WO1986006179A1 - Application of the electrolytic process to change the degree of reflection of mirrors - Google Patents

Application of the electrolytic process to change the degree of reflection of mirrors Download PDF

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Publication number
WO1986006179A1
WO1986006179A1 PCT/DE1986/000104 DE8600104W WO8606179A1 WO 1986006179 A1 WO1986006179 A1 WO 1986006179A1 DE 8600104 W DE8600104 W DE 8600104W WO 8606179 A1 WO8606179 A1 WO 8606179A1
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WO
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Application
Patent type
Prior art keywords
mirror
electrode
characterized
layer
according
Prior art date
Application number
PCT/DE1986/000104
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German (de)
French (fr)
Inventor
Peter Knoll
Original Assignee
Robert Bosch Gmbh
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Publication date

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Classifications

    • GPHYSICS
    • G02OPTICS
    • G02FDEVICES OR ARRANGEMENTS, THE OPTICAL OPERATION OF WHICH IS MODIFIED BY CHANGING THE OPTICAL PROPERTIES OF THE MEDIUM OF THE DEVICES OR ARRANGEMENTS FOR THE CONTROL OF THE INTENSITY, COLOUR, PHASE, POLARISATION OR DIRECTION OF LIGHT, e.g. SWITCHING, GATING, MODULATING OR DEMODULATING; TECHNIQUES OR PROCEDURES FOR THE OPERATION THEREOF; FREQUENCY-CHANGING; NON-LINEAR OPTICS; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices 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
    • G02F1/01Devices 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
    • G02F1/15Devices 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 electrochromic elements
    • G02F1/1506Devices 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 electrochromic elements based on electrolytic deposition of a non-organic material on or in the vicinity of an electrode
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B60VEHICLES IN GENERAL
    • B60RVEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R1/00Optical viewing arrangements
    • B60R1/02Rear-view mirror arrangements
    • B60R1/08Rear-view mirror arrangements involving special optical features, e.g. avoiding blind spots, e.g. convex mirrors; Side-by-side associations of rear-view and other mirrors
    • B60R1/083Anti-glare mirrors, e.g. "day-night" mirrors
    • B60R1/088Anti-glare mirrors, e.g. "day-night" mirrors using a cell of electrically changeable optical characteristic, e.g. liquid-crystal or electrochromic mirrors
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • C03C17/10Surface treatment of glass, not in the form of fibres or filaments, by coating with metals by deposition from the liquid phase

Abstract

Through the production and removal by means of electrolysis of a reflecting metal layer (12) on a flat electrode (4), the degree of reflexion of a mirror, in particular a rear view mirror for vehicles, can be changed in a reversible manner.

Description

Application of the electrolysis process to change the reflectivity of mirrors

State of the art

There has long been dimmable rearview mirror for motor vehicles, in which an optically active disc is disposed within the tiltable mirror and can be tilted by a tilting mechanism in one of two predetermined positions. In one position of the disc, the entire incident on the mirror is reflected practical, so that a bright image. In the second position, however, passes only an attenuated reflected image in the eye of the beholder, whereby the risk of glare is reduced. Such mechanical structures are relatively complex and not user-friendly. It is also known to dim mirror "electronically". To this end it is proposed in DE-PS 19 48 362, the absorbance of an electrochromic layer, which is located between the spectator and a reflector to change by applying a voltage to two, the electrochromic layer enclosing electrodes continuously. Although this mirror satisfies the legal requirements (5% ≦ R ≦ 55%), but the response times are on the order of several seconds and thus are unacceptably long. From DE-OS 29 34 451, a dimming Rückspie¬gel is also become known, which uses a liquid crystal cell of twisted nematic type (TN-LCD) between crossed polarizers. Since polarizers absorb about 50% of the incident light are difficult to meet legal requirements. Typical values ​​for the reflectivity of such mirrors are 7% ≦ R ≦ 3T%. One of the company Murakami Kameido (Japan) developed LCD rear-view mirror does not require polarizers. In the liquid crystal dye molecules are embedded as a light absorber, which can be folded by applying an electric field from a non-absorbent layer in an absorbent sheet. The efficiency of this mirror is bad. It is located by the manufacturer at 27% ≦ R ≦ 51%. Vehicle mirror whose reflectance means verfärbbarer or neutral-color liquid crystal layers can be varied in conjunction with polarization filters are also described in German Offenlegungsschriften 29 48 514 describes 31 44 143 and 33 02 195th From EP-A 0,006,811, an electrolytic cell is known, finally, having a transparent electrode and a metallic counter-electrode, between which an electrolyte is located. Depending on the polarity of an applied voltage to the two electrodes, a layer of the metal of the metal electrode is deposited or removed from the latter to the transparent electrode. The cell serves as a display device for displaying symbols, numbers and letters.

