WO2006128805A1 - Matieres pour couches electrochromes - Google Patents

Matieres pour couches electrochromes Download PDF

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Publication number
WO2006128805A1
WO2006128805A1 PCT/EP2006/062524 EP2006062524W WO2006128805A1 WO 2006128805 A1 WO2006128805 A1 WO 2006128805A1 EP 2006062524 W EP2006062524 W EP 2006062524W WO 2006128805 A1 WO2006128805 A1 WO 2006128805A1
Authority
WO
WIPO (PCT)
Prior art keywords
dye
redox
chromophore
electrochromic
polymeric
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2006/062524
Other languages
German (de)
English (en)
Inventor
Andreas Kanitz
Wolfgang Roth
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Siemens AG, Siemens Corp filed Critical Siemens AG
Publication of WO2006128805A1 publication Critical patent/WO2006128805A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material

Definitions

  • the invention relates to a material for electrochromic layers based on an activated by redox reaction color change.
  • Electrochromic displays based on organic materials normally comprise an active electrochromic layer, which in the case of a display is located between electrodes arranged perpendicular to one another.
  • Essential components of the active layer are a redox system and a pH-active dye.
  • a voltage By applying a voltage, the concentration ratio of the redox partners to one another in the material is shifted. In this reaction protons and / or ions are released or bound in the material, which has an effect on the pH.
  • a voltage is applied to the material, the shift in the equilibrium of the redox partners on the two electrodes is in the opposite direction. As a result, the pH of one of the electrodes rises while it sinks on the counter electrode. Via a pH dye, the change in the pH value is then converted into a color change of the material and the application of the voltage is made visible.
  • a pasty formulation which represents the electrochromic system, is located between the electrodes.
  • the composition of this electrochromic system comprises as essential components a polymer as a solid electrolyte, a conductive salt, a redox system, TiO 2 as a white pigment, a solvent and a dye. This is usually a pH indicator.
  • the disadvantage of this formulation is the free, low molecular weight chromophore.
  • its solubility in the other components is a prerequisite. This makes the selection of chro- restricted to mophores.
  • Another problem is that the low molecular weight redox system and / or the low molecular weight dye tend in principle to diffusion and migration. As a result, it comes z. B. on pixel edges to their blurring, resulting in a blurred image impression after prolonged presentation of an image.
  • the object of the present invention is therefore to specify a material for an electrochromic formulation which on the one hand manages without a redox system based on hydroquinone / quinone and on the other hand has a not so limited coloration as the electrochromic formulations based on Viologens or polythiophenes.
  • the object of the invention and solution of the problem is a material for an electrochromic formulation comprising at least one polymer as a solid electrolyte, a conducting salt, a redox system, a white pigment, a solvent and a chromophore, wherein the functionalities of the polymeric solid electrolyte, the redox -System and the chromophore are contained in one component.
  • the polymer present component comprises an organic redox chromophore such as the merocyanine and / or polymethine dyes.
  • organic polymer-bound redox chromophores used according to the invention are all dyes of the so-called merocyanine and polymethine dye type.
  • a structural element in these dye types is basically quinoidal. This quinoid structural element can be reduced chemically as well as electrically (cathodically) to the leuco form of the dye. In this process, the quinoid substructure is hydrogenated and converted into an aromatic compound that is conjugatively decoupled from the rest of the system. Conversely, both chemically and electrically (anodically), the dye (the fully conjugated form) can be oxidatively recovered.
  • Such chromophores used in an electrochromic arrangement are thus a redox couple and a coloring structure in one.
  • A is a donor substituent
  • B is an acceptor substituent which carries a positive or negative charge in the case of a polymethine dye
  • R 1 and R 1 * independently of one another are H, alkyl (branched or unbranched Cl to ClO), aryl (preferably phenyl) or both are connected via an oxygen atom or sulfur atom,
  • merocyanines derived from 1,3-diketones or from their cyclic ureides are of interest, such as the donor-substituted barbituric acid derivatives and thiobarbituric acid derivatives
  • substituents A, B, R n or a substituent on any aromatic structural element of the defined redox dye is designed as a structural element for chemical attachment to a polymeric matrix, this may be a hydroxy function, a be organic or inorganic acid function or optionally also an amine function.
  • polymers On the side of the polymers, a wide range of commercially available polymers with appropriate functional groups are available. However, suitable polymers can also be synthesized for the specific application.
  • redox chromophores from the classes of merocyanines and methine dye betaines are known in principle, they are not the specific representatives of the respective chromophore classes that are suitable for use as electrochromes.
  • the known methine dye betaines usually lack the required te solubility and stability in specific solvents for the preparation of the formulations.
  • suitable for use redox chromophores from the above classes can not be easily prepared from the known and commercially available dyes, but can be prepared only from previously synthesized, appropriately substituted synthons by condensation.
  • the following components are mixed in the amount indicated: TiC> 2 (Ig), polyethylene oxide (Ig), tetrabutylammonium tetrafluoroborate (0.06 g), propylene carbonate (3 ml) and the polymer prepared bound redox chromophore (0.06g). All ingredients are mixed thoroughly after mixing together using a speed mixer.
  • the paste-like formulation obtained is applied according to the prior art in the case of a display between intersecting electrodes.
  • a voltage is applied, a color change from blue to colorless (white) is achieved.
  • the prior art formulation is improved in that the redox system becomes part of the electroactive chromophore and the polymeric solid electrolyte. Since here the solid electrolyte contains the organic chromophore and the redox system itself, can be dispensed with the addition of a redox system based on quinone / hydroquinone. This can reduce the number of components in the formulation. It is of particular advantage that the elimination of the chlorine / hydroquinone system improves the long-term stability of the electrodes compared to the now neutral formulation.
  • the electrochromic material (the redox chromophore) carried out together in one component of the formulation thereby the number of components of the formulation is reduced whereby the long-term stability of the formulation and the life of the display can be improved. Since the redox chromophore is polymer-bound, diffusion can no longer occur. As a result, color changes are permanently restricted to the active pixel area. This allows edge-to-edge imaging of pixels and thus improved image reproduction with improved lifetime.
  • the advantage of the redox chromophores according to the invention is that a large variety of structural changes is available in the coloring part of the molecule, whereby a large selection of different colors can be represented.

