WO2001001192A1 - An electro-optic device having a self-cleaning hydrophilic coating - Google Patents
An electro-optic device having a self-cleaning hydrophilic coating Download PDFInfo
- Publication number
- WO2001001192A1 WO2001001192A1 PCT/US2000/017402 US0017402W WO0101192A1 WO 2001001192 A1 WO2001001192 A1 WO 2001001192A1 US 0017402 W US0017402 W US 0017402W WO 0101192 A1 WO0101192 A1 WO 0101192A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- hydrophilic
- coating
- mirror
- electrochromic
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60Q—ARRANGEMENT OF SIGNALLING OR LIGHTING DEVICES, THE MOUNTING OR SUPPORTING THEREOF OR CIRCUITS THEREFOR, FOR VEHICLES IN GENERAL
- B60Q1/00—Arrangement of optical signalling or lighting devices, the mounting or supporting thereof or circuits therefor
- B60Q1/26—Arrangement of optical signalling or lighting devices, the mounting or supporting thereof or circuits therefor the devices being primarily intended to indicate the vehicle, or parts thereof, or to give signals, to other traffic
- B60Q1/2661—Arrangement of optical signalling or lighting devices, the mounting or supporting thereof or circuits therefor the devices being primarily intended to indicate the vehicle, or parts thereof, or to give signals, to other traffic mounted on parts having other functions
- B60Q1/2665—Arrangement of optical signalling or lighting devices, the mounting or supporting thereof or circuits therefor the devices being primarily intended to indicate the vehicle, or parts thereof, or to give signals, to other traffic mounted on parts having other functions on rear-view mirrors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R1/00—Optical viewing arrangements; Real-time viewing arrangements for drivers or passengers using optical image capturing systems, e.g. cameras or video systems specially adapted for use in or on vehicles
- B60R1/02—Rear-view mirror arrangements
- B60R1/06—Rear-view mirror arrangements mounted on vehicle exterior
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R1/00—Optical viewing arrangements; Real-time viewing arrangements for drivers or passengers using optical image capturing systems, e.g. cameras or video systems specially adapted for use in or on vehicles
- B60R1/02—Rear-view mirror arrangements
- B60R1/06—Rear-view mirror arrangements mounted on vehicle exterior
- B60R1/0602—Rear-view mirror arrangements mounted on vehicle exterior comprising means for cleaning or deicing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R1/00—Optical viewing arrangements; Real-time viewing arrangements for drivers or passengers using optical image capturing systems, e.g. cameras or video systems specially adapted for use in or on vehicles
- B60R1/02—Rear-view mirror arrangements
- B60R1/08—Rear-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
- B60R1/083—Anti-glare mirrors, e.g. "day-night" mirrors
- B60R1/088—Anti-glare mirrors, e.g. "day-night" mirrors using a cell of electrically changeable optical characteristic, e.g. liquid-crystal or electrochromic mirrors
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
- G02B27/0006—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 with means to keep optical surfaces clean, e.g. by preventing or removing dirt, stains, contamination, condensation
-
- 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
- G02F1/153—Constructional details
- G02F1/157—Structural association of cells with optical devices, e.g. reflectors or illuminating devices
Definitions
- the present invention generally relates to electro-optic devices, and more specifically relates to rearview mirrors of a vehicle.
- the windows are typically coated with a hydrophobic material that causes the water droplets to bead up on the outer surface of the window. These water beads are then either swept away by windshield wipers or are blown off the window as the vehicle moves.
- hydrophilic coating on the outer surface of the external mirrors. See U.S. Patent No. 5,594,585.
- One such hydrophilic coating includes a single layer of silicon dioxide (SiO 2 ).
- the Si ⁇ layer is relatively porous. Water on the mirror is absorbed uniformly across the surface of the mirror into the pores of the SiO 2 layer and subsequently evaporates leaving no water spots.
- One problem with such single layer coatings of SiO 2 is that oil, grease, and other contaminants can also fill the pores of the SiO 2 layer. Many such contaminants, particularly hydrocarbons like oil and grease, do not readily evaporate and hence clog the pores of the SiO ⁇ layer. When the pores of the pores of the SiO 2
- a solution to the above problem pertaining to hydrophilic layers is to form the coating of a relatively thick layer (e.g. , about 1000-3000 A or more) of titanium dioxide (TiO 2 ).
- TiO 2 titanium dioxide
- This coating exhibits photocatalytic properties when exposed to ultraviolet (UV) radiation. More specifically, the coating absorbs UV photons and, in the presence of water, generates highly reactive hydroxyl radicals that tend to oxidize organic materials that have collected in its pores or on its surface. Consequently, hydrocarbons, such as oil and grease, that have collected on the mirror are converted to carbon dioxide (CO2) and hence are eventually removed from the mirror whenever UV radiation impinges upon the mirror surface.