Advantages of the Invention

The invention proposed use of the electrolysis process to generate and detachment of a reflective metal layer on a flat electrode by reversing the current flow in the electrolyte at a level, in particular in a rear-view mirror for motor vehicles, in contrast, provides the advantage that such a mirror is very responsive to polarity reversals of the voltage so thatsaid results in short discounts and Aufblendzeiten. He also meets the legal requirements for reflectivity in light and dark conditions, the achievable contrasts are higher than in the previously known dimming mirrors. Further, the mirror does not require polarizers, and can be prepared using commercially available materials.

By the provisions recited in the dependent claims, advantageous developments and improvements of the method and a mirror manufactured by applying the method are possible. to reduce the reflection degree of the mirror-reflective metal is preferably replaced by a viewer facing the front electrode and a rear electrode deposited on the mirror. Another method that simplifies the layer construction, is that replaced to reduce the reflectance of reflective metal from a rear electrode and is deposited in a granular form on a beholder facing the front electrode of the mirror. The mirror itself can have two connectable to a umpolbare voltage source area electrodes, each enclosing on a the electrolyte carrier plate is arranged, which faces the viewer front electrode and its support plate are made of transparent materials, while the rear electrode formed of a reflective metal is. At levels where reflecting material is displaced from the front to the rear electrode to reduce the reflectance, it is expedient to achieve a sufficient Abblendeffektes that a permeable carrier insulation layer of a dark, preferably black color, is applied to the rear electrode. drawing

Further features and details of the invention will become apparent from the following description with reference to an embodiment shown in the drawing. 1 shows the electrolytic cell of an anti-glare mirror in a perspective view, Figure 2 a section through the cell of Figure 1, shown enlarged, with electrical wiring.

Be scription of the embodiment

In the drawing, 1 is a 2 to the eye of a spectator facing upper support plate and designated by 3, a lower support plate. The upper support plate 1 is made of a transparent material, preferably glass. As a material for the lower carrier plate 3 is preferably also used glass. an active electrode 4 is located on the inside of the upper support plate 1 made of transparent material, preferably indium tin oxide. A counter electrode 5 made of reflective metal such as silver or aluminum, is applied to the inside of the lower support plate. 3 The carrier plate assembly 1, 3 is hermetically sealed around the edges. DerAAbstand of the plates from each other is set to the required level of between 100 .mu.m and 200 .mu.m over a frame. 6 The volume thus created between the two support plates is filled with an electrolyte. 7 Serving as the counter electrode 5 metal layer is coated with a permeable insulating layer for charge carriers. 8 This layer is colored preferably black to improve the Abblendeffekts. It is expediently designed as a porous film layer having a thickness of 0.1 to 0.5 mm. The layer material, for example PTFE, polypropylene or polyethylene may be used. In the initial state the light emitted from a light source 9 is reflected to about 4% at the surface of the carrier plate. 1 This value is derived from the different refractive indices of air (n = 1) and glass (n = 1.52). The remainder of penetrating into the cell, light is absorbed by the insulating layer 8, if it is deeply colored black. This condition is provided in automotive rearview mirrors to night mode, to protect the driver from glare from the headlights of vehicles on rising.

If the mirrors are switched on day mode, then to the electrodes 4, applied 5 by means of the changeover switch 10, the voltage of a battery 11 with a polarity such that on through the now begins electrolytic process, a metal layer 12 (Figure 1) made of metal the electrode 5 the electrolyte is deposited on the originally transparent electrode 4. 7 In the case of silver, the reaction is carried out according to the scheme:

Figure imgf000007_0001

wherein at the counter electrode 5 runs each opposite reaction. The process is reversible, that is, when re-reversal of the voltage reflected from the active electrode metal layer h is decomposed and deposited on the counter electrode. 5 So that the mirror is switched back for night operation.

With a suitable composition of the electrolyte, the deposited on the active electrode 4 metal layer 12 depends on the appearance and action of a metal mirror whose Re flexionsvermögen the reflectivity of the deposited metal. The reflectance is for silver layers from 0.90 to 0.94 and for Aluminiumschich- th from 0.80 to 0.85. Other suitable reflective layers are layers of tin, zinc layers, nickel layers, and platinum layers, but their Ηeflexionsgrad is lower than that of silver and aluminum layers.

