin layer having a refractive index at least intermediate to the index of refraction of the material in contact with each surface of the coating. This may be a thin layer with a refractive index of 1.6 to 1.9, especially aluminum oxide Al.2O3, Aluminum Nitride AlN, or Yttrium Oxide Y2O3, Silicon Carbide SiOC and / or Silicon Nitride SiON, or a mixture of at least two of these materials. This thin layer can also be deposited by sputtering type decompression technology or by pyrolysis type technology, which is most often used to deposit layers of silicon derivatives. [0036] The coating may have a plurality of layers instead of one layer, and may be in the form of a laminate of at least two layers, in particular having an average refractive index of, for example, 1.6 to 1.9. This is, for example, SnO2/ SiO2Or SnO2/ SiO2/ SnO2It is in the form of a stack of. [0037] This coating、One layer having a refractive index gradient with respect to its thickness direction may thereby optimize the adjustment of the index of refraction of the surrounding material. The formation of such a refractive index gradient layer using steam phase pyrolysis technology (chemical vapor deposition, also referred to as CVD) is described, for example, in WO 97/03029 (see above).Anti-reflective coatingThis document can also be referred to in the index of refraction gradient layer of.) [0038] The glazing of the present invention is a primer for a functional system with respect to its carrier substrate.-CoIt also includes the arting. This proves to be particularly advantageous when the properties of the substrate are of a polymeric / thermoplastic material and not of a glass-type inorganic material. This coating is a thin metal layer, SiO2Layer of type silicon derivative, or Al2O3A layer of suitable metal oxide of type can be included. is thisPrimerIt may be a varnish. This is advantageousPrimerThe coating is gray in reflection, similar to the particular coating material described above, especially if its index of refraction is in harmony with the index of refraction of the functional layer with which it is in contact and the index of refraction of the thermoplastic substrate. It can be made to play a role in weakening the color of Jing. [0039] The glazing of the present invention has a drip-proof hydrophobic coating or an anti-fog hydrophilic coating on at least one of its outer surfaces.ToYou can also have. Suitable hydrophobic coatings can be referred to, for example, European Patent Nos. 799,873 and 692,463. This is in particular at least one type of fluoroalkoxy grouper in which the alkoxy functional group is directly attached to the silicon atom.,System of one or more aqueous solvents,AndAt least one catalyst selected from acids and / or Bronsted basesComposition containingIt may be at least one layer consisting of. This coating is hydrophobic to glasssexA primer layer that promotes layer adhesion, for example, a primer layer based on silanes may be included. [0040] The glazing of the present invention is a photocatalyst that imparts stain resistance to glazing, especially on at least one of its outer surfaces.SexArtingToTo haveAlsoit can.Photocatalytic coatingIn particular, may be a coating containing a crystallized oxide or sulfide type semiconductor material having this type of property, in particular ZnO, WO.3orIs SnO2Type of crystallized oxide, more specialTo a littleAt least partiallyTo anatase typeThe coating may contain crystallized titanium oxide. This type of coating and various methods for obtaining this type of coating are described in particular in WO 97/10186 and 97/10185. These coatings can remove any stains that have organic properties. In addition, they are hydrophilic, which can also facilitate the removal of inorganic stains. [0041] The glazing of the present invention may also include at least one coating having electromagnetic screen properties, in particular at least one coating having screen properties for radiation by a plasma screen type radioactive screen. This type of coating has, for example, at least one thin layer essentially made of metal or conductive metal oxide, and / or one or more stacked arrays of metal conductive wire and / or metal mesh. are doing. [0042] As mentioned above, glazing functional systems are generally hard and semi-hard.QualityIs in the form of a laminate of functional layers arranged between two carriers / protective substrates that may be flexible. Consists of glazingare doingHard base materialOne ofConsists of at least one flexible carrier substrate and / or glazing that can be combined withare doingOf hard base materialOurIt is advantageous to use at least one as a carrier substrateNaSometimes. Functional