WO2008037643A1 - Electrochromic formulation, method for the production thereof, and electrochromic organic component - Google Patents
Electrochromic formulation, method for the production thereof, and electrochromic organic component Download PDFInfo
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- WO2008037643A1 WO2008037643A1 PCT/EP2007/059931 EP2007059931W WO2008037643A1 WO 2008037643 A1 WO2008037643 A1 WO 2008037643A1 EP 2007059931 W EP2007059931 W EP 2007059931W WO 2008037643 A1 WO2008037643 A1 WO 2008037643A1
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
- G02F1/15165—Polymers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F2001/1502—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 complementary cell
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F2001/15145—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material the electrochromic layer comprises a mixture of anodic and cathodic compounds
Definitions
- Electrochromic formulation method of preparation and electrochromic organic device
- the invention relates to formulations and their use in organically based electrochromic components, for example for the production of status indicators whose switched state remains as long as possible without current.
- These electrochromic organic based formulations are characterized by a high bistability.
- Electrochromic displays based on organic materials to take ⁇ normally an active electrochromic layer, which is in the case of a display between the electrodes arranged perpendicular to each other.
- Essential components of the active layer are a redox system and a pH-active dye.
- the concent ⁇ rations collapse the redox partner is shifted from each other in the material.
- 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 at ⁇ , then the displacement of the equilibrium of the redox partners of the two electrodes run in the opposite direction overall translated. This means that at an electric ⁇ de pH increases, while it decreases at 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 comprising as essential constituents loading a polymer as a solid electrolyte, a supporting electrolyte, a redox system, TiO2 as a white pigment, a solvent and ei ⁇ NEN dye.
- This is usually a pH indicator.
- Another principle to realize electrochromic displays is not to cause the color change by changing the pH in the display, but to use the already taking place redox processes to produce high-contrast color changes by the formation of reductive and / or oxidative states in suitable materials.
- the so-called viologens and polythiophenes have become known as classes of materials. Examples in the literature for this are disclosed in MOM Edwards, Appl. Phys. Lett. 2005, 86 (7) and
- electrochromic active formulations are sought, which change the color state rapidly when a voltage is applied, and quickly return to the ground state in the de-energized state. This behavior is desirable for displays.
- status displays eg. B. on / off, it is advantageous to have formulations that remain after reaching the switched state without further tension long in this state.
- the object of the present disclosure was the development of electrochromically active formulations which remain in the de-energized state for a long time in the switched state, ie electrochromically active formulations with high bistability.
- the object of the invention and solution of the problem is an electrochromic formulation comprising a zwitterionic component.
- the electrochromic active component itself is a zwitterion.
- a zwitterionic compound is included in the formulation.
- the electrochromic active component is a polymeric Bipyridini- um derivative, as it is known for example from DE 10 2005 032 316.
- Additives with at least one of these functional groups can be used in a wide concentration range, but preferably in a stoichiometric ratio, based on the electrochromically active component.
- the functional group may also be present in the electrochromically active component.
- the character of the bipolarity of the additive can be varied by Substi ⁇ tution on one or both N atoms.
- a formulation according to the invention contains an electrochromically active component, for.
- a 4,4'-bipyridinium derivative eg a polymeric 4,4'-bipyridinium salt such as the poly (dodecyl-4,4'-bipyridinium) dibromide, and e.g. B. urea.
- This ⁇ For formulation is due to its bistability particularly for display Elements that are to indicate the state of a system ge ⁇ suitable. Since it remains long in the currentless state in the switched color state indicators with particularly ge ⁇ ringem power consumption can be realized. To maintain a sufficient color contrast of a entspre ⁇ sponding temporal sequence of voltage pulses is sufficient.
- 6g TiC> 2 were mixed with 0.6g of a polymer 4, 4 '-Bipyridinium- derivative (poly (dodecyl-4, 4' -bipyridinium dibromide)) and with 2g Diethylengklykol by means of a Speed Mixer intensively mixed with one another ⁇ .