A for depositing a highly reflective silver layer on the cathode electrode 4 is connected as a suitable electrolyte may for example consist of a highly diluted, silver nitrate-containing nitric acid. Another electrolyte composition (AgI + UAJ in methanol) allows a reversal of the functions described above as follows:

On the carrier plate 3, a mirror layer of silver is deposited as an electrode. 5 The insulating layer 8 is omitted. The light emitted from the light source 9 passes through the light transparent electrolyte 7 and is reflected by the mirror layer 5 in the eye 2 of the beholder. When a voltage of such graininess at the electrode 4 is deposited at a current density of 20 to 25 A / cm 2 of silver that it appears black and thus absorbs incident light. The absorption of such silver layers with a thickness of 500 nm to 1.5 microns is very high. The deposition takes place at voltages in the order of 1 V in 50 to 200 ms.

Claims

claims
1. Application of the electrolysis process to generate and detachment of a reflective metal layer (12) on a planar electrode (4) by reversing the flow of current in the electrolyte (7) in a mirror, in particular a rear view mirror for motor vehicles, for reversibly changing the reflectance.
2. The method according to claim 1, characterized in that replaced to reduce the reflectance of the mirror reflective metal by a viewer facing the front electrode (4) and on a rear electrode (5) of the mirror is deposited.
3. The method according to claim 1, characterized in that replaced to reduce the reflectance of the mirror reflective metal from a rear electrode (5) and facing in a granular form on a the viewer (2) the front electrode (4) of the mirror is deposited.
H . Sp iegel according to any one of claims 1 to 3, characterized in that it can be connected two at a umpolbare voltage source (11), flat electrodes (4, 5), each enclosing on a the electrolyte (7) support plate (1 or 3 is disposed), and that (the viewer 2) facing front electrode (4) and the carrier plate (1) are made of transparent materials, while the rear electrode is formed of a reflective metal.
5. Mirror according to claim 4, characterized in that is applied to the rear electrode (5) a permeable carrier insulation layer (8) of a dark, preferably black color.
6. A mirror according to claim 5, characterized in that the permeable insulating layer is formed as a porous film layer having a thickness of 0.1 to 0.5 mm.
7. A mirror according to claim 6, characterized in that the porous film layer (8) consists of PTFE, polypropylene or polyethylene.
8. A mirror according to one of claims 4 to 7, characterized in that the the observer (2) facing the electrode (4) (ITO), and of transparent tin-indium oxide that as a carrier plate (1) for this electrode, a glass plate serves.
PCT/DE1986/000104 1985-04-18 1986-03-14 Application of the electrolytic process to change the degree of reflection of mirrors WO1986006179A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE19853513988 DE3513988A1 (en) 1985-04-18 1985-04-18 reflect application of electrolysis method to change in yourself the reflection degree of
DEP3513988.9 1985-04-18

Publications (1)

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WO (1) WO1986006179A1 (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0728618A2 (en) * 1995-02-22 1996-08-28 Gentex Corporation Dimmable rearview mirror for motor vehicles
EP1700151A2 (en) * 2003-12-23 2006-09-13 Donnelly Corporation Electro-optic mirror cell
US8833987B2 (en) 2005-09-14 2014-09-16 Donnelly Corporation Mirror reflective element sub-assembly for exterior rearview mirror of a vehicle
US8884788B2 (en) 1998-04-08 2014-11-11 Donnelly Corporation Automotive communication system
US8908039B2 (en) 2000-03-02 2014-12-09 Donnelly Corporation Vehicular video mirror system
US9014966B2 (en) 2000-03-02 2015-04-21 Magna Electronics Inc. Driver assist system for vehicle
US9019091B2 (en) 1999-11-24 2015-04-28 Donnelly Corporation Interior rearview mirror system
US9019090B2 (en) 2000-03-02 2015-04-28 Magna Electronics Inc. Vision system for vehicle
US9073491B2 (en) 2002-09-20 2015-07-07 Donnelly Corporation Exterior rearview mirror assembly
US9090211B2 (en) 2002-09-20 2015-07-28 Donnelly Corporation Variable reflectance mirror reflective element for exterior mirror assembly
US9278654B2 (en) 1999-11-24 2016-03-08 Donnelly Corporation Interior rearview mirror system for vehicle
US9352623B2 (en) 2001-01-23 2016-05-31 Magna Electronics Inc. Trailer hitching aid system for vehicle
US9557584B2 (en) 2003-05-19 2017-01-31 Donnelly Corporation Rearview mirror assembly for vehicle

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5903382A (en) * 1997-12-19 1999-05-11 Rockwell International Corporation Electrodeposition cell with high light transmission
JP2003522338A (en) * 1998-12-15 2003-07-22 ロックウェル・サイエンス・センター・エルエルシー Reversible electrochemical mirror for adjusting the reflected radiation
DE10256645A1 (en) * 2002-12-03 2004-06-17 Hella Kg Hueck & Co. sensor device

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3153113A (en) * 1961-01-26 1964-10-13 Eastman Kodak Co Electroplating light valve
DE2934451A1 (en) * 1979-08-25 1981-03-12 Vdo Schindling Dimming Rearview Mirror, particularly for motor vehicles.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3153113A (en) * 1961-01-26 1964-10-13 Eastman Kodak Co Electroplating light valve
DE2934451A1 (en) * 1979-08-25 1981-03-12 Vdo Schindling Dimming Rearview Mirror, particularly for motor vehicles.