Landscapes

  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

Matières pour couches électrochromes à base d'un changement de couleur activé par une réaction redox. Selon la présente invention, les fonctionnalités du système redox, du chromophore électroactif et de l'électrolyte solide polymère sont réunies en un constituant. Cette réunion des fonctionnalités permet d'économiser des constituants individuels de la composition électrochrome et d'augmenter la durée de vie de ladite composition électrochrome.
PCT/EP2006/062524 2005-05-31 2006-05-23 Matieres pour couches electrochromes Ceased WO2006128805A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102005024948 2005-05-31
DE102005024948.5 2005-05-31
DE102005031636 2005-07-06
DE102005031636.0 2005-07-06

Publications (1)

Publication Number Publication Date
WO2006128805A1 true WO2006128805A1 (fr) 2006-12-07

Family

ID=36838520

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2006/062524 Ceased WO2006128805A1 (fr) 2005-05-31 2006-05-23 Matieres pour couches electrochromes

Country Status (1)

Country Link
WO (1) WO2006128805A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2534713A1 (de) * 1975-08-04 1977-02-17 Dirk Dr Basting Farbstofflaser
WO1996007487A1 (fr) * 1994-09-10 1996-03-14 The University Of Liverpool Procede de synthese de materiaux aux proprietes electroniques, magnetiques et/ou optiques regulees
WO2001027690A2 (fr) * 1999-10-11 2001-04-19 University College Dublin Dispositif electrochromique
WO2002075441A2 (fr) * 2001-03-19 2002-09-26 Dow Global Technologies Inc. Dispositif d'affichage electrochromique et compositions utilisees pour fabriquer de tels dispositifs
WO2006056550A1 (fr) * 2004-11-24 2006-06-01 Siemens Aktiengesellschaft Composant electrochrome comportant un hydrogel rempli d'electrolyte

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2534713A1 (de) * 1975-08-04 1977-02-17 Dirk Dr Basting Farbstofflaser
WO1996007487A1 (fr) * 1994-09-10 1996-03-14 The University Of Liverpool Procede de synthese de materiaux aux proprietes electroniques, magnetiques et/ou optiques regulees
WO2001027690A2 (fr) * 1999-10-11 2001-04-19 University College Dublin Dispositif electrochromique
WO2002075441A2 (fr) * 2001-03-19 2002-09-26 Dow Global Technologies Inc. Dispositif d'affichage electrochromique et compositions utilisees pour fabriquer de tels dispositifs
WO2006056550A1 (fr) * 2004-11-24 2006-06-01 Siemens Aktiengesellschaft Composant electrochrome comportant un hydrogel rempli d'electrolyte

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