- a white paste is obtained.
- a layer with a thickness of 50 ⁇ m is produced by means of the doctor blade technique between two ITO-coated films.
- a voltage of 1.5 V is applied for 10 s, a blue color impression is produced at the cathode, which is defined as a 100% contrast to the initial state, and which drops to 20% of the initial contrast in the unconnected state within about 30 seconds. The discoloration is therefore visible to the viewer of the display in the unconnected state for 30 seconds under the given wiring conditions.
- the invention relates to formulations and their use in organically based electrochromic components, for example for the production of status displays whose switched
- electrochromic organic based formulations are characterized by a high bistability.
- the wording ments contain at least one component which contains a zwitterionic ⁇ structural element.
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Abstract
The invention relates to formulations and the use thereof in organically based electrochromic components, such as for the production of status indicators, whose switched status is maintained extremely long, even in the deenergized state. These electrochromic organically based formulations are characterized by high bistability. The formulations comprised at least one component that has at least one zwitterionic structural element.
Description
Beschreibungdescription
Elektrochrome Formulierung, Herstellungsverfahren dazu und elektrochromes organisches BauelementElectrochromic formulation, method of preparation and electrochromic organic device
Die Erfindung betrifft Formulierungen und deren Anwendung in organisch basierten elektrochromen Bauteilen, beispielsweise zur Herstellung von Zustandsanzeigen, deren geschalteter Zustand möglichst lange auch stromlos erhalten bleibt. Diese elektrochromen organisch basierten Formulierungen zeichnen sich durch eine hohe Bistabilität aus.The invention relates to formulations and their use in organically based electrochromic components, for example for the production of status indicators whose switched state remains as long as possible without current. These electrochromic organic based formulations are characterized by a high bistability.
Elektrochrome Displays auf Basis organischer Materialien um¬ fassen im Normalfall eine aktive elektrochrome Schicht, die sich im Falle eines Displays zwischen senkrecht zueinander angeordneten Elektroden befindet. Wesentliche Bestandteile der aktiven Schicht sind ein Redox-System und ein pH-aktiver Farbstoff. Durch das Anlegen einer Spannung wird das Konzent¬ rationsverhältnis der Redox-Partner zueinander im Material verschoben. Bei dieser Reaktion werden im Material Protonen und/oder Ionen freigesetzt bzw. gebunden, welches sich auf den pH-Wert auswirkt. Wenn eine Spannung an das Material an¬ gelegt wird, dann läuft die Verschiebung des Gleichgewichts der Redox-Partner an den beiden Elektroden in entgegen ge- setzter Richtung. Dies führt dazu, dass an der einen Elektro¬ de der pH-Wert steigt, während er an der Gegenelektrode sinkt. Über einen pH-Farbstoff wird die Änderung des pH- Wertes dann in eine Farbänderung des Materials umgesetzt und das Anlegen der Spannung sichtbar gemacht.Electrochromic displays based on organic materials to take ¬ normally an active electrochromic layer, which is in the case of a display between the electrodes arranged perpendicular to each other. Essential components of the active layer are a redox system and a pH-active dye. By applying a voltage, the concent ¬ rationsverhältnis the redox partner is shifted from each other in the material. In this reaction protons and / or ions are released or bound in the material, which has an effect on the pH. When a voltage is applied to the material at ¬, then the displacement of the equilibrium of the redox partners of the two electrodes run in the opposite direction overall translated. This means that at an electric ¬ de pH increases, while it decreases at 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.
Aus WO 02/075441A2 und WO 02/075442 Al ist bekannt, dass sich zwischen den Elektroden eine pastöse Formulierung, die das elektrochrome System darstellt, befindet. Die Zusammensetzung dieses elektrochromen Systems umfasst als essentielle Be- standteile ein Polymer als Festelektrolyt, ein Leitsalz, ein Redox-System, TiÜ2 als Weißpigment, ein Lösungsmittel und ei¬ nen Farbstoff. Dieser ist in der Regel ein pH-Indikator.