- This particular coating is thus a self-cleaning hydrophilic coating.
- One measure of the hydrophilicity of a particular coating is to measure the contact angle that the sides of a water drop form with the surface of the coating.
- An acceptable level of hydrophilicity is present in a mirror when the contact angle is less than about 30°, and more preferably, the hydrophilicity is less than about 20°, and most preferably is less than about 10°.
- the above self-cleaning hydrophilic coating exhibits contact angles that decrease when exposed to UV radiation as a result of the self- cleaning action and the hydrophilic effect of the coating. The hydrophilic effect of this coating, however, tends to reverse over time when the mirror is not exposed to UV radiation.
- the above self-cleaning hydrophilic coating can be improved by providing a film of about 150 to 1000 A of Si ⁇ 2 on top of the relatively thick T1O2 layer. See U.S. Patent No. 5,854,708. This seems to enhance the self-cleaning nature of the ⁇ O2 layer by reducing the dosage of UV radiation required and by maintaining the hydrophilic effect of the mirror over a longer period of time after the mirror is no longer exposed to UV radiation.
- variable reflectance mirrors such as electrochromic mirrors
- a first reason is that many of the above-noted hydrophilic coatings introduce colored double images and increase the low-end reflectivity of the variable reflectance mirror.
- commercially available, outside electrochromic mirrors exist that have a low-end reflectivity of about 10 percent and a high-end reflectivity of about 50 to 65 percent.
- a hydrophilic coating including a material such as ⁇ O2, which has a high index of refraction, on a glass surface of the mirror a significant amount of the incident light is reflected at the glass/Ti ⁇ 2 layer interface regardless of the variable reflectivity level of the mirror.
- the low-end reflectivity would be increased accordingly.
- Such a higher low-end reflectivity obviously significantly reduces the range of variable reflectance the mirror exhibits and thus reduces the effectiveness of the mirror in reducing annoying glare from the headlights of rearward vehicles.
- haze Another reason that prior art coatings have not been considered for use on many electro-optic elements is haze. This haze is particularly evident in hydrophilic coatings comprising dispersed ⁇ O2 particles in a binding media such as Si ⁇ 2. Titanium dioxide particles have a high refractive index and are very effective at scattering light. The amount of light scattered by such a first surface hydrophilic coating is small relative to the total light reflected in a conventional mirror. In an electro-optic mirror in the low reflectance state, however, most of the light is reflected off of the first surface and the ratio of scattered light to total reflected light is much higher, creating a foggy or unclear reflected image.
- a rearview mirror comprises a variable reflectance mirror element having a reflectivity that may be varied in response to an applied voltage so as to exhibit at least a high reflectance state and low reflectance state, and a hydrophilic optical coating applied to a front surface of the mirror element.
- the rearview mirror preferably exhibits a reflectance of less than 20 percent in said low reflectance state, and also preferably exhibits a C* value less than about 25 in both said high and low reflectance states so as to exhibit substantial color neutrality and is substantially haze free in both high and low reflectance states.
- Fig. 1 is a front perspective view of an external rearview mirror assembly constructed in accordance with the present invention
- Fig. 2 is a cross section of a first embodiment of the external rearview mirror assembly shown in Fig. 1 along line 2-2' ;
- Fig. 3 is a cross section of a second embodiment of the external rearview mirror assembly shown in Fig. 1 along line 3-3';
- Fig. 4 is a cross section of a third embodiment of the external rearview mirror assembly shown in Fig. 1 along line 4-4 ' ;
- Fig. 5 is a partial cross section of an electrochromic insulated window constructed in accordance with the present invention.
- FIG. 1 shows an external rearview mirror assembly 10 constructed in accordance with the present invention.
- mirror assembly 10 generally includes a housing 15 and a mirror 20 movably mounted in housing 15.
- Housing 15 may have any conventional structure suitably adapted for mounting assembly 10 to the exterior of a vehicle.
- Fig. 2 shows an exemplary construction of a first embodiment of mirror 20.
- mirror 20 includes a reflective element 100 having a reflectivity that may be varied in response to an applied voltage and an optical coating 130 applied to a front surface 112a of reflective element 100.
- Reflective element 100 preferably includes a first (or front) element 112 and a second (or rear) element 114 sealably bonded in spaced-apart relation to define a chamber.
- Front element 112 has a front surface 112a and a rear surface 112b
- rear element 114 has a front surface 114a and a rear surface 114b.
- front surface 112a of front element 112 shall be referred to as the first surface
- rear surface 112b of front element 112 shall be referred to as the second surface
- Reflective element 100 also includes a transparent first electrode 118 carried on one of second surface 112b and third surface 114a, and a second electrode 120 carried on one of second surface 112b and third surface 114a.