systemToNon-placed on a suitable substrate and providing the given mechanical protection to this functional systemTransparentBy sexual protective coating, This functional systemIt can also be simply protected / covered. This is SiO2Or Si3N4It may be a type of inorganic layer. It may also be of the polymer type, in particular in the form of varnish (epoxy or polyparaxylene) or lacquer (polyurethane or polyacrylic). Preferably, this may be a single layer of polymer deposited under reduced pressure. [0043] An object of the present invention is also the use of the above-mentioned glazing as glazing for buildings and glazing attached to moving media. Here, the glazing for this building is particularly glazing for outer windows, inner partition windows, or doors that use glazing (eg, "Velux" type sunroofs). Also, glazing for mounting on this mobile medium is especially glass for car windows (sunroofs and front and rear windows), train windows, or aircraft windows, especially windshields, above the windshield glazing. Used as a colored band or as a guest room windowRutaIt is a glazing for. It is also intended to attach such glazing to display screens, especially television or computer screens, to enhance image contrast.Be doneTo. Such glazing is a solar panel (satellite)As a protective material, Camera lens, aircraft pilotGlasses, SanguraSumataFittingThe rootsCan also be used for, orSensitive to heat or strong lightObjects / plantsThoseIt can also be mounted, for example, in greenhouses or store windows to protect against. [0044] As mentioned above, the present invention applies to various types of glazing that can be electrochemically controlled.Be done.. As mentioned above, this may be glazing with variable light transmittance / absorptance, in particular glazing with a biologene-based system or an electrochromic system. In particular, these may be of the types described in the European Patents No. 0,338,876, 0,408,427, 0,575,203, and 0,628,849 described above. This is preferably in the form of a laminate of functional layers. Here, this laminate is continuously a transparent conductor layer., H+, Li+, Na+, Ag+Reversible cations likeSo-called casso that can be insertedDoeLectrochromic layer, electrolyte layer, optionalMosquitoesThioketoneReversiblyIn the form of a second electrochromic layer of the so-called anode that can be insertedversusIt is preferably a laminate of an electrode and finally a functional layer containing a second conductive layer. [0045]thisRegarding the properties of the conductive layer of the device, there are two possibilities:AspectThere is.That is,Materials based on doped metal oxides, such as fluorine-doped tin oxide F: SnO2、Alternatively, tin-doped iridium oxide ITO can be used. It is also possible to use a layer of metal or metal alloy, such as a layer of metal or metal alloy based on gold Au, silver Ag, or aluminum Al.Also thisThe device generally has two conductive layers, so that both are layers on a metal, both are based on a doped oxide, or one is based on a metal and the other is on a doped oxide. It is possible to be based. Further, it is possible to stack a plurality of different types of conductive layers, for example, in an ITO / Ag or Au / ITO type laminate, at least one metal layer and a doped oxide layer. It is possible to combine. [0046] These layers (or at least one of these layers) may be made from one or more conductive polymers. [0047] Tungsten trioxide WO to make a layer of cathode electrochromic material3, Molybdenum oxide MoO3, Vanadium oxide V2O5, Niobium oxide Nb2O5, Titanium oxide TiO2, "Cermet" materials (combinations of metal materials and ceramics, especially combinations of the shape of metal particles in the ceramic matrix), eg WO3/ Au or WO3/ Ag, and a mixture of tungsten oxide and rhenium oxide WO3/ ReO3Material selected from the group consisting of、Alternatively, a mixture of these materials can be selected. These materials are especially、Suitable for reversible insertion of lithium ions. The same material can be used when operating the device by reversible insertion of protons, but in this case in hydrated form. [0048] To make a layer of anode electrochromic material, MxAyUzA material that satisfies the formula of can be selected. Where M is a transition metal, A is an ion used for reversible insertion, such as an alkali metal or proton, and U is a chalcogen, such as oxygen or sulfur. [0049] Especially proton ion H+If you want to insertAnode electrochromic material, LiNiOx, IrOxHy, IrOxHyNz, NiOx, NiOxHyNz, RhOx, CoOx, MnOx, And RuOxIt may be a compound belonging to the group containing, or a mixture of these compounds. Also, lithium ion Li+When inserting