Ein weiteres Prinzip elektrochrome Displays zu verwirklichen besteht darin, die Farbänderung nicht durch die Änderung des pH-Wertes im Display herbeizuführen, sondern die ohnehin stattfindenden Redoxprozesse zu nutzen, um kontrastreiche Farbwechsel durch die Bildung reduktiver und/oder oxidativer Zustände in geeigneten Materialien zu erzeugen. Dabei sind vor allem die so genannten Viologene und Polythiophene als Materialklassen bekannt geworden. Beispiele in der Literatur hierfür sind in M. O. M. Edwards, Appl . Phys . Lett . 2005, 86(7) undIt is known from WO 02 / 075441A2 and WO 02/075442 A1 that a pasty formulation, which represents the electrochromic system, is located between the electrodes. The composition of this electrochromic system comprising as essential constituents loading a polymer as a solid electrolyte, a supporting electrolyte, a redox system, TiO2 as a white pigment, a solvent and ei ¬ NEN dye. This is usually a pH indicator. Another principle to realize electrochromic displays is not to cause the color change by changing the pH in the display, but to use the already taking place redox processes to produce high-contrast color changes by the formation of reductive and / or oxidative states in suitable materials. In particular, the so-called viologens and polythiophenes have become known as classes of materials. Examples in the literature for this are disclosed in MOM Edwards, Appl. Phys. Lett. 2005, 86 (7) and
Helmut W. Heuer, Rolf Wehrmann, Stephan Kirchmeyer Adv. Funct. Mater. 2002, 89.Helmut W. Heuer, Rolf Wehrmann, Stephan Kirchmeyer Adv. Funct. Mater. 2002, 89.
In der Regel werden elektrochrom aktive Formulierungen ange- strebt, die beim Anlegen einer Spannung schnell den Farbzu- stand wechseln und im spannungslosen Zustand auch wieder schnell in den Grundzustand zurückkehren. Dieses Verhalten ist für Displays erwünscht. Für Zustandsanzeigen, z. B. ein/aus, ist es vorteilhaft, Formulierungen zu haben, die nach Erreichen des geschalteten Zustands ohne weitere Spannung lange in diesen Zustand verbleiben.As a rule, electrochromic active formulations are sought, which change the color state rapidly when a voltage is applied, and quickly return to the ground state in the de-energized state. This behavior is desirable for displays. For status displays, eg. B. on / off, it is advantageous to have formulations that remain after reaching the switched state without further tension long in this state.
Aufgabe der vorliegenden Erfindungsmeldung war die Entwicklung elektrochrom aktiver Formulierungen, die lange im ge- schalteten Zustand im spannungslosen Zustand bleiben, also elektrochrom aktive Formulierungen mit hoher Bistabilität .The object of the present disclosure was the development of electrochromically active formulations which remain in the de-energized state for a long time in the switched state, ie electrochromically active formulations with high bistability.
Gegenstand der Erfindung und Lösung der Aufgabe ist eine e- lektrochrome Formulierung, die eine zwitterionische Komponen- te umfasst.The object of the invention and solution of the problem is an electrochromic formulation comprising a zwitterionic component.
Nach einer vorteilhaften Ausführungsform ist die elektrochrom aktive Komponente selbst ein Zwitterion. Nach einer Ausführungsform ist eine zwitterionische Verbindung in der Formu- lierung enthalten.According to an advantageous embodiment, the electrochromic active component itself is a zwitterion. In one embodiment, a zwitterionic compound is included in the formulation.
Völlig überraschend wurde gefunden, dass Moleküle, die als Zwitterion vorliegen können, die Bistabilität stark erhöhen
können. Ohne eine solche Form des Moleküls oder Polymers oder einen entsprechenden Zusatz kehrt die elektrochrom aktive Komponente und mit ihr die elektrochrome Zelle im stromlosen Zustand schnell wieder in den Ausgangszustand zurück.Quite surprisingly, it has been found that molecules that can exist as zwitterion greatly increase the bistability can. Without such a form of the molecule or polymer or a corresponding additive, the electrochromic active component and, with it, the electrochromic cell rapidly returns to its original state when de-energized.