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0728618A3 (en) * 1995-02-22 1996-11-06 Gentex Corp Dimmable rearview mirror for motor vehicles
EP0728618A2 (en) * 1995-02-22 1996-08-28 Gentex Corporation Dimmable rearview mirror for motor vehicles
US9481306B2 (en) 1998-04-08 2016-11-01 Donnelly Corporation Automotive communication system
US9221399B2 (en) 1998-04-08 2015-12-29 Magna Mirrors Of America, Inc. Automotive communication system
US8884788B2 (en) 1998-04-08 2014-11-11 Donnelly Corporation Automotive communication system
US9376061B2 (en) 1999-11-24 2016-06-28 Donnelly Corporation Accessory system of a vehicle
US9019091B2 (en) 1999-11-24 2015-04-28 Donnelly Corporation Interior rearview mirror system
US9278654B2 (en) 1999-11-24 2016-03-08 Donnelly Corporation Interior rearview mirror system for vehicle
US9014966B2 (en) 2000-03-02 2015-04-21 Magna Electronics Inc. Driver assist system for vehicle
US9019090B2 (en) 2000-03-02 2015-04-28 Magna Electronics Inc. Vision system for vehicle
US8908039B2 (en) 2000-03-02 2014-12-09 Donnelly Corporation Vehicular video mirror system
US9783114B2 (en) 2000-03-02 2017-10-10 Donnelly Corporation Vehicular video mirror system
US9809171B2 (en) 2000-03-02 2017-11-07 Magna Electronics Inc. Vision system for vehicle
US9809168B2 (en) 2000-03-02 2017-11-07 Magna Electronics Inc. Driver assist system for vehicle
US9315151B2 (en) 2000-03-02 2016-04-19 Magna Electronics Inc. Driver assist system for vehicle
US10053013B2 (en) 2000-03-02 2018-08-21 Magna Electronics Inc. Vision system for vehicle
US9694749B2 (en) 2001-01-23 2017-07-04 Magna Electronics Inc. Trailer hitching aid system for vehicle
US9352623B2 (en) 2001-01-23 2016-05-31 Magna Electronics Inc. Trailer hitching aid system for vehicle
US9073491B2 (en) 2002-09-20 2015-07-07 Donnelly Corporation Exterior rearview mirror assembly
US10029616B2 (en) 2002-09-20 2018-07-24 Donnelly Corporation Rearview mirror assembly for vehicle
US9545883B2 (en) 2002-09-20 2017-01-17 Donnelly Corporation Exterior rearview mirror assembly
US9878670B2 (en) 2002-09-20 2018-01-30 Donnelly Corporation Variable reflectance mirror reflective element for exterior mirror assembly
US9090211B2 (en) 2002-09-20 2015-07-28 Donnelly Corporation Variable reflectance mirror reflective element for exterior mirror assembly
US9341914B2 (en) 2002-09-20 2016-05-17 Donnelly Corporation Variable reflectance mirror reflective element for exterior mirror assembly
US9783115B2 (en) 2003-05-19 2017-10-10 Donnelly Corporation Rearview mirror assembly for vehicle
US9557584B2 (en) 2003-05-19 2017-01-31 Donnelly Corporation Rearview mirror assembly for vehicle
EP1700151A4 (en) * 2003-12-23 2011-07-06 Donnelly Corp Electro-optic mirror cell
EP1700151A2 (en) * 2003-12-23 2006-09-13 Donnelly Corporation Electro-optic mirror cell
US9694753B2 (en) 2005-09-14 2017-07-04 Magna Mirrors Of America, Inc. Mirror reflective element sub-assembly for exterior rearview mirror of a vehicle
US8833987B2 (en) 2005-09-14 2014-09-16 Donnelly Corporation Mirror reflective element sub-assembly for exterior rearview mirror of a vehicle
US9045091B2 (en) 2005-09-14 2015-06-02 Donnelly Corporation Mirror reflective element sub-assembly for exterior rearview mirror of a vehicle
US9758102B1 (en) 2005-09-14 2017-09-12 Magna Mirrors Of America, Inc. Mirror reflective element sub-assembly for exterior rearview mirror of a vehicle

Also Published As

Publication number Publication date Type
EP0218610A1 (en) 1987-04-22 application
DE3513988A1 (en) 1986-10-23 application

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