reversiblyAs an anode electrochromic material,LiNiOx, LiMn2O4, LixSnOy, IrOx, LixIrOy, LixSnOy, NiOx, CeOx, TiOx, CeOx-TiOx, RhOx, CoOx, CrOx, And MnOxA compound belonging to the group containing the above or a mixture of these compounds is selected. [0050] As for the selection of electrolyte materials, there are actually two types as mentioned above. [0051] For reversible insertion of protons, this may be an aqueous solution, such as a layer of water supplemented with sulfuric acid or phosphate, and for reversible insertion of Li ions, this may contain a non-aqueous solution, such as lithium salt. It may be a layer of propylene carbonate. This may be a layer of gel or polymer, especially the solid solution POE-H of polyoxyethylene and phosphoric acid.3PO4It may be a proton conductive polymer of the type containing. [0052] However, this may be an electrolyte in the form of a solid material, especially an electrolyte based on a metal oxide. According to the modifications of the present invention, the system has only a layer of solid material.、You can select the system. In the description of the present invention, the term "solid material" is used.、Any material with a solid mechanical state, in particular any essentially inorganic or organic material, or any hybrid material, i.e. partially inorganic and partially organic.materialIt should be understood that it means a material obtained from an organic-inorganic precursor material, for example by sol-gel deposition. This shape is one of the so-called "all-solid-state" systems, which is advantageous in terms of ease of manufacture. This is done, for example, if the system has an electrolyte in the form of a polymer that does not have a solid mechanical state, it is manufactured in parallel with two "half-cells", and the electrolyte is inserted and bonded between these two half-cells. To letButActually neededBy becoming.. Here, these two "half-cells" are each the first layer of conductivity.Coated with, andIt consists of a carrier substrate coated with an electrochemically active second layer. The "all-solid-state" form allows all layers of the system to be deposited one after another on a single carrier substrate.、Manufacturing is simplified.. ThisIn Case of, Because there is one base material to deposit layers instead of two, All operations to manufacture glazing are simplified. [0053] Furthermore, whether the electrolyte is a "solid" electrolyte or not, it has a layer made of an ionic conductive material capable of reversibly inserting ions while essentially maintaining the degree of oxidation. Can be done. This is in particular European Patent Application No. 97/400702.3It may be a material having electrochromic properties as described in the specification. [0054] Thus, the functional system of the components of the invention is between two substrates, or especially on one substrate in the case of "all-solid" systems.、Can be placed. The rigid carrier substrate can preferably be made from glass, acrylic polymer, polycarbonate, or certain types of polyurethane. Further, the carrier base material may be soft and flexible and intended to be laminated on a hard base material. Therefore, this may be soft polycarbonate, polyethylene terephthalate (PET), or the like. Lamination can be done with a thermoplastic type polymer such as polyvinyl butyral (PVB), ethylene-vinyl acetate (EVA), or some type of polyurethane interlayer sheet. If the lamination is not performed, the system may be provided with a protective varnish or film as described above. [0055] Such glazing is a "monolithic" structure, i.e. a structure with a single hard substrate, or a stack of multiple rigid substrates.ConstructionAnd / or multiple glazingGu structureIt may be constructed, or such glass may have a so-called asymmetric glazing structure with a layer of plastic on the outside, especially a plastic based on polyurethane. Here, this structure is specifically described in European Patents 191,666, 190,953, 241,337, 344,045, 402,212, 430,769, and 676,757. [0056] For example, the glazing of the present inventionIt can have the following types of structures or orders:Anti-reflective coating/ Glass 1 / Coating that changes or weakens the color in reflection / Functional system / PU type polymer interlayer sheet / Glass 2。[0057] This system can also be combined with other glasses to create a double glazing structure.Also,It is also possible to provide an interlayer sheet of PU-type polymer and another glass between glass 1 and a coating that diminishes the color in reflection.To. That is,One structure (Anti-reflective coatingIt is possible to juxtapose / glass 1) and another structure (functional system / color-weakening coating / glass) and laminate these structures with a polymer sheet. [0058] [0058] Further details and advantageous features of the present invention, Refer to the attached drawingIt is clear from the following various non-limiting aspectsTo.[0059] This figure is approximate、Reflects the ratio between the various components shownContact TeNotsimplyIt is intended to help understanding. In particular, all electrical connections that are known in their own right are not shown. [0060] The hard substrates used in all of the examples below are substrates made of silicon-soda-lime glass with a thickness of 4 mm (these thicknesses are actually selected specifically in the range 0.7-6 mm). be able to). [0061] These so-called "transparent" glass substrates are sold by Saint-Gobain Vitrage under the trade name Planilux. [0062] [Example 1] FIG. 1 shows electrochromic glazing with a laminated structure with two glass plates in the structure, which is suitable for use, for example, as a display screen in a flat screen television. This figure shows two transparent glass plates 1 and an "all-solid-state" type electrochromic functional system 3.There is. hereThis functional system、It consists of a laminate of the following functional layers and a polyurethane sheet 13. F: SnO2First conductive layer 4 (thickness 500 nm), made of (Hydrated) Iridium Oxide IrOxFirst electrochromic layer 5 (thickness 30 nm) of anode electrochromic material made of (this layer can be replaced with a layer of nickel oxide hydrate), Tantalum pentoxide hydrate Ta with binding layer function2O5HxLayer 6 (thickness 5 nm), Tungsten oxide layer 7 (thickness 200 nm), Second tantalum pentoxide hydrate layer 8 (thickness 200 nm), Tungsten trioxide(Hydration type)HxWO3Second electrochromic layer of cathode electrochromic material based on (thickness 380 nm), ITO's second conductive layer 10 (thickness 280 nm). [0063] Between the conductive layer 4 and the glass 2, there is a coating 11 that has the function of weakening the glazing color in reflection, and this layer has a refractive index of about 1.7 and a geometric thickness of about 50 ~. A layer of silicon carbide acid carbide at 55 nm (deposited on glass 2 by CVD in a known manner). This refractive index is between the refractive index of the material sandwiching this layer, that is, the refractive index of glass 1 (about 1.5) and F: SnO.2It is in the middle of the refractive index (about 2) of the layer of. [0064] What is deposited on the outer surface of glass 2Anti-reflective coating12 which constitutes the following series of layers (starting from the surface of glass 2): SnO2(19nm) / SiO2(33nm) / Nb2O5(115nm) / SiO2(88nm)。[0065] The coating was deposited on glass 2 in a known manner by magnetic field accelerated reactive sputtering in the presence of oxygen using a suitable metal / silicon target. [0066] The coating 12 / glass 2 / coating 11 / functional 3 assembly was laminated on glass 1 by a polyurethane-type organic polymer sheet 13 with a thickness of at least 1.24 nm. [0067] This glazing was mounted with the glass 2 facing the outside of the screen. [0068] Achievable T by combining functional system 3 with two types of optical coatings 11 and 12.LIt was found that the range of was relatively large, and the intensity of the residual color in reflection decreased in the decolorized state and the colored state. [0069] [Example 2] Example 2 was provided on the same glass 2 with the same coatings 11 and 12 and the same functional system 3. The only difference that followed was the method of mounting the glass, in which case a decompression deposit of polyparaxylene varnish was provided on top of the last ITO layer 10 of the functional system. The result is a single glass structure of the type coating 12 / glass 1 / coating 11 / functional system 3 / varnish. [0070] [Example 3] Example 3 was manufactured in the same manner as in Example 1.However,Here, only some of the thickness of the electrochromic layer was slightly modified, and layer 6 of tantalum pentoxide hydrate was omitted. Therefore, the electrochromic laminate in Example 3 is as follows. F: SnO21st conductive layer 4'(thickness 500 nm), (Hydrated) Iridium Oxide IrOxFirst electrochromic layer 5'(thickness 37 nm) of anode electrochromic material made of (this layer can be replaced with a layer of nickel oxide hydrate), Tungsten oxide layer 7'(thickness 100 nm), Second tantalum pentoxide hydrate layer 8'(thickness 100 nm), Tungsten trioxide(Hydration type)HxWO3Second electrochromic layer 9'(thickness 280 nm) of cathode electrochromic material based on ITO's second conductive layer 10 (thickness 270 nm). [0071] Also, the coating 11 and coating 12 are attached to the electrochromic system in the same manner as in Example 1.is there.. [0072] [Example 4] Example 4 was manufactured in the same manner as in Example 3. However, in this exampleAnti-reflective coating12 does not exist. [0073] At least one coating (coating 11) orAnti-reflective coatingIt was confirmed that the provision of (coating 12) improved the optical properties of glazing and that the best improvement was achieved when both of these coatings were used. SecondAnti-reflective coatingIt is possible to provide (thus treating each of the outer surfaces of the outer substrates 1 and 2). [0074]For Example 3 and Example 4,In the decolorized state (+ 1.2V supply) and the colored state (-1.6V supply)RuiCompared the optical properties below: Light transmittance TL(%), In transparency (L*, A*, B*) System*TL and b*TL value, Light reflectance R on the "inside"L1And the corresponding a*And b*The value of the, Light reflectance R on the "outside"L2And the corresponding a*And b*The value of the。[0075] This data is given in Table 1 below. [0076] Table 2 below shows two of these same examples.about,Gives data on energetic properties. Here, the energetic property is the energy transmittance T.E(%), Energy reflectance RE1(Outsideside), And energy reflectance RE2(Insideside)Is. [0077] These solar constants SF were also measured (this solar constant is the ratio of the total energy entering the room through glazing to the incident solar energy). In Example 3, SF is 33% in the color-developed state (-1.6V) and 73% in the decolorized state (+ 1.2V). In Example 4, SF is 32% in the color-developed state and 67% in the decolorized state. [0078] From this data, in the case of Example 3 of the present invention, a relatively wide range of light transmittance can be achieved, especially in the decolorized state, T of about 80%.LIt turns out that can be achieved. Further, the energy transmittance in the decolorized state of Example 3 is lower than the energy transmittance of Example 4, and the energy reflectance of Example 3 is higher than the energy reflectance of Example 4 in the colored or decolorized state. Example 4 with only a coating that prevents color development has already shown an improvement over standard electrochromic glazing, especially in reflection.L1And RL2Regarding the color system of, it shows an improvement beyond the standard electrochromic. However,Anti-reflective coatingExample 3 with TLIt is possible to extend the range of to a relatively large value, and also to make glazing more effective with respect to the filtering function of thermal radiation, especially solar radiation. [0079] [table 1]<img file="JP4782283B2_D0001.tif" /> 【0080】In addition, as the embodiment of the present invention, the following embodiment can be mentioned.(Embodiment 1) It comprises at least one electrically controllable system having variable optical and / or energetic properties, and in particular this electrically controllable system is capable of reversible insertion. Glazing, which is an electrochromic (3) or gas chromic form with one or more possible materials, an optical bulb or biologen-based system form, or a liquid crystal or cholesteric gel system form.It also has at least one means of adjusting the optical appearance that the electrically controllable system gives to this glazing, which means includes at least one antireflection coating (12) in the visible light region. Glazing comprising at least one electrically controllable system having variable optical and / or energetic properties.(Embodiment 2) The antireflection coating (12) is deposited on at least one of the outer surfaces, and the antireflection coating (12) is a thin layer having a high refractive index and a thin layer having a low refractive index. The glazing according to the first embodiment, characterized in that it has a laminated body or a layer having a gradient of refractive index.(Embodiment 3) The antireflection coating (12) also has antistatic properties by having a laminate in which at least one thin layer is formed from a doped metal oxide or conductive polymer type conductive material. The glazing according to embodiment 1 or 2, characterized in that it has.(4) A means of adjusting the optical appearance of the electrically controllable system on the glazing, comprising at least one coating (11) that attenuates / changes the color of the glazing in reflection. The glazing according to any one of embodiments 1 to 3, further comprising means.(Embodiment 5) A thin layer in which the coating (11), which diminishes / changes the color of this glazing in reflection, has an index of refraction intermediate to that of the material in contact with each surface of the coating (11). The glazing according to embodiment 4, characterized in that it is in contact with the electrically controllable system in the form of.(Embodiment 6) The coating (11) that diminishes / changes the color of this glazing in reflection has a thin layer with a refractive index of 1.6 to 1.9 or at least two stacked thin layers with an average refractive index of 1.6 to 1.9. In particular, the thin layer is made of aluminum oxide Al.2O3, Yttrium oxide Y2O3, Silicon Carbide SiOC and / or Silicon Nitride SiON, or a mixture of at least two of these materials, and the at least two stacked thin layers are SnO.2/ SiO2Or SnO2/ SiO2/ SnO2The glazing according to embodiment 4 or 5, characterized in that it is a laminated body of.(Embodiment 7) The electrically controllable system with respect to this carrier substrate, especially when the carrier substrate (2) of the electrically controllable system (3) is a polymer material / thermoplastic material. The glazing according to any one of embodiments 1-6, characterized in that it has a primer / binding layer coating for (3).8. The glazing according to any one of embodiments 1-7, comprising a hydrophilic / anti-fog coating or a hydrophobic / drip-proof coating on at least one of the outer surfaces.(Embodiment 9) The hydrophobic coating comprises at least one fluoroalkoxysilane in which an alkoxy functional group is directly attached to a silicon atom, a system of one or more aqueous solvents, and an acid and / or bren. The glazing according to embodiment 8, wherein the glazing comprises at least one layer consisting of a composition comprising at least one catalyst selected from the steady bases.Embodiment 10 TiO further having a photocatalytic / antifouling coating, especially on at least one of the outer surfaces, in particular at least partially crystallized in an anatase form.2The glazing according to any one of embodiments 1 to 9, wherein the glazing comprises.(Embodiment 11) The glazing according to any one of embodiments 1 to 10, further comprising at least one coating having electromagnetic screen properties.(Embodiment 12) The electrically controllable system (3) is a stack of functional layers arranged between two carrier base materials (1, 2), and each of the two carrier base materials. The glazing according to any one of embodiments 1 to 11, wherein the glazing may be rigid, semi-rigid or flexible.(Embodiment 13) The electrically controllable system (3) constitutes at least one (2) and / or glazing of hard substrates constituting glazing as a carrier substrate. The glazing according to embodiment 12, wherein at least one flexible carrier substrate (13) is attached to one of the rigid substrates (1) by lamination.(Embodiment 14) The electrically controllable system (3) is a laminate of functional layers arranged on a carrier substrate (2) and is an inorganic layer or polymer layer type protective film, particularly a lacquer or. The glazing according to any one of embodiments 1 to 11, characterized in that it comprises a protective film in the form of a varnish.(Embodiment 15) As glazing of buildings, especially as glazing of outer windows or windows of inner partitions or doors with glazing; on windows of train, aircraft, automobile or ship type transportation or inner partitions. As a glazing provided; as a glazing of a display screen of the type of computer or television screen; as a glazing of eyeglasses or camera lenses; or as a protective material for solar panels, as described in any of embodiments 1-14. Use of glazing.[Simple explanation of drawings] FIG. 1 is a cross-sectional view showing electrochromic glazing having a laminated structure.

Citations
Document	Relation	Office	Cited during
FR2738813A1	Cites	France	Examiner
JPH0883581A	Cites	Japan	Examiner
JP08083581A	Cites	Japan	–
FR02738813A1	Cites	France	–

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Document	Office	Kind	Date
9808808	France	–	1998-07-09
9808808	France	A	1998-07-09
9808808	France	A	1998-07-09
9901652	France	W	1999-07-08
9901652	France	W	1999-07-08
19989808808	–	–	–
1999001652	–	–	–
FR19980008808	–	–	–
WO1999FR01652	–	–	–

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Document	Office	Kind
FR2781062A1	France	A1	2000-01-14
WO0003290A1	World Intellectual Property Organization (WIPO)	A1	2000-01-20
EP1012663A1	European Patent Office (EPO)	A1	2000-06-28
JP2002520654A	Japan	A	2002-07-09
FR2781062B1	France	B1	2002-07-12
US6746775B1	United States of America	B1	2004-06-08
US2004229049A1	United States of America	A1	2004-11-18
US7074486B2	United States of America	B2	2006-07-11
JP4782283B2This record	Japan	B2	2011-09-28

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