Nach einer vorteilhaften Ausführungsform der Erfindung ist die elektrochrom aktive Komponente ein polymeres Bipyridini- um-Derivat, wie sie beispielsweise aus der DE 10 2005 032 316 bekannt ist.According to an advantageous embodiment of the invention, the electrochromic active component is a polymeric Bipyridini- um derivative, as it is known for example from DE 10 2005 032 316.
Vorteilhafte Strukturen der elektrochrom aktiven Komponente enthalten das Amid- und/oder Thioamid-Strukturelement , allge¬ meinAdvantageous structures of the electrochromically active component containing the amide and / or thioamide structure element general ¬ my
R-CO-NR-R-CO-NR-
und/oderand or
R-CS-NR-R.R-CS-NR-R.
Dieses kann in acyclischen Strukturen enthalten sein, aber auch in cyclischen. Besonders geeignet sind z. B. Harnstoff, Thioharnstoff und/oder Derivate davon, Amide, Thioamide bzw. Derivate davon und/oder Barbitursäure, Thiobarbitursäure, Pa- rabansäure, Thiobarabansäure und/oder Derivate davon.
This may be present in acyclic structures, but also in cyclic ones. Particularly suitable z. For example, urea, thiourea and / or derivatives thereof, amides, thioamides or derivatives thereof and / or barbituric acid, thiobarbituric acid, rabanic acid, thiobarabanic acid and / or derivatives thereof.
Beispielhaft genannt seien folgende Strukturen:Examples include the following structures:
O OO O
++
-N-C — -N=C--N-C - -N = C-
Zusätze mit zumindest einer dieser funktionellen Gruppen kön- nen in einem weiten Konzentrationsbereich eingesetzt werden, vorzugsweise aber im stöchiometrischen Verhältnis, bezogen auf die elektrochrom aktive Komponente.Additives with at least one of these functional groups can be used in a wide concentration range, but preferably in a stoichiometric ratio, based on the electrochromically active component.
Die funktionelle Gruppe kann aber auch in der elektrochrom aktiven Komponente vorliegen.However, the functional group may also be present in the electrochromically active component.
Der Charakter der Bipolarität des Zusatzes kann durch Substi¬ tution an einem oder beiden N-Atomen variiert werden.The character of the bipolarity of the additive can be varied by Substi ¬ tution on one or both N atoms.
Eine erfindungsgemäße Formulierung enthält eine elektrochrom aktive Komponente, z. B. ein 4, 4' -Bipyridiniumderivat , z.B. ein polymeres 4, 4' -Bipyridiniumsalz wie das PoIy- (dodecyl- 4, 4' -bipyridinium) -dibromid, und z. B. Harnstoff. Diese For¬ mulierung ist wegen ihrer Bistabilität besonders für Anzeige-
elemente, die den Zustand eines Systems anzeigen sollen, ge¬ eignet. Da sie im stromlosen Zustand lange im geschalteten Farbzustand bleibt, können Anzeigeelemente mit besonders ge¬ ringem Stromverbrauch realisiert werden. Zur Aufrechterhaltung eines ausreichenden Farbkontrasts genügt eine entspre¬ chende zeitliche Folge von Spannungspulsen.A formulation according to the invention contains an electrochromically active component, for. A 4,4'-bipyridinium derivative, eg a polymeric 4,4'-bipyridinium salt such as the poly (dodecyl-4,4'-bipyridinium) dibromide, and e.g. B. urea. This ¬ For formulation is due to its bistability particularly for display Elements that are to indicate the state of a system ge ¬ suitable. Since it remains long in the currentless state in the switched color state indicators with particularly ge ¬ ringem power consumption can be realized. To maintain a sufficient color contrast of a entspre ¬ sponding temporal sequence of voltage pulses is sufficient.