- First electrode 118 may have one or more layers and may function as a color suppression coating.
- Second electrode 120 may be reflective or transflective, or a separate reflector 122 may be provided on fourth surface 114b of mirror 100 in which case electrode 120 would be transparent.
- second electrode 120 is reflective or transflective and the layer referenced by numeral 122 is an opaque layer or omitted entirely.
- Reflective element 100 also preferably includes an electrochromic medium 124 contained in the chamber in electrical contact with first and second electrodes 118 and 120.
- Electrochromic medium 124 includes electrochromic anodic and cathodic materials that can be grouped into the following categories:
- Single layer - the electrochromic medium is a single layer of material which may include small nonhomogeneous regions and includes solution-phase devices where a material is contained in solution in the ionically conducting electrolyte and remains in solution in the electrolyte when electrochemically oxidized or reduced.
- Solution-phase electroactive materials may be contained in the continuous solution phase of a cross-linked polymer matrix in accordance with the teachings of U.S. Patent No. 5,928,572, entitled "IMPROVED ELECTROCHROMIC LAYER AND DEVICES
- the anodic and cathodic materials can be combined or linked by a bridging unit as described in International Application No. PCT/WO97/EP498 entitled
- a single layer medium includes the medium where the anodic and cathodic materials can be incorporated into the polymer matrix as described in
- a medium where one or more materials in the medium undergoes a change in phase during the operation of the device, for example, a deposition system where a material contained in solution in the ionically conducting electrolyte, which forms a layer or partial layer on the electronically conducting electrode when electrochemically oxidized or reduced.
- Multilayer - the medium is made up in layers and includes at least one material attached directly to an electronically conducting electrode or confined in close proximity thereto, which remains attached or confined when electrochemically oxidized or reduced.
- electrochromic medium examples include the metal oxide films, such as tungsten oxide, iridium oxide, nickel oxide, and vanadium oxide.
- the electrochromic medium may also contain other materials, such as light absorbers, light stabilizers, thermal stabilizers, antioxidants, thickeners, or viscosity modifiers.
- reflective element 100 may have essentially any structure, the details of such structures are not further described.
- Examples of preferred electrochromic mirror constructions are disclosed in U.S. Patent No. 4,902,108, entitled “SINGLE- COMPARTMENT, SELF-ERASING, SOLUTION-PHASE ELECTROCHROMIC DEVICES SOLUTIONS FOR USE THEREIN, AND USES THEREOF," issued February 20, 1990, to H.J. Byker; Canadian Patent No. 1,300,945, entitled “AUTOMATIC REARVIEW MIRROR SYSTEM FOR AUTOMOTIVE VEHICLES, " issued May 19, 1992, to J. H. Bechtel et al.; U.S. Patent No.
- reflective element 100 is preferably constructed as disclosed in commonly assigned International Patent Application No. PCT/US99/24682 (Publication No. WO 00/23826), entitled "ELECTROCHROMIC REARVIEW MIRROR INCORPORATING A THIRD
- reflective element 100 is convex or aspheric, as is common for passenger-side external rearview mirrors as well as external driver-side rearview mirrors of cars in Japan and Europe, reflective element 100 may be made using thinner elements 112 and 114 while using a polymer matrix in the chamber formed therebetween as is disclosed in commonly assigned U.S. Patent No. 5,940,201 entitled
- the electrochromic element of the present invention is preferably color neutral.
- a color neutral electrochromic element the element darkens to a gray color, which is more ascetically pleasing than any other color when used in an electrochromic mirror.
- U.S. Patent No. 6,020,987, entitled "ELECTROCHROMIC MEDIUM CAPABLE OF PRODUCING A PRE-SELECTED COLOR” discloses electrochromic media that are perceived to be gray throughout their normal range of operation.
- International Patent Application No. PCT/US99/24682 Publication No.
- WO 00/23826 entitled “ELECTROCHROMIC REARVIEW MIRROR INCORPORATING A THIRD SURFACE METAL REFLECTOR” discloses additional electrochromic mirrors that exhibit substantial color neutrality while enabling displays to be positioned behind the reflective surface of the electrochromic mirror.
- mirror 20 further includes an optical coating 130.
- Optical coating 130 is a self-cleaning hydrophilic optical coating.
- Optical coating 130 preferably exhibits a reflectance at first surface 112a of reflective element 100 that is less than about 20 percent. If the reflectance at first surface 112a is greater than about 20 percent, noticeable double-imaging results, and the range of variable reflectance of reflective element 100 is significantly reduced.
- the variable reflectance mirror as a unit should have a reflectance of less than about 20 percent in its lowest reflectance state, and more preferably less than 15 percent, and most preferably less than 10 percent in most instances.
- Optical coating 130 also is preferably sufficiently hydