WO2001004696A1 - Electrochromy device, process for obtaining such device and use thereof - Google Patents

Electrochromy device, process for obtaining such device and use thereof Download PDF

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Publication number
WO2001004696A1
WO2001004696A1 PCT/ES2000/000251 ES0000251W WO0104696A1 WO 2001004696 A1 WO2001004696 A1 WO 2001004696A1 ES 0000251 W ES0000251 W ES 0000251W WO 0104696 A1 WO0104696 A1 WO 0104696A1
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Prior art keywords
sheet
electrochromic
electrochromic material
electrically conductive
conductive material
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PCT/ES2000/000251
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Spanish (es)
French (fr)
Inventor
Antonio IBAÑEZ DE ALBA
Original Assignee
Cisterra S.L.
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Publication date
Application filed by Cisterra S.L. filed Critical Cisterra S.L.
Priority to AU58292/00A priority Critical patent/AU5829200A/en
Publication of WO2001004696A1 publication Critical patent/WO2001004696A1/en

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/061—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 electro-optical organic material

Definitions

  • the present invention relates to the field of optics and in particular to the electrochromic devices sector.
  • Electrochromic devices for modulating light are known in the art, consisting of an electrochromic product confined between two conductive layers, each formed by a transparent plate, electrodes on each of said conductive layers and means for selectively providing current. electric Such devices are described in European patent EP-A-0532942 and are applicable to windows in construction, or in the automobile industry.
  • the electrochromic product described in patent application EP-A-0532942 is an electrolytic material that includes, for example, metal salts dissolved in an organic solvent, in addition to organic acids and / or other products, therefore it is an electrical conductor.
  • the immediate consequence is that the mechanism by which the optical change is obtained - from transparent to opaque - must be the deposition of metal ions on the sheets of material and therefore a chemical transformation takes place, which has the disadvantage of a limited reversibility.
  • Another problem not solved by the prior art is to achieve that the change of visible optic is uniform over the entire surface of the device, for which it is avoid, for example, the generation of stray currents inside the device.
  • EP-A-0532942 aims to improve all aspects mentioned; However, it does not solve all problems effectively.
  • the device obtained according to the present invention allows to overcome the aforementioned difficulties, making possible an immediate optical change of a glazing.
  • the present invention has as an object an electrochromic device capable of undergoing a visible optical change in response to a change of a first electric current value applied to said device to a second electric current value, which activates a birefringent polymeric material incorporated in said device.
  • the present invention also relates to a method for obtaining an electrochromic device capable of undergoing a visible optical change in response to a change of a first electric current value applied to said device to a second electric current value, which activates a material birefringent polymer incorporated in said device.
  • the present invention has as its object first an electrochromic device capable of experiencing a visible optical change in response to a change of a first electric current value applied to said device to a second electric current value, which activates a birefringent polymeric material incorporated in said device.
  • An electrochromic device capable of producing a visible optical change in response to an electric current, comprising a first sheet of a first electrically non-conductive material at least translucent, and a second sheet of a second material, an electrochromic material disposed between said first and said second sheet, an electrically conductive and at least translucent material, disposed between said electrochromic material and at least one of said first sheet and said second sheet, spacer means that distance the first sheet from the second sheet, and means for applying at least an electric current to the electrochromic material, characterized in that the electrochromic material comprises at least one birefringent polymeric material with a first molecular orientation that reversibly changes to a second molecular orientation in response to a change from a first electric current to a second electric current delicious, The electrically conductive material has no ability to react with the electrochromic material.
  • Said electrochromic material comprises the birefringent polymeric material obtained by reacting an ethylene glycol polymer with a crosslinking agent and at least one at least translucent epoxy polymer.
  • Said birefringent polymeric material may be conductive or non-conductive.
  • said ethylene glycol polymer is a polyethylene glycol with a molecular weight ranging from 5000 to 7000 and a melting range between 592C and 749C.
  • said polyethylene glycol has a composition corresponding to the formula C3 2 or H 6 4 ⁇ ° i 6 o.
  • said polyethylene glycol has an amount of hydroxyl groups between 16 and 23.
  • the solubility in water is of the order of 550 g / 1 at 203C.
  • the amount of birefringent polymeric material used is of the order of 10 g of polymer per square meter of sheet of material.
  • the epoxy polymer used to prepare the electrochromic material can be any type of epoxy.
  • said epoxy polymer is transparent epoxy NOA65 from Thorlabs.
  • the ratio of ethylene glycol polymer to epoxy polymer can vary between 40:60 and 60:40, a 50:50 ratio being preferred.
  • the crosslinking agent selected from a monounsaturated secondary alcohol comprising a cyclopentephenanthrene system, and an ionic surfactant of the sodium dodecyl sulfate type.
  • said agent is cholesterol.
  • the amount of crosslinking agent against the ethylene glycol polymer may vary between a proportion. from 1: 3 to 1: 5. In a preferred embodiment said ratio is 1: 2.
  • the thickness of the electrochromic material is determined by the spacers, which can be solid spheres mixed with the electrochromic material and selected from glass spheres, glass spheres, plastic spheres, and mixtures thereof. Said spacer means can also be roughnesses of the sheets of the material used, which act as such, so that the separation between sheets in the electrochromic device is determined by the presence and size of said spacer means.
  • said spacer means are glass spheres. More preferably, said spheres are microspheres such as those currently sold by AGFA.
  • the diameter of said spacers can vary between 5 ⁇ and 200 ⁇ .
  • the electrochromic material can therefore have a thickness between 5 and 200 ⁇ .
  • the electrochromic material may include a dye in order to achieve visible optical changes that imply a color change.
  • the dye must be a compound with a minimum conductive capacity to adhere to the conductive material.
  • a dichroic dye is used, that is, a dye that rotates the polarized light. Suitable dichroic dyes are marketed, for example, by DuPont and Merck.
  • the amount of dye used varies from 0.05 g / kg of prepared electrochromic material to 0.5 g / kg of electrochromic material.
  • the electric current used to produce the optical change can be alternating current or direct current.
  • direct currents they can be less than 50V or even less than 15V. If of alternating currents can be less than 220V.
  • the current used is direct current.
  • the electrically conductive material has a resistance between 10 "4 and 200 ⁇ / mm 2. Preferably it varies between 0.0005 ⁇ / mm 2 and 100 ⁇ / mm 2. More preferably it still varies between 10 ⁇ 3 ⁇ / mm 2 and 50 ⁇ / mm 2. Even more preferably said resistance is 0.01 ⁇ .
  • the conductive material disposed between the electrochromic material and the first sheet is preferably non-toxic, and must not react with the birefringent polymeric material.
  • Said conductive material may be liquid, gel or even solid, and may be selected from varnishes, metal salts (for example silver halides), metal salts dissolved in at least one organic solvent, and combinations thereof.
  • said material is a metal salt dissolved in an organic solvent.
  • said salt is 99% pure potassium iodide dissolved in 99% pure dimethylsulfoxide.
  • said conductive material is a metal oxide: preferably said metal oxide is tin or indium oxide readily applicable as a very thin laminate.
  • the material of the first and second sheets may be the same or different. Said material may be glass, glass or plastic.
  • the material of the second sheet can be a non-conductive material at least translucent, or an opaque material of a certain color.
  • the means for applying electric current to the electrochromic material can be electrodes of various kinds, which are attached to the electrochromic material by gluing or welding. In a preferred embodiment they are joined by welding, and particularly, by welding with indium oxide and / or tin.
  • a further object of the present invention is a process for preparing an electrochromic device comprising a first sheet of a first non-translucent non-conductive material, and a second sheet of a second material, an electrochromic material disposed between said first and said second sheet, an electrically conductive and at least translucent material, disposed between said electrochromic material and at least one of said first sheet and said second sheet, as well as spacer means that distance the first sheet of the second sheet, characterized in that it comprises: a first stage in which an electrically conductive and at least translucent coating is applied, on a surface of at least one of said sheets; a second stage in which a layer of a fragile electrochromic material comprising a homogeneous and at least semi-liquid mixture of a birefringent polymeric material obtained by reacting an ethylene glycol polymer with a crosslinking agent is applied homogeneously onto said conductive coating less an at least translucent epoxy polymer; a third stage in which a second sheet is applied on said electrochromic material layer; a
  • the viscosity of the fragile electrochromic material that is applied in the second stage varies between 650 cp and 1,500 cp. Preferably said viscosity varies between 1,000 cp and 1,200 cp.
  • the elongation at break of the electrochromic material obtained can be up to 80%, particularly if the material is plastic. Drying or curing of the electrochromic device is carried out by ultraviolet rays with a 100 W lamp, for a time of 5 min to 45 min, depending on the thickness of the layer of electrochromic material obtained between the two sheets.
  • a further object of the present invention is the use of the device obtained by the procedure described for the glazing of buildings as well as for the glazing of all types of vehicles.
  • Another use of the device of the present invention is for the manufacture of screens in general, as well as for the manufacture of space separators inside buildings, for example, in hospitals, offices.
  • the mechanism by which the optical change occurs consists of an alignment or orientation of the molecules of the birefringent polymeric material contained between the plates or sheets of material that make up the electrochromic device, whereby the optical change does not involve a chemical reaction and Device deterioration in general is much less.
  • the electrochromic material does not necessarily have to be conductive.
  • Another additional advantage is that the electrodes do not have to have a definite shape.
  • the device object of the present invention it is possible to: - modulate the entry of light into a vehicle, by activating a potentiometer that immediately produces the optical change of the glazing, regulate the light entering a building according to the time of the day and / or weather conditions
  • the present invention solves important problems related to daily necessities of life such as the problem of the uncomfortable situation that occurs in a place subject to permanent sun exposure in buildings with glass facades, without using Blinds.
  • Another problem solved by the present invention is to avoid the danger of leaving a vehicle, for example parked on the street, with its interior visible.
  • Another potentially dangerous situation resolved by the present invention is to drive a vehicle under a sun exposure that could not be controlled at will according to the state of the art.
  • FIGURES Figure 1 schematically shows a first embodiment of an electrochromic device according to the invention.
  • Figure 2 schematically shows a second embodiment of an electrochromic device according to the invention.
  • EMBODIMENTS OF THE INVENTION the device will be described based on figures in which:
  • Figure 1 shows an electrochromic device comprising a first sheet 1 and a second sheet 2, which They enclose the electrochromic material 3, the first electrically conductive material layer 4 applied on said first sheet 1, the spacer means 5 and the electric current application means 6.
  • Figure 2 illustrates in addition, the first sheet 1 and the second sheet 2, the electrochromic material 3, the electrically conductive material layer 4 applied on said first sheet 1, the spacer means 5, the application means of electric current 6, and a second layer of conductive material applied on the second sheet 2a.
  • a glass sheet, 1, of 1 m 2 of surface is covered, for example, by spraying on one of its faces with a conductive material 4 consisting of a 99% pure silver iodide solution in 99% pure dimethylsulfoxide. It is allowed to dry for an approximate time of 45 min.
  • the electrochromic material 3 is prepared by mixing transparent epoxy NOA65 from Thorlabs, with polyethylene glycol of formula C 32 or H 64 or 6 or 6 in a 1 to 1 ratio of both substances, and together with cholesterol in a proportion of the latter, which is equivalent to 20% of the total mixture of the three components. It is stirred until a homogeneous mixture is obtained, which constitutes the electrochromic material 3.
  • the resulting mixture is added with space microspheres 5, from the AGFA firm, and stirred until a homogeneous mixture is obtained again.
  • the final mixture obtained is poured onto the sheet of glass, 1, coated with conductive material 4, distributing it evenly.
  • a second sheet of glass 2 is placed on top of the face having the electrochromic material 3 and curing or drying with UV radiation, for a time of about 45 min.

Abstract

The invention relates to an electrochromy device susceptible of undergoing a visible optical change as a response to a change from a first value of an electric current applied to said device to a second value of electric current, which response activates a birefringent polymer material which is incorporated with said device. The device is comprised of a first sheet of a first non electroconducting material which is at least translucid, and a second sheet of a second material, and electrochromic material which is arranged between said first sheet and said second sheet, an electroconducting material which is at least translucid and arranged between said electrochomic material and at least one of said first and second sheets, spacing means which separate the first sheet from the second sheet, and means for applying at least one electric current to the electrochromic material. The electrochromic material is comprised of birefringent polymer material obtained by reaction of ethyleneglycol polymer with a cross-linking agent and at least one epoxy polymer which is at least translucid. The invention also refers to a process for obtaining said electrochromic device and also to the use of such device for its industrial application, in particular in any type of window pane for buildings and in the car industry and also in the fabrication of screens.

Description

DISPOSITIVO ELECTROCRÓMICO, PROCEDIMIENTO PARA SU OBTENCIÓN Y USO DEL MISMO ELECTROCROMIC DEVICE, PROCEDURE FOR OBTAINING AND USING THE SAME
La presente invención se refiere al campo de la óptica y en particular, al sector de los dispositivos electrocrómicos .The present invention relates to the field of optics and in particular to the electrochromic devices sector.
ANTECEDENTES DE LA INVENCIÓN Se conocen en la técnica dispositivos electrocrómicos para modular la luz, que consisten en un producto electrocrómico confinado entre dos capas conductoras, cada una formada por una placa transparente, electrodos sobre cada una de dichas capas conductoras y medios para proporcionar selectivamente corriente eléctrica. Tales dispositivos se describen en la patente europea EP-A- 0532942 y son aplicables a ventanas en la construcción, o en la industria del automóvil. El producto electrocrómico descrito en la solicitud de patente EP-A-0532942 es un material electrolítico que incluye por ejemplo sales metálicas disueltas en un disolvente orgánico, además de ácidos orgánicos y/u otros productos, por lo tanto es conductor de electricidad. La consecuencia inmediata es que el mecanismo mediante el cual se obtiene el cambio óptico - de transparente a opaco - debe de ser la deposición de iones metálicos sobre las láminas de material y por lo tanto se produce una transformación química, lo cual tiene el inconveniente de una reversibilidad limitada.BACKGROUND OF THE INVENTION Electrochromic devices for modulating light are known in the art, consisting of an electrochromic product confined between two conductive layers, each formed by a transparent plate, electrodes on each of said conductive layers and means for selectively providing current. electric Such devices are described in European patent EP-A-0532942 and are applicable to windows in construction, or in the automobile industry. The electrochromic product described in patent application EP-A-0532942 is an electrolytic material that includes, for example, metal salts dissolved in an organic solvent, in addition to organic acids and / or other products, therefore it is an electrical conductor. The immediate consequence is that the mechanism by which the optical change is obtained - from transparent to opaque - must be the deposition of metal ions on the sheets of material and therefore a chemical transformation takes place, which has the disadvantage of a limited reversibility.
De igual modo es necesario conseguir que la conductividad eléctrica de las capas conductoras no se vea disminuida con el paso del tiempo.Likewise, it is necessary to ensure that the electrical conductivity of the conductive layers is not diminished with the passage of time.
Otro problema no resuelto por la técnica anterior es conseguir que el cambio de óptico visible sea uniforme en toda la superficie del dispositivo, para lo cual es preciso evitar, por ejemplo, la generación de corrientes parásitas dentro del dispositivo.Another problem not solved by the prior art is to achieve that the change of visible optic is uniform over the entire surface of the device, for which it is avoid, for example, the generation of stray currents inside the device.
Finalmente es deseable conseguir un consumo de energía eléctrica mínimo. Según la técnica anterior existe una necesidad en la industria del automóvil, por ejemplo, de conseguir un material con el que se produzca un cambio óptico visible inmediato del acristalamiento para poder actuar frente a los cambios bruscos de luz . EP-A-0532942 tiene como objeto mejorar todos los aspectos mencionados; sin embargo no resuelve todos los problemas de forma eficaz.Finally it is desirable to achieve a minimum electrical energy consumption. According to the prior art, there is a need in the automobile industry, for example, to obtain a material with which an immediate visible optical change of the glazing takes place in order to be able to act against sudden changes of light. EP-A-0532942 aims to improve all aspects mentioned; However, it does not solve all problems effectively.
El dispositivo obtenido según la presente invención permite superar las dificultades citadas anteriormente haciendo posible un cambio óptico inmediato de un acristalamiento .The device obtained according to the present invention allows to overcome the aforementioned difficulties, making possible an immediate optical change of a glazing.
OBJETO DE LA INVENCIÓNOBJECT OF THE INVENTION
La presente invención tiene como objeto un dispositivo electrocrómico susceptible de experimentar un cambio óptico visible como respuesta a un cambio de un primer valor de corriente eléctrica aplicada a dicho dispositivo a un segundo valor de corriente eléctrica, la cual activa un material polimérico birrefringente incorporado en dicho dispositivo.The present invention has as an object an electrochromic device capable of undergoing a visible optical change in response to a change of a first electric current value applied to said device to a second electric current value, which activates a birefringent polymeric material incorporated in said device.
La presente invención se refiere también a un procedimiento para obtener un dispositivo electrocrómico susceptible de experimentar un cambio óptico visible como respuesta a un cambio de un primer valor de corriente eléctrica aplicada a dicho dispositivo a un segundo valor de corriente eléctrica, la cual activa un material polimérico birrefringente incorporado en dicho dispositivo.The present invention also relates to a method for obtaining an electrochromic device capable of undergoing a visible optical change in response to a change of a first electric current value applied to said device to a second electric current value, which activates a material birefringent polymer incorporated in said device.
Por último se refiere también al uso de dicho dispositivo para su aplicación con fines industriales, en particular en todo tipo de acristalamiento de edificios, pantallas, y en la industria del automóvil.Finally, it also refers to the use of said device for its application for industrial purposes, in particular in all types of glazing of buildings, screens, and in the automobile industry.
DESCRIPCIÓN DETALLADA DE LA INVENCIÓN Para lograr los objetos más arriba especificados, la presente invención tiene como objeto en primer lugar un dispositivo electrocrómico susceptible de experimentar un cambio óptico visible como respuesta a un cambio de un primer valor de corriente eléctrica aplicada a dicho dispositivo a un segundo valor de corriente eléctrica, la cual activa un material polimérico birrefringente incorporado en dicho dispositivo. Un dispositivo electrocrómico susceptible de producir un cambio óptico visible en respuesta a una corriente eléctrica, que comprende una primera lámina de un primer material eléctricamente no-conductor al menos translúcido, y una segunda lámina de un segundo material, un material electrocrómico dispuesto entre dicha primera y dicha segunda lámina, un material eléctricamente conductor y al menos translúcido, dispuesto entre dicho material electrocrómico y al menos una de dicha primera lámina y dicha segunda lámina, medios espaciadores que distancian la primera lámina de la segunda lámina, y medios para aplicar al menos una corriente eléctrica al material electrocrómico, caracterizado porque el material electrocrómico comprende al menos un material polimérico birrefringente con una primera orientación molecular que cambia reversiblemente a una segunda orientación molecular en respuesta a un cambio desde una primera corriente eléctrica a una segunda corriente eléctrica, el material eléctricamente conductor no tiene capacidad de reacción con el material electrocrómico.DETAILED DESCRIPTION OF THE INVENTION To achieve the objects specified above, the present invention has as its object first an electrochromic device capable of experiencing a visible optical change in response to a change of a first electric current value applied to said device to a second electric current value, which activates a birefringent polymeric material incorporated in said device. An electrochromic device capable of producing a visible optical change in response to an electric current, comprising a first sheet of a first electrically non-conductive material at least translucent, and a second sheet of a second material, an electrochromic material disposed between said first and said second sheet, an electrically conductive and at least translucent material, disposed between said electrochromic material and at least one of said first sheet and said second sheet, spacer means that distance the first sheet from the second sheet, and means for applying at least an electric current to the electrochromic material, characterized in that the electrochromic material comprises at least one birefringent polymeric material with a first molecular orientation that reversibly changes to a second molecular orientation in response to a change from a first electric current to a second electric current delicious, The electrically conductive material has no ability to react with the electrochromic material.
Dicho material electrocrómico comprende el material polimérico birrefringente obtenido por reacción de un polímero de etilénglicol con un agente de entrecruzamiento y al menos un polímero epoxi al menos traslúcido.Said electrochromic material comprises the birefringent polymeric material obtained by reacting an ethylene glycol polymer with a crosslinking agent and at least one at least translucent epoxy polymer.
Dicho material polimérico birrefringente puede ser conductor o no conductor.Said birefringent polymeric material may be conductive or non-conductive.
En una realización preferida dicho polímero de etilénglicol es un polietilénglicol con un peso molecular que oscila entre 5000 y 7000 y un intervalo de fusión entre 592C y 749C.In a preferred embodiment said ethylene glycol polymer is a polyethylene glycol with a molecular weight ranging from 5000 to 7000 and a melting range between 592C and 749C.
En otra realización preferente dicho polietilénglicol presenta una composición que corresponde a la fórmula C32 oH64θ°i 6 o . En una realización más preferente aún dicho polietilénglicol presenta una cantidad de grupos hidroxilo entre 16 y 23. La solubilidad en agua es del orden de 550 g/1 a 203C.In another preferred embodiment said polyethylene glycol has a composition corresponding to the formula C3 2 or H 6 4θ ° i 6 o. In a more preferred embodiment, said polyethylene glycol has an amount of hydroxyl groups between 16 and 23. The solubility in water is of the order of 550 g / 1 at 203C.
La cantidad de material polimérico birrefringente que se utiliza es del orden de 10 g de polímero por metro cuadrado de lámina de material .The amount of birefringent polymeric material used is of the order of 10 g of polymer per square meter of sheet of material.
El polímero epoxi utilizado para preparar el material electrocrómico puede ser cualquier tipo de epoxi. En una realización preferida dicho polímero epoxi es epoxi transparente NOA65 de la empresa Thorlabs.The epoxy polymer used to prepare the electrochromic material can be any type of epoxy. In a preferred embodiment said epoxy polymer is transparent epoxy NOA65 from Thorlabs.
La proporción de polímero de etilénglicol a polímero epoxi puede variar entre 40:60 y 60:40, siendo preferida una proporción de 50:50.The ratio of ethylene glycol polymer to epoxy polymer can vary between 40:60 and 60:40, a 50:50 ratio being preferred.
El agente de entrecruzamiento seleccionado entre un alcohol secundario monoinsaturado que comprende un sistema ciclopentenofenantreno, y un tensioactivo iónico del tipo del dodecilsulfato sódico. En una realización preferida dicho agente es el colesterol.The crosslinking agent selected from a monounsaturated secondary alcohol comprising a cyclopentephenanthrene system, and an ionic surfactant of the sodium dodecyl sulfate type. In a preferred embodiment said agent is cholesterol.
La cantidad de agente de entrecruzamiento frente al polímero de etilénglicol puede variar entre una proporción de 1:3 a 1:5. En una realización preferida dicha proporción es 1:2.The amount of crosslinking agent against the ethylene glycol polymer may vary between a proportion. from 1: 3 to 1: 5. In a preferred embodiment said ratio is 1: 2.
El grosor del material electrocrómico está determinado por los espaciadores, los cuales pueden ser esferas sólidas mezcladas con el material electrocrómico y seleccionadas entre esferas de cristal, esferas de vidrio, esferas de material plástico, y mezclas de las mismas. Dichos medios espaciadores pueden ser también rugosidades de las propias láminas del material usado, que actúan como tales, de modo que la separación entre láminas en el dispositivo electrocrómico está determinada por la presencia y por el tamaño de dichos medios espaciadores . En una realización preferida dichos medios espaciadores son esferas de cristal. De forma más preferida aún dichas esferas son microesferas tales como las que comercializa actualmente la empresa AGFA.The thickness of the electrochromic material is determined by the spacers, which can be solid spheres mixed with the electrochromic material and selected from glass spheres, glass spheres, plastic spheres, and mixtures thereof. Said spacer means can also be roughnesses of the sheets of the material used, which act as such, so that the separation between sheets in the electrochromic device is determined by the presence and size of said spacer means. In a preferred embodiment said spacer means are glass spheres. More preferably, said spheres are microspheres such as those currently sold by AGFA.
El diámetro de dichas esferas espaciadoras puede variar entre 5μ y 200μ. El material electrocrómico puede por lo tanto tener un grosor entre 5 y 200 μ. Opcionalmente el material electrocrómico puede incluir un colorante con el fin de conseguir cambios ópticos visibles que impliquen un cambio de color. El colorante debe ser un compuesto con una capacidad conductora mínima para que se adhiera al material conductor. De manera preferida se usa un colorante dicroico, es decir un colorante que hace rotar la luz polarizada. Colorantes dicroicos adecuados son comercializados por ejemplo por las empresas DuPont y Merck.The diameter of said spacers can vary between 5μ and 200μ. The electrochromic material can therefore have a thickness between 5 and 200 μ. Optionally, the electrochromic material may include a dye in order to achieve visible optical changes that imply a color change. The dye must be a compound with a minimum conductive capacity to adhere to the conductive material. Preferably, a dichroic dye is used, that is, a dye that rotates the polarized light. Suitable dichroic dyes are marketed, for example, by DuPont and Merck.
La cantidad de colorante que se utiliza varía desde 0,05 g/Kg de material electrocrómico preparado hasta 0,5 g/Kg de material electrocrómico.The amount of dye used varies from 0.05 g / kg of prepared electrochromic material to 0.5 g / kg of electrochromic material.
La corriente eléctrica utilizada para producir el cambio óptico puede ser corriente alterna o corriente continua En el caso de corrientes continuas pueden ser inferiores a 50V o incluso inferiores a 15V. En el caso de corrientes alternas pueden ser inferiores a 220V. En una realización preferida de la invención la corriente usada es corriente continua.The electric current used to produce the optical change can be alternating current or direct current. In the case of direct currents they can be less than 50V or even less than 15V. If of alternating currents can be less than 220V. In a preferred embodiment of the invention the current used is direct current.
El material eléctricamente conductor tiene una resistencia entre 10"4 y 200 Ω / mm2. Preferentemente varía entre 0.0005 Ω/mm2 y 100 Ω/mm2. De manera más preferente aún varía entre 10~3 Ω/mm2 y 50 Ω/mm2. De forma más preferida aún dicha resistencia es de 0.01 Ω.The electrically conductive material has a resistance between 10 "4 and 200 Ω / mm 2. Preferably it varies between 0.0005 Ω / mm 2 and 100 Ω / mm 2. More preferably it still varies between 10 ~ 3 Ω / mm 2 and 50 Ω / mm 2. Even more preferably said resistance is 0.01 Ω.
El material conductor dispuesto entre el material electrocrómico y la primera lámina es preferentemente no tóxico, y no debe reaccionar con el material polimérico birrefringente .The conductive material disposed between the electrochromic material and the first sheet is preferably non-toxic, and must not react with the birefringent polymeric material.
Dicho material conductor puede ser líquido, gel o incluso sólido, y puede estar seleccionado entre barnices, sales metálicas (por ejemplo haluros de plata), sales metálicas disueltas en al menos un disolvente orgánico, y combinaciones de los mismos.Said conductive material may be liquid, gel or even solid, and may be selected from varnishes, metal salts (for example silver halides), metal salts dissolved in at least one organic solvent, and combinations thereof.
En una realización dicho material es una sal metálica disuelta en un disolvente orgánico. En una realización otra específica dicha sal es ioduro potásico de 99% de pureza disuelto en dimetilsulfóxido de 99% de pureza.In one embodiment said material is a metal salt dissolved in an organic solvent. In a specific embodiment, said salt is 99% pure potassium iodide dissolved in 99% pure dimethylsulfoxide.
En otra realización alternativa preferida dicho material conductor es un óxido metálico: de manera preferida dicho óxido metálico es óxido de estaño o de indio fácilmente aplicable como un laminado muy fino.In another preferred alternative embodiment said conductive material is a metal oxide: preferably said metal oxide is tin or indium oxide readily applicable as a very thin laminate.
El material de la primera y segunda láminas puede ser igual o distinto. Dicho material puede ser vidrio, cristal o plástico. Así, el material de la segunda lámina puede ser un material no-conductor al menos translúcido, o un material opaco de un determinado color.The material of the first and second sheets may be the same or different. Said material may be glass, glass or plastic. Thus, the material of the second sheet can be a non-conductive material at least translucent, or an opaque material of a certain color.
Los medios para aplicar corriente eléctrica al material electrocrómico pueden ser electrodos de diversa naturaleza, que se unen al material electrocrómico por pegado o soldadura. En una realización preferida se unen por soldadura, y particularmente, por soldadura con óxido de indio y/o estaño.The means for applying electric current to the electrochromic material can be electrodes of various kinds, which are attached to the electrochromic material by gluing or welding. In a preferred embodiment they are joined by welding, and particularly, by welding with indium oxide and / or tin.
La presencia de un material conductor asociado al uso de un material polimérico birrefringente, en lugar de materiales electrolíticos como los que se describen en EP- A-0532942, evita la degradación de la capacidad conductora del dispositivo debido a la deposición metálica, y la pérdida de uniformidad en el cambio óptico.The presence of a conductive material associated with the use of a birefringent polymeric material, instead of electrolytic materials such as those described in EP-A-0532942, prevents degradation of the conductive capacity of the device due to metallic deposition, and loss of uniformity in optical change.
Un objeto adicional de la presente invención es un procedimiento para preparar un dispositivo electrocrómico que comprende una primera lámina de un primer material no- conductor al menos translúcido, y una segunda lámina de un segundo material, un material electrocrómico dispuesto entre dicha primera y dicha segunda lámina, un material eléctricamente conductor y al menos translúcido, dispuesto entre dicho material electrocrómico y al menos una de dicha primera lámina y dicha segunda lámina, así como medios espaciadores que distancian la primera lámina de la segunda lámina, caracterizado porque comprende: una primera etapa en la que se aplica un recubrimiento eléctricamente conductor y al menos traslúcido, sobre una superficie de al menos una de dichas láminas; una segunda etapa en la que se aplica homogéneamente sobre dicho recubrimiento conductor, una capa de un material electrocrómico fraguable que comprende una mezcla homogénea y al menos semilíquida de un material polimérico birrefringente obtenido por reacción de un polímero de etilénglicol con un agente de entrecruzamiento y al menos un polímero epoxi al menos traslúcido; una tercera etapa en la que se aplica una segunda lámina sobre dicha capa de material electrocrómico; una cuarta etapa en la que el material electrocrómico dispuesto entre dichas láminas se somete a fraguado mediante rayos ultavioleta; una quinta etapa en la que se aplican medios para aplicar una corriente eléctrica.A further object of the present invention is a process for preparing an electrochromic device comprising a first sheet of a first non-translucent non-conductive material, and a second sheet of a second material, an electrochromic material disposed between said first and said second sheet, an electrically conductive and at least translucent material, disposed between said electrochromic material and at least one of said first sheet and said second sheet, as well as spacer means that distance the first sheet of the second sheet, characterized in that it comprises: a first stage in which an electrically conductive and at least translucent coating is applied, on a surface of at least one of said sheets; a second stage in which a layer of a fragile electrochromic material comprising a homogeneous and at least semi-liquid mixture of a birefringent polymeric material obtained by reacting an ethylene glycol polymer with a crosslinking agent is applied homogeneously onto said conductive coating less an at least translucent epoxy polymer; a third stage in which a second sheet is applied on said electrochromic material layer; a fourth stage in which the electrochromic material disposed between said sheets is subjected to setting by ultaviolet rays; a fifth stage in which means are applied to apply an electric current.
La viscosidad del material electrocrómico fraguable que se aplica en la segunda etapa varía entre 650 cp y 1.500 cp. De manera preferida dicha viscosidad varía entre 1.000 cp y 1.200 cp.The viscosity of the fragile electrochromic material that is applied in the second stage varies between 650 cp and 1,500 cp. Preferably said viscosity varies between 1,000 cp and 1,200 cp.
La elongación a la rotura del material electrocrómico obtenido puede ser hasta del 80%, particularmente si el material es plástico. El secado o curado del dispositivo electrocrómico se realiza mediante rayos ultravioleta con una lámpara de 100 W, durante un tiempo de 5 min a 45 min, dependiendo del grosor de la capa de material electrocrómico obtenida entre las dos láminas . Un objeto adicional de la presente invención es el uso del dispositivo obtenido mediante el procedimiento descrito para el acristalamiento de edificios así como para el acristalamiento de todo tipo de vehículos .The elongation at break of the electrochromic material obtained can be up to 80%, particularly if the material is plastic. Drying or curing of the electrochromic device is carried out by ultraviolet rays with a 100 W lamp, for a time of 5 min to 45 min, depending on the thickness of the layer of electrochromic material obtained between the two sheets. A further object of the present invention is the use of the device obtained by the procedure described for the glazing of buildings as well as for the glazing of all types of vehicles.
Otro uso del dispositivo de la presente invención es para la fabricación de pantallas en general, así como para fabricación de separadores de espacios en el interior de edificios, por ejemplo, en hospitales, oficinas.Another use of the device of the present invention is for the manufacture of screens in general, as well as for the manufacture of space separators inside buildings, for example, in hospitals, offices.
La presente invención proporciona una serie de ventajas frente al estado de la técnica como son las siguientes:The present invention provides a series of advantages over the state of the art such as the following:
El mecanismo por el cual se produce el cambio óptico consiste en una alineación u orientación de las moléculas del material polimérico birrefringente contenido entre las placas o láminas de material que conforman el dispositivo electrocrómico, por lo cual el cambio óptico no implica una reacción química y el deterioro del dispositivo en general es mucho menor.The mechanism by which the optical change occurs consists of an alignment or orientation of the molecules of the birefringent polymeric material contained between the plates or sheets of material that make up the electrochromic device, whereby the optical change does not involve a chemical reaction and Device deterioration in general is much less.
Según la presente invención el material electrocrómico no tiene que ser necesariamente conductor. Otra ventaja adicional es que los electrodos no tienen por qué tener una forma definida.According to the present invention the electrochromic material does not necessarily have to be conductive. Another additional advantage is that the electrodes do not have to have a definite shape.
Con el dispositivo objeto de la presente invención se puede conseguir: - modular la entrada de luz en un vehículo, por el accionamiento de un potenciómetro que produzca de forma inmediata el cambio óptico del acristalamiento, regular la luz que entra en un edificio según la hora del día y/o las condiciones meteorológicasWith the device object of the present invention it is possible to: - modulate the entry of light into a vehicle, by activating a potentiometer that immediately produces the optical change of the glazing, regulate the light entering a building according to the time of the day and / or weather conditions
Por lo tanto es evidente que la presente invención resuelve problemas importantes relacionados con necesidades diarias de la vida como es el problema de la incómoda situación que se produce en un lugar sometido a la exposición solar permanente en edificios con fachadas de cristal, sin necesidad de utilizar persianas.Therefore it is evident that the present invention solves important problems related to daily necessities of life such as the problem of the uncomfortable situation that occurs in a place subject to permanent sun exposure in buildings with glass facades, without using Blinds.
Otro problema que resuelve la presente invención es evitar el peligro que representa dejar un vehículo, por ejemplo aparcado en la calle, con su interior visible. Otra situación de peligro potencial que resuelve la presente invención es conducir un vehículo bajo una exposición solar que no se podía controlar a voluntad según el estado de la técnica.Another problem solved by the present invention is to avoid the danger of leaving a vehicle, for example parked on the street, with its interior visible. Another potentially dangerous situation resolved by the present invention is to drive a vehicle under a sun exposure that could not be controlled at will according to the state of the art.
El siguiente ejemplo tiene como finalidad ilustrar la invención, sin que deba considerarse limitativo del alcance de la misma.The following example is intended to illustrate the invention, without it being considered as limiting its scope.
BREVE DESCRIPCIÓN DE LAS FIGURAS La figura 1 muestra esquemáticamente una primera realización de un dispositivo electrocrómico según la invención.BRIEF DESCRIPTION OF THE FIGURES Figure 1 schematically shows a first embodiment of an electrochromic device according to the invention.
La figura 2 muestra esquemáticamente una segunda realización de un dispositivo electrocrómico según la invención. MODOS DE REALIZACIÓN DE LA INVENCIÓN A continuación, para ilustrar algunos aspectos de la invención, el dispositivo se describirá en base a unas figuras en las que: La figura 1 muestra un dispositivo electrocrómico que comprende una primera lámina 1 y una segunda lámina 2, que encierran el material electrocrómico 3, la primera capa de material eléctricamente conductor 4 aplicado sobre dicha primera lámina 1 , los medios espaciadores 5 y los medios de aplicación de corriente eléctrica 6.Figure 2 schematically shows a second embodiment of an electrochromic device according to the invention. EMBODIMENTS OF THE INVENTION Next, to illustrate some aspects of the invention, the device will be described based on figures in which: Figure 1 shows an electrochromic device comprising a first sheet 1 and a second sheet 2, which They enclose the electrochromic material 3, the first electrically conductive material layer 4 applied on said first sheet 1, the spacer means 5 and the electric current application means 6.
Por otra parte, la figura 2 ilustra en adición, la primera lámina 1 y la segunda lámina 2, el material electrocrómico 3, la capa de material eléctricamente conductor 4 aplicado sobre dicha primera lámina 1, los medios espaciadores 5, los medios de aplicación de corriente eléctrica 6, y una segunda capa de material conductor aplicado sobre la segunda lámina 2a.On the other hand, Figure 2 illustrates in addition, the first sheet 1 and the second sheet 2, the electrochromic material 3, the electrically conductive material layer 4 applied on said first sheet 1, the spacer means 5, the application means of electric current 6, and a second layer of conductive material applied on the second sheet 2a.
Para preparar el dispositivo mostrado en la figura 1, puede seguirse el siguiente proceso: Una lámina de vidrio, 1, de 1 m2 de superficie se recubre por ejemplo, por pulverización por una de sus caras con un material conductor 4 que consiste en una disolución de ioduro de plata de 99% de pureza en dimetilsulfóxido de 99% de pureza. Se deja secar durante un tiempo aproximado de 45 min. Se prepara el material electrocrómico 3 mediante la mezcla de epoxi transparente NOA65 de la firma Thorlabs, con polietilénglicol de fórmula C32 oH 64 o°ι 6 o / en una proporción 1 a 1 de ambas sustancias, y junto con colesterol en una proporción de este último que equivale al 20% del total de la mezcla de los tres componentes. Se agita hasta obtener una mezcla homogénea, que constituye el material electrocrómico 3. A la mezcla resultante se le añaden microesferas espaciadoras 5, de la firma AGFA, y se agita hasta obtener de nuevo una mezcla homogénea. La mezcla final obtenida se vierte sobre la lámina de vidrio, 1, recubierta con el material conductor 4, repartiéndola de manera uniforme. Se coloca encima de la cara que tiene el material electrocrómico 3 una segunda lámina de vidrio 2 y se procede al curado o secado con radiación UV, durante un tiempo de unos 45 min. Una vez seco el dispositivo obtenido se sueldan a él dos electrodos 5, mediante el uso de óxido de estaño, de manera que dichos electrodos estén en contacto con el material eléctricamente conductor 4 contenido entre la primera lámina 1 y el material electrocrómico 3. To prepare the device shown in Figure 1, the following process can be followed: A glass sheet, 1, of 1 m 2 of surface is covered, for example, by spraying on one of its faces with a conductive material 4 consisting of a 99% pure silver iodide solution in 99% pure dimethylsulfoxide. It is allowed to dry for an approximate time of 45 min. The electrochromic material 3 is prepared by mixing transparent epoxy NOA65 from Thorlabs, with polyethylene glycol of formula C 32 or H 64 or 6 or 6 in a 1 to 1 ratio of both substances, and together with cholesterol in a proportion of the latter, which is equivalent to 20% of the total mixture of the three components. It is stirred until a homogeneous mixture is obtained, which constitutes the electrochromic material 3. The resulting mixture is added with space microspheres 5, from the AGFA firm, and stirred until a homogeneous mixture is obtained again. The final mixture obtained is poured onto the sheet of glass, 1, coated with conductive material 4, distributing it evenly. A second sheet of glass 2 is placed on top of the face having the electrochromic material 3 and curing or drying with UV radiation, for a time of about 45 min. Once the device obtained is dry, two electrodes 5 are welded to it, by means of the use of tin oxide, so that said electrodes are in contact with the electrically conductive material 4 contained between the first sheet 1 and the electrochromic material 3.

Claims

REIVINDICACIONES
1. Un dispositivo electrocrómico susceptible de producir un cambio óptico visible en respuesta a una corriente eléctrica, que comprende una primera lámina ( 1 ) de un primer material eléctricamente no-conductor al menos translúcido, y una segunda lámina (2) de un segundo material, un material electrocrómico (3) dispuesto entre dicha primera y dicha segunda lámina (2), un material eléctricamente conductor (4) y al menos translúcido, dispuesto entre dicho material electrocrómico (3) y al menos una de dichas primera lámina (1) y dicha segunda lámina (2), medios espaciadores (5) que distancian la primera lámina ( 1 ) de la segunda lámina ( 2 ) , y medios ( 6 ) para aplicar al menos una corriente eléctrica al material electrocrómico (AB), caracterizado porque el material electrocrómico (3) comprende al menos un material polimérico birrefringente con una primera orientación molecular que cambia reversiblemente a una segunda orientación molecular en respuesta a un cambio desde una primera corriente eléctrica a una segunda corriente eléctrica, el material eléctricamente conductor (4) no tiene capacidad de reacción con el material electrocrómico (AB).1. An electrochromic device capable of producing a visible optical change in response to an electric current, comprising a first sheet (1) of a first electrically non-conductive material at least translucent, and a second sheet (2) of a second material , an electrochromic material (3) disposed between said first and said second sheet (2), an electrically conductive material (4) and at least translucent, disposed between said electrochromic material (3) and at least one of said first sheet (1) and said second sheet (2), spacer means (5) that distance the first sheet (1) from the second sheet (2), and means (6) for applying at least one electric current to the electrochromic material (AB), characterized in that The electrochromic material (3) comprises at least one birefringent polymeric material with a first molecular orientation that reversibly changes to a second molecular orientation in response to a change From a first electric current to a second electric current, the electrically conductive material (4) has no capacity to react with the electrochromic material (AB).
2. Un dispositivo según la reivindicación 1, caracterizado porque el material electrocrómico (3) comprende el material polimérico birrefringente obtenido por reacción de un polímero de etilénglicol con un agente de entrecruzamiento; al menos un polímero epoxi al menos traslúcido. 2. A device according to claim 1, characterized in that the electrochromic material (3) comprises the birefringent polymeric material obtained by reacting an ethylene glycol polymer with a crosslinking agent; at least one at least translucent epoxy polymer.
3. Un dispositivo según la reivindicación 2, caracterizado porque el agente de entrecruzamiento y el polímero de etilénglicol están presentes en una proporción de 1:3 a 1:5.3. A device according to claim 2, characterized in that the crosslinking agent and the ethylene glycol polymer are present in a ratio of 1: 3 to 1: 5.
4. Un dispositivo según la reivindicación 2 o 3, caracterizado porque el agente de entrecruzamiento y el polímero de etilénglicol están presentes en una proporción de 1:2.4. A device according to claim 2 or 3, characterized in that the crosslinking agent and the ethylene glycol polymer are present in a ratio of 1: 2.
5. Un dispositivo según la reivindicación 2, caracterizado porque el polímero epoxi y el polímero de etilénglicol están presentes en una proporción de 40:60 a 60:40.5. A device according to claim 2, characterized in that the epoxy polymer and the ethylene glycol polymer are present in a ratio of 40:60 to 60:40.
6. Un dispositivo según la reivindicación 2, caracterizado porque el polímero epoxi y el polímero de etilénglicol están presentes en una proporción de 50:50.A device according to claim 2, characterized in that the epoxy polymer and the ethylene glycol polymer are present in a 50:50 ratio.
7. Un dispositivo según cualquiera de las reivindicaciones 2 a 6, caracterizado porque el polímero de etilénglicol es un polietilénglicol con un peso molecular entre 5000 y 7000 y un intervalo de fusión entre 59°C y 74QC.7. A device according to any of claims 2 to 6, characterized in that the ethylene glycol polymer is a polyethylene glycol with a molecular weight between 5000 and 7000 and a melting range between 59 ° C and 74 QC .
8. Un dispositivo según la reivindicación 7, caracterizado porque el polietilénglicol tiene la fórmula
Figure imgf000015_0001
8. A device according to claim 7, characterized in that the polyethylene glycol has the formula
Figure imgf000015_0001
9. Un dispositivo según la reivindicación 8, caracterizado porque el polietilénglicol tiene entre 16 y 23 hidroxilos.9. A device according to claim 8, characterized in that the polyethylene glycol has between 16 and 23 hydroxyls.
10. Un dispositivo según la reivindicación 9, caracterizado porque el polietilénglicol tiene una solubilidad en agua de 550g/l a 202C.10. A device according to claim 9, characterized in that the polyethylene glycol has a Water solubility of 550g / 202C.
11. Un dispositivo según la reivindicación 2, caracterizado porque el agente de entrecruzamiento está seleccionado entre un alcohol secundario monoinsaturado que comprende un sistema ciclopentenofenantreno, y un tensioactivo iónico.A device according to claim 2, characterized in that the crosslinking agent is selected from a monounsaturated secondary alcohol comprising a cyclopentephenanthrene system, and an ionic surfactant.
12. Un dispositivo según la reivindicación 2, caracterizado porque el agente de entrecruzamiento es colesterol.12. A device according to claim 2, characterized in that the cross-linking agent is cholesterol.
13. Un dispositivo según la reivindicación 1, caracterizado porque el grosor del material electrocrómico (3) está determinado por los espaciadores.13. A device according to claim 1, characterized in that the thickness of the electrochromic material (3) is determined by the spacers.
14. Un dispositivo según la reivindicación 1 o 13, caracterizado porque los espaciadores son esferas sólidas mezcladas con el material electrocrómico (3) y seleccionadas entre esferas de cristal, esferas de vidrio, esferas de material plástico, y mezclas de las mismas.14. A device according to claim 1 or 13, characterized in that the spacers are solid spheres mixed with the electrochromic material (3) and selected from glass spheres, glass spheres, plastic spheres, and mixtures thereof.
15. Un dispositivo según la reivindicación 1, 13 o 14, caracterizado porque el material electrocrómico (3) tiene un grosor entre 5 y 200 μm.15. A device according to claim 1, 13 or 14, characterized in that the electrochromic material (3) has a thickness between 5 and 200 μm.
16. Un dispositivo según la reivindicación 1, 13, 14 o 15, caracterizado porque el material electrocrómico (3) comprende un colorante.16. A device according to claim 1, 13, 14 or 15, characterized in that the electrochromic material (3) comprises a dye.
17. Un dispositivo según la reivindicación 16, caracterizado poique el colorante es un colorante dicróico.17. A device according to claim 16, characterized in that the dye is a dichroic dye.
18. Un dispositivo según la reivindicación 1, 13, 14, 15 o 16, caracterizado porque el material electrocrómico (3) produce un cambio óptico visible en respuesta a la aplicación de corrientes continuas inferiores a 50V.18. A device according to claim 1, 13, 14, 15 or 16, characterized in that the electrochromic material (3) produces a visible optical change in response to the application of direct currents below 50V.
19. Un dispositivo según la reivindicación 18, caracterizado porque el material electrocrómico (AB) produce un cambio óptico visible en respuesta a la aplicación de corrientes continuas inferiores a 15V.19. A device according to claim 18, characterized in that the electrochromic material (AB) produces a visible optical change in response to the application of direct currents below 15V.
20. Un dispositivo según la reivindicación 1, 13, 14, 15 o 16, caracterizado porque el material electrocrómico (3) produce un cambio óptico visible en respuesta a la aplicación de corrientes alternas inferiores a 220V.20. A device according to claim 1, 13, 14, 15 or 16, characterized in that the electrochromic material (3) produces a visible optical change in response to the application of alternating currents below 220V.
21. Un dispositivo según la reivindicación 1, caracterizado porque el material eléctricamente conductor21. A device according to claim 1, characterized in that the electrically conductive material
—A 0—A 0
(4) tiene una resistencia entre 10 y 200 Ω / mm .(4) has a resistance between 10 and 200 Ω / mm.
22. Un dispositivo según la reivindicación 1 o 21, caracterizado porque el material eléctricamente conductor22. A device according to claim 1 or 21, characterized in that the electrically conductive material
(4) tiene una resistencia entre 10"3 y 50 Ω / mm .(4) has a resistance between 10 "3 and 50 Ω / mm.
23. Un dispositivo según la reivindicación 1, 21 o 22, caracterizado porque el material eléctricamente conductor (4) está seleccionado entre geles, sólidos y líquidos.23. A device according to claim 1, 21 or 22, characterized in that the electrically conductive material (4) is selected from gels, solids and liquids.
24. Un dispositivo según la reivindicación 1, 21, 22 o 23, caracterizado porque el material eléctricamente conductor (4) está seleccionado entre barnices, sales metálicas, sales metálicas disueltas en al menos un disolvente orgánico, y combinaciones de los mismos.24. A device according to claim 1, 21, 22 or 23, characterized in that the electrically conductive material (4) is selected from varnishes, metal salts, metal salts dissolved in at least one organic solvent, and combinations thereof.
25. Un dispositivo según la reivindicación 24, caracterizado porque la sal metálica es ioduro potásico y porque el disolvente metálico es dimetilsulfóxido. 25. A device according to claim 24, characterized in that the metal salt is potassium iodide and that the metal solvent is dimethylsulfoxide.
26. Un dispositivo según la reivindicación 1, 21, 22 o 23, caracterizado porque el material eléctricamente conductor (4) es un óxido metálico.26. A device according to claim 1, 21, 22 or 23, characterized in that the electrically conductive material (4) is a metal oxide.
27. Un dispositivo según la reivindicación 26, caracterizado porque el óxido metálico está seleccionado entre óxido de indio y óxido de estaño.27. A device according to claim 26, characterized in that the metal oxide is selected from indium oxide and tin oxide.
28. Un dispositivo según la reivindicación 1, caracterizado porque el material de la segunda lámina (2) es un material no-conductor al menos translúcido.28. A device according to claim 1, characterized in that the material of the second sheet (2) is a non-conductive material at least translucent.
29. Un procedimiento para preparar un dispositivo electrocrómico que comprende una primera lámina (1) de un primer material no-conductor al menos translúcido, y una segunda lámina (2) de un segundo material, un material electrocrómico ( 3 ) dispuesto entre dicha primera y dicha segunda lámina (2), un material eléctricamente conductor (4) y al menos translúcido, dispuesto entre dicho material electrocrómico ( 3 ) y al menos una de dicha primera lámina (1) y dicha segunda lámina (2), así como medios espaciadores (5) que distancian la primera lámina (1) de la segunda lámina (2), caracterizado porque comprende una primera etapa en la que se aplica un recubrimiento eléctricamente conductor y al menos translúcido, sobre una superficie de al menos una de dichas láminas; una segunda etapa en la que se aplica homogéneamente sobre dicho recubrimiento conductor, una capa de un material electrocrómico (3) fraguable que comprende una mezcla homogénea y al menos semilíquida de un material polimérico birrefringente obtenido por reacción de un polímero de etilénglicol con un agente de entrecruzamiento y al menos un polímero epoxi al menos translúcido; una tercera etapa en la que se aplica una segunda lámina (2) sobre dicha capa de material electrocrómico (3); una cuarta etapa en la que el material electrocrómico (3) dispuesto entre dichas láminas se somete a fraguado mediante rayos ultravioleta; una quinta etapa en la que se aplican medios para aplicar una corriente eléctrica.29. A method for preparing an electrochromic device comprising a first sheet (1) of a first at least translucent non-conductive material, and a second sheet (2) of a second material, an electrochromic material (3) disposed between said first and said second sheet (2), an electrically conductive material (4) and at least translucent, disposed between said electrochromic material (3) and at least one of said first sheet (1) and said second sheet (2), as well as means spacers (5) that distance the first sheet (1) from the second sheet (2), characterized in that it comprises a first stage in which an electrically conductive and at least translucent coating is applied, on a surface of at least one of said sheets ; a second stage in which a layer of a fragile electrochromic material (3) comprising a homogeneous and at least semi-liquid mixture of a birefringent polymeric material obtained by reacting an ethylene glycol polymer with an agent of homogeneously is applied onto said conductive coating crosslinking and at least one at least translucent epoxy polymer; a third stage in which a second sheet (2) is applied on said electrochromic material layer (3); a fourth stage in which the electrochromic material (3) disposed between said sheets is subjected to setting by ultraviolet rays; a fifth stage in which means are applied to apply an electric current.
30. Un procedimiento según la reivindicación 29, caracterizado porque el material electrocrómico (3) fraguable que se aplica en la segunda etapa, tiene una viscosidad entre 650 y 1.500 cp.30. A method according to claim 29, characterized in that the fragile electrochromic material (3) applied in the second stage has a viscosity between 650 and 1,500 cp.
31. Un procedimiento según la reivindicación 30, caracterizado porque la viscosidad del material electrocrómico (3) fraguable es de 1.000 a 1.200 cp.31. A method according to claim 30, characterized in that the viscosity of the fragile electrochromic material (3) is 1,000 to 1,200 cp.
32. Un procedimiento según la reivindicación 29, 30 o 31, caracterizado porque la elongación a la rotura del material electrocrómico (3) fraguable es menor del 80%.32. A method according to claim 29, 30 or 31, characterized in that the elongation at breakage of the fragile electrochromic material (3) is less than 80%.
33. Un procedimiento según la reivindicación 29, caracterizado porque el agente de entrecruzamiento y el polímero de etilénglicol están presentes en una proporción de 1:3 a 1:5.33. A process according to claim 29, characterized in that the crosslinking agent and the ethylene glycol polymer are present in a ratio of 1: 3 to 1: 5.
34. Un procedimiento según la reivindicación 33, caracterizado porque el agente de entrecruzamiento y el polímero de etilénglicol están presentes en una proporción de 1:2.34. A process according to claim 33, characterized in that the crosslinking agent and the ethylene glycol polymer are present in a ratio of 1: 2.
35. Un procedimiento según la reivindicación 29, caracterizado porque el polímero epoxi y el polímero de etilénglicol están presentes en una proporción de 40:60 a 60 : 40 ,35. A process according to claim 29, characterized in that the epoxy polymer and the ethylene glycol polymer are present in a ratio of 40:60 to 60: 40,
36. Un procedimiento según la reivindicación 29, caracterizado porque el polímero epoxi y el polímero de etilénglicol están presentes en una proporción de 50:50.36. A process according to claim 29, characterized in that the epoxy polymer and the ethylene glycol polymer are present in a 50:50 ratio.
37. Un procedimiento según cualquiera de las reivindicaciones 29 a 36, caracterizado porque el polímero de etilénglicol es un polietilénglicol con un peso molecular entre 5000 y 7000 y un intervalo de fusión entre 592C y 74°C.37. A process according to any of claims 29 to 36, characterized in that the ethylene glycol polymer is a polyethylene glycol with a molecular weight between 5000 and 7000 and a melting range between 592C and 74 ° C.
38. Un procedimiento según la reivindicación 37, caracterizado porque el polietilénglicol tiene la fórmula C32 o H6 0 O16o •38. A process according to claim 37, characterized in that the polyethylene glycol has the formula C 32 or H 6 0 O 16 or •
39. Un procedimiento según la reivindicación 38, caracterizado porque el polietilénglicol tiene entre 16 y 23 hidroxilos.39. A process according to claim 38, characterized in that the polyethylene glycol has between 16 and 23 hydroxyls.
40. Un procedimiento según la reivindicación 39, caracterizado porque el polietilénglicol tiene una solubilidad en agua de 550g/l a 202C.40. A process according to claim 39, characterized in that the polyethylene glycol has a water solubility of 550g / l at 202C.
41. Un procedimiento según la reivindicación 29, caracterizado porque el agente de entrecruzamiento está seleccionado entre un alcohol secundario monoinsaturado que comprende un sistema ciclopentenofenantreno, y un tensioactivo iónico.41. A method according to claim 29, characterized in that the cross-linking agent is selected from a monounsaturated secondary alcohol comprising a cyclopentephenanthrene system, and an ionic surfactant.
42. Un procedimiento según la reivindicación 29, caracterizado porque el agente de entrecruzamiento es colesterol.42. A method according to claim 29, characterized in that the cross-linking agent is cholesterol.
43. Un procedimiento según la reivindicación 29, caracterizado porque el grosor del material electrocrómico (AB) está determinado por los espaciadores.43. A method according to claim 29, characterized in that the thickness of the electrochromic material (AB) is determined by the spacers.
44. Un procedimiento según la reivindicación 29 o 43, caracterizado porque los espaciadores son esferas sólidas mezcladas con el material electrocrómico (3) y seleccionadas entre esferas de cristal, esferas de vidrio, esferas de material plástico, y mezclas de las mismas.44. A method according to claim 29 or 43, characterized in that the spacers are solid spheres mixed with the electrochromic material (3) and selected from glass spheres, glass spheres, plastic spheres, and mixtures thereof.
45. Un procedimiento según la reivindicación 29, 43 o 44, caracterizado porque el material electrocrómico (3) tiene un grosor entre 5 y 200 μm.45. A method according to claim 29, 43 or 44, characterized in that the electrochromic material (3) has a thickness between 5 and 200 μm.
46. Un procedimiento según la reivindicación 29, 43, 44 o 45, caracterizado porque el material electrocrómico (3) comprende un colorante .46. A method according to claim 29, 43, 44 or 45, characterized in that the electrochromic material (3) comprises a dye.
47. Un procedimiento según la reivindicación 46, caracterizado porque el colorante es un colorante dicróico.47. A method according to claim 46, characterized in that the dye is a dichroic dye.
48. Un procedimiento según la reivindicación 29, 43, 44, 45 o 46, caracterizado porque el material electrocrómico (3) produce un cambio óptico visible en respuesta a la aplicación de corrientes continuas inferiores a 50V.48. A method according to claim 29, 43, 44, 45 or 46, characterized in that the electrochromic material (3) produces a visible optical change in response to the application of continuous currents below 50V.
49. Un procedimiento según la reivindicación 48, caracterizado porque el material electrocrómico (3) produce un cambio óptico visible en respuesta a la aplicación de corrientes continuas inferiores a 15V.49. A method according to claim 48, characterized in that the electrochromic material (3) produces a visible optical change in response to the application of direct currents below 15V.
50. Un procedimiento según la reivindicación 29, 43, 44, 45 o 46, caracterizado porque el material electrocrómico (3) produce un cambio óptico visible en respuesta a la aplicación de corrientes alternas inferiores a 220V. 50. A method according to claim 29, 43, 44, 45 or 46, characterized in that the electrochromic material (3) produces a visible optical change in response to the application of alternating currents below 220V.
51. Un procedimiento según la reivindicación 29, caracterizado porque el material eléctricamente conductor (4) tiene una resistencia entre 10"4 y 200 Ω / mm2.51. A method according to claim 29, characterized in that the electrically conductive material (4) has a resistance between 10 "4 and 200 Ω / mm 2 .
52. Un procedimiento según la reivindicación 29 o 51, caracterizado porque el material eléctricamente conductor (4) tiene una resistencia entre 10"3 y 50 Ω / mm2.52. A method according to claim 29 or 51, characterized in that the electrically conductive material (4) has a resistance between 10 "3 and 50 Ω / mm 2 .
53. Un procedimiento según la reivindicación 29, 51 o 52, caracterizado porque el material eléctricamente conductor (4) está seleccionado entre geles, sólidos y líquidos.53. A method according to claim 29, 51 or 52, characterized in that the electrically conductive material (4) is selected from gels, solids and liquids.
54. Un procedimiento según la reivindicación 29, 51, 52 o 53, caracterizado porque el material eléctricamente conductor (4) está seleccionado entre barnices, sales metálicas disueltas en al menos un disolvente orgánico, y combinaciones de los mismos .54. A method according to claim 29, 51, 52 or 53, characterized in that the electrically conductive material (4) is selected from varnishes, metal salts dissolved in at least one organic solvent, and combinations thereof.
55. Un procedimiento según la reivindicación 54, caracterizado porque la sal metálica es ioduro potásico y porque el disolvente metálico es dimetilsulfóxido.55. A process according to claim 54, characterized in that the metal salt is potassium iodide and that the metal solvent is dimethylsulfoxide.
56. Un procedimiento según la reivindicación 29, 51, 52 o 53, caracterizado caracterizada porque el material eléctricamente conductor (4) es un óxido metálico.56. A method according to claim 29, 51, 52 or 53, characterized in that the electrically conductive material (4) is a metal oxide.
57. Un procedimiento según la reivindicación 56, caracterizado porque el óxido metálico está seleccionado entre óxido de indio y óxido de estaño.57. A method according to claim 56, characterized in that the metal oxide is selected from indium oxide and tin oxide.
58. Un procedimiento según la reivindicación 29, caracterizado porque el material de la segunda lámina (2) es un material no-conductor al menos translúcido. 58. A method according to claim 29, characterized in that the material of the second sheet (2) is a non-conductive material at least translucent.
59. Un procedimiento según la reivindicación 29, caracterizado porque el material electrocrómico (3) se aplica mediante un proceso seleccionado entre procesos de pintado, inmersión y pulverización.59. A method according to claim 29, characterized in that the electrochromic material (3) is applied by a process selected from painting, immersion and spraying processes.
60. Un procedimiento según la reivindicación 29, caracterizado porque el material eléctricamente conductor (4) se aplica mediante un proceso seleccionado entre procesos de pintado, inmersión y pulverización.60. A method according to claim 29, characterized in that the electrically conductive material (4) is applied by a process selected from painting, immersion and spraying processes.
61. Un dispositivo electrocrómico susceptible de producir un cambio óptico visible en respuesta a una corriente eléctrica, preparado de acuerdo con una cualquiera de las reivindicaciones 29 a 61.61. An electrochromic device capable of producing a visible optical change in response to an electric current, prepared according to any one of claims 29 to 61.
62. Uso de un dispositivo electrocrómico según cualquiera de las reivindicaciones 1 a 28 para su aplicación en la construcción de edificios, en la industria del automóvil y para la fabricación de pantallas.62. Use of an electrochromic device according to any one of claims 1 to 28 for application in the construction of buildings, in the automobile industry and for the manufacture of screens.
63. Uso de un dispositivo electrocrómico preparado de acuerdo con una cualquiera de las reivindicaciones 29 a 61, para su aplicación en la construcción de edificios, en la industria del automóvil y para la fabricación de pantallas. 63. Use of an electrochromic device prepared according to any one of claims 29 to 61, for application in the construction of buildings, in the automobile industry and for the manufacture of screens.
PCT/ES2000/000251 1999-07-13 2000-07-13 Electrochromy device, process for obtaining such device and use thereof WO2001004696A1 (en)

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ESP9901575 1999-07-13
ES9901575A ES2153328B1 (en) 1999-07-13 1999-07-13 PRODUCTION OF COLOR CHANGES IN GLASS AND PLASTIC.

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Citations (5)

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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
US5264950A (en) * 1992-01-06 1993-11-23 Kent State University Light modulating device with polarizer and liquid crystal interspersed as spherical or randomly distorted droplets in isotropic polymer
WO1996013751A1 (en) * 1994-10-27 1996-05-09 Friedman, Mark, M. Regulating systems
EP0823653A1 (en) * 1996-07-10 1998-02-11 Saint-Gobain Vitrage Element with variable optical/energetic properties
US5940201A (en) * 1997-04-02 1999-08-17 Gentex Corporation Electrochromic mirror with two thin glass elements and a gelled electrochromic medium

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
US5264950A (en) * 1992-01-06 1993-11-23 Kent State University Light modulating device with polarizer and liquid crystal interspersed as spherical or randomly distorted droplets in isotropic polymer
WO1996013751A1 (en) * 1994-10-27 1996-05-09 Friedman, Mark, M. Regulating systems
EP0823653A1 (en) * 1996-07-10 1998-02-11 Saint-Gobain Vitrage Element with variable optical/energetic properties
US5940201A (en) * 1997-04-02 1999-08-17 Gentex Corporation Electrochromic mirror with two thin glass elements and a gelled electrochromic medium

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