Ausführungsbeispieleembodiments
1 Herstellung einer elektrochrom aktiven Formulierung und einer elektrochromen Zelle daraus.1 Preparation of an electrochromically active formulation and an electrochromic cell thereof.
6g TiC>2 werden mit 0.6g eines polymeren 4, 4' -Bipyridinium- Derivats (PoIy- (dodecyl-4, 4' -bipyridinium-dibromid) ) und mit 2g Diethylengklykol mittels eines Speed-Mixers intensiv mit¬ einander vermischt. Es wird eine weiße Paste erhalten. Aus dieser wird mittels der Rakel-Technik zwischen zwei ITO- beschichteten Folien eine Schicht der Dicke 50 μm herge- stellt. Beim Anlegen einer Spannung von 1.5 V für 10 s wird an der Kathode ein blauer Farbeindruck erzeugt, welcher als 100% Kontrast gegenüber dem Ausgangszustand definiert wird, und der im nicht beschalteten Zustand innerhalb von etwa 30 Sekunden auf 20% des Anfangskontrastes abfällt. Die Verfär- bung ist also bei den angegebenen Beschaltungsbedingungen für den Betrachter des Displays im nicht beschalteten Zustand 30 Sekunden lang sichtbar.6g TiC> 2 were mixed with 0.6g of a polymer 4, 4 '-Bipyridinium- derivative (poly (dodecyl-4, 4' -bipyridinium dibromide)) and with 2g Diethylengklykol by means of a Speed Mixer intensively mixed with one another ¬. A white paste is obtained. From this, a layer with a thickness of 50 μm is produced by means of the doctor blade technique between two ITO-coated films. When a voltage of 1.5 V is applied for 10 s, a blue color impression is produced at the cathode, which is defined as a 100% contrast to the initial state, and which drops to 20% of the initial contrast in the unconnected state within about 30 seconds. The discoloration is therefore visible to the viewer of the display in the unconnected state for 30 seconds under the given wiring conditions.
2 Herstellung einer elektrochrom aktiven Formulierung mit Harnstoff-Zusatz und einer bistabilen elektrochromen Zelle daraus .2 Preparation of an electrochromically active formulation with added urea and a bistable electrochromic cell thereof.
6g TiÜ2, 0.6g eines polymeren 4, 4' -Bipyridinium-Derivats (Po- Iy- (dodecyl-4, 4' -bipyridinium-dibromid) ), 0.1g Harnstoff wer¬ den mit 2g Diethylengklykol mittels eines Speed-Mixers inten¬ siv miteinander vermischt. Es wird eine weiße Paste erhalten, Aus dieser wird mittels der Rakel-Technik zwischen zwei ITO-
beschichteten Folien eine Schicht der Dicke 50 μm herge¬ stellt. Beim Anlegen einer Spannung von 1.5 V für 10 s wird an der Kathode ein blauer Farbeindruck erzeugt, welcher als 100% Kontrast gegenüber dem Ausgangszustand definiert wird, und der im nicht beschalteten Zustand innerhalb von etwa 110 Sekunden auf 20% des Anfangskontrastes abfällt. Die Verfär¬ bung ist also bei den angegebenen Beschaltungsbedingungen für den Betrachter des Displays im nicht beschalteten Zustand 110 Sekunden lang sichtbar. Es wird eine 3.6-fache Verbesserung der Bistabilität erreicht.6 g of TiO 2, 0.6 g of a polymeric 4, 4'-bipyridinium derivative (poly (dodecyl-4, 4'-bipyridinium-dibromide)), 0.1 g of urea ¬ with 2g Diethylengklykol by means of a speed mixer inten ¬ mixed together. A white paste is obtained, from which, by means of the doctor blade technique, between two ITO coated films a layer of thickness 50 microns Herge ¬ provides. When a voltage of 1.5 V is applied for 10 s, a blue color impression is produced at the cathode, which is defined as 100% contrast with respect to the initial state and which in the unconnected state drops to 20% of the initial contrast within about 110 seconds. The Verfär ¬ environment is therefore 110 seconds long visible in the specified Beschaltungsbedingungen for the viewer of the display in the non-connected state. It achieves a 3.6-fold improvement in bistability.
3 Herstellung einer elektrochrom aktiven Formulierung mit einem Thioharnstoff-Derivat und einer bistabilen elektrochromen Zelle daraus.3 Preparation of an electrochromically active formulation comprising a thiourea derivative and a bistable electrochromic cell thereof.
6g TiO2, 0.6 g eines polymeren 4, 4' -Bipyridinium-Derivats (PoIy- (dodecyl-4, 4' -bipyridinium-dibromid) ), 0.41g N, N'- Dinaphthyl-thioharnstoff werden mit 2 g Diethylengklykol mit- tels eines Speed-Mixers intensiv miteinander vermischt. Es wird eine weiße Paste erhalten. Aus dieser wird mittels der Rakel-Technik zwischen zwei ITO-beschichteten Folien eine Schicht der Dicke 50 μm hergestellt. Beim Anlegen einer Span¬ nung von 1.5 V für 10 s wird an der Kathode ein blauer Farb- eindruck erzeugt, welcher als 100% Kontrast gegenüber dem6 g of TiO 2 , 0.6 g of a polymeric 4, 4'-bipyridinium derivative (poly (dodecyl-4, 4'-bipyridinium-dibromide)), 0.41 g of N, N'-dinaphthyl-thiourea are mixed with 2 g of diethylene glycol. of a speed mixer are mixed intensively. A white paste is obtained. From this, a layer of thickness 50 μm is produced by means of the doctoring technique between two ITO-coated films. Upon application of a clamping ¬ voltage of 1.5 V for 10 s, a blue color impression is produced at the cathode, which as a 100% contrast with the
Ausgangszustand definiert wird, und der im nicht beschalteten Zustand innerhalb von etwa 130 Sekunden auf 20% des Anfangs¬ kontrastes abfällt. Die Verfärbung ist also bei den angegebe¬ nen Beschaltungsbedingungen für den Betrachter des Displays im nicht beschalteten Zustand 130 Sekunden lang sichtbar. Es wird eine 4.3-fache Verbesserung der Bistabilität erreicht.Initial state is defined, and in the unconnected state drops within about 130 seconds to 20% of the initial ¬ contrast. The discoloration is therefore for 130 seconds visible to the viewer of the display in the non-connected state in the attached admit ¬ nen Beschaltungsbedingungen. It achieves a 4.3-fold improvement in bistability.
Die Erfindung betrifft Formulierungen und deren Anwendung in organisch basierten elektrochromen Bauteilen, beispielsweise zur Herstellung von Zustandsanzeigen, deren geschalteterThe invention relates to formulations and their use in organically based electrochromic components, for example for the production of status displays whose switched
Farbzustand möglichst lange auch stromlos erhalten bleibt. Diese elektrochromen organisch basierten Formulierungen zeichnen sich durch eine hohe Bistabilität aus. Die Formulie-
rungen enthalten zumindest eine Komponente, die ein zwitter¬ ionisches Strukturelement enthält.
Color state as long as possible also remains currentless. These electrochromic organic based formulations are characterized by a high bistability. The wording ments contain at least one component which contains a zwitterionic ¬ structural element.
Claims
1. Elektrochrome Formulierung, die zumindest ein elektro- chrom aktives Chromophor und einen dazugehörigen Redox- Partner in einer Matrix, ein Weißpigment und ein Lösungsmittel umfasst, wobei in der Formulierung zumindest eine Verbin¬ dung mit einem zwitterionischen Strukturelement enthalten ist.1. Electrochromic formulation containing at least one electro-chrome comprises active chromophore and an associated redox partner in a matrix, a white pigment and a solvent, wherein the formulation has a Verbin ¬ dung at least contain a zwitterionic structural element.
2. Elektrochrome Formulierung nach Anspruch 1, wobei die zwitterionische Struktur in der elektrochrom aktiven Komponente enthalten ist.2. The electrochromic formulation according to claim 1, wherein the zwitterionic structure is contained in the electrochromic active component.
3. Elektrochrome Formulierung nach einem der Ansprüche 1 oder 2, wobei eine Verbindung mit zwitterionischer Struktur der elektrochromen Formulierung zugesetzt ist.3. An electrochromic formulation according to any one of claims 1 or 2, wherein a compound having a zwitterionic structure is added to the electrochromic formulation.
4. Elektrochrome Formulierung nach einem der vorstehenden Ansprüche, wobei in der Formulierung zumindest eine Verbin- düng mit einem Amid- und/oder Thioamid-Strukturelement ent¬ halten ist.4. Electrochromic formulation according to any of the preceding claims, wherein in the formulation at least one fertil connects with an amide and / or thioamide structure element is hold ¬ ent.
5. Elektrochrome Formulierung nach einem der vorstehenden Ansprüche, wobei in der Formulierung zumindest eine Verbin- düng enthalten ist, die aus der folgenden Gruppe ausgewählt ist: Harnstoff, Thioharnstoff und/oder Derivate davon, Ami- de, Thioamide bzw. Derivate davon und/oder Barbitursäure, Thiobarbitursäure, Parabansäure, Thiobarabansäure und/oder Derivate davon.5. An electrochromic formulation according to any one of the preceding claims, wherein the formulation contains at least one compound selected from the group consisting of: urea, thiourea and / or derivatives thereof, amides, thioamides or derivatives thereof and / or or barbituric acid, thiobarbituric acid, parabanic acid, thiobarabanic acid and / or derivatives thereof.
6. Elektrochrome Formulierung nach einem der vorstehenden Ansprüche, wobei in der Formulierung zumindest eine Verbin¬ dung mit einem der folgenden Strukturelemente enthalten ist: 
6. Electrochromic formulation according to any of the preceding claims, wherein in the formulation at least one Verbin ¬ tion with one of the following structural elements is included:
7. Elektrochrome Formulierung nach einem der vorstehenden Ansprüche, wobei in der Formulierung eine zwitterionische Verbindung im stöchiometrischen Verhältnis, bezogen auf die elektrochrom aktive Komponente, vorliegt.7. Electrochromic formulation according to one of the preceding claims, wherein in the formulation a zwitterionic compound in the stoichiometric ratio, based on the electrochromic active component, is present.
8. Elektrochrome Formulierung nach einem der vorstehenden Ansprüche, die als elektrochrom aktive Komponente ein polyme- res 4 , 4 ' -Bipyridiniumsalz umfasst.8. Electrochromic formulation according to one of the preceding claims, which comprises a polymeric 4, 4 '-bipyridinium salt as the electrochromically active component.
9. Verwendung der elektrochromen Formulierung nach einem der Ansprüche 1 bis 8 zur Herstellung eines elektrochromen Bauteils .9. Use of the electrochromic formulation according to one of claims 1 to 8 for the preparation of an electrochromic component.
10. Zustandsanzeige mit elektrochromen organisch basiertem Bauteil, wobei eine Formulierung nach einem der Ansprüche 1 bis 8 enthalten ist.10. An electrochromic organically based device status display, wherein a formulation according to any one of claims 1 to 8 is included.
11. Verwendung der elektrochromen Formulierung nach einem der Ansprüche 1 bis 8 zur Herstellung eines elektrochromen Bauteils mit hoher Bistabilität . 11. Use of the electrochromic formulation according to one of claims 1 to 8 for the preparation of an electrochromic component with high bistability.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006045307.7 | 2006-09-26 | ||
| DE102006045307A DE102006045307A1 (en) | 2006-09-26 | 2006-09-26 | Electrochromic formulation, method of preparation and electrochromic organic device |
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| Publication Number | Publication Date |
|---|---|
| WO2008037643A1 true WO2008037643A1 (en) | 2008-04-03 |
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ID=38935962
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2007/059931 WO2008037643A1 (en) | 2006-09-26 | 2007-09-20 | Electrochromic formulation, method for the production thereof, and electrochromic organic component |
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| Country | Link |
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| DE (1) | DE102006045307A1 (en) |
| WO (1) | WO2008037643A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009141302A1 (en) * | 2008-05-20 | 2009-11-26 | Siemens Aktiengesellschaft | Electrochromic formulation and organic electrochromic switchable electronic component |
| WO2009141303A1 (en) * | 2008-05-19 | 2009-11-26 | Siemens Aktiengesellschaft | Electrochromic formulation with at least two dye systems method for production thereof and electrochromic component |
| US8115984B2 (en) | 2007-06-18 | 2012-02-14 | Ajjer Llc | Laminated electrochromic devices and processes for forming the same |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008024259A1 (en) | 2008-05-20 | 2009-12-31 | Siemens Aktiengesellschaft | Electrochromic formulation, useful for an electrochromic active paste and an organic electronic electrochromic component, comprises an electrochromic switchable pigment and a white pigment |
| DE102009023303A1 (en) | 2009-05-29 | 2010-12-09 | Siemens Aktiengesellschaft | Electrochromic formulation, method of preparation and electrochromic organic device |
| DE102009023309A1 (en) | 2009-05-29 | 2010-12-16 | Siemens Aktiengesellschaft | Electrochromic formulation, method of preparation and electrochromic organic device |
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| WO1989008686A1 (en) * | 1988-03-12 | 1989-09-21 | MERCK Patent Gesellschaft mit beschränkter Haftung | Zwitterion nlo-chromophores |
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| JPS5643623A (en) * | 1979-09-18 | 1981-04-22 | Sharp Corp | Electrochromic display device |
| JPH11183942A (en) * | 1997-12-19 | 1999-07-09 | Nippon Mitsubishi Oil Corp | Electrochromic element |
| DE19825371A1 (en) * | 1998-06-06 | 1999-12-09 | Bayer Ag | Electrochromic display device with insulated leads |
| WO2006128818A1 (en) * | 2005-05-31 | 2006-12-07 | Siemens Aktiengesellschaft | Material for an electrochromic formualtion, use thereof and display |
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| WO1989008686A1 (en) * | 1988-03-12 | 1989-09-21 | MERCK Patent Gesellschaft mit beschränkter Haftung | Zwitterion nlo-chromophores |
| WO1995007275A1 (en) * | 1993-09-10 | 1995-03-16 | Ciba-Geigy Ag | Photochromic compounds, methods and intermediates for producing them and their use |
| WO2002000662A1 (en) * | 2000-06-26 | 2002-01-03 | Catalyst Biomedica Limited | Improvements in and relating to chromophores |
| WO2002075441A2 (en) * | 2001-03-19 | 2002-09-26 | Dow Global Technologies Inc. | Electrochromic display device and compositions useful in making such devices |
| WO2006128806A2 (en) * | 2005-05-31 | 2006-12-07 | Siemens Aktiengesellschaft | Material for electrochromic layers |
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| US8115984B2 (en) | 2007-06-18 | 2012-02-14 | Ajjer Llc | Laminated electrochromic devices and processes for forming the same |
| WO2009141303A1 (en) * | 2008-05-19 | 2009-11-26 | Siemens Aktiengesellschaft | Electrochromic formulation with at least two dye systems method for production thereof and electrochromic component |
| WO2009141302A1 (en) * | 2008-05-20 | 2009-11-26 | Siemens Aktiengesellschaft | Electrochromic formulation and organic electrochromic switchable electronic component |
| US8300296B2 (en) | 2008-05-20 | 2012-10-30 | Siemens Aktiengesellschaft | Electrochromic formulation and organic electrochromic switchable electronic component |
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| DE102006045307A1 (en) | 2008-04-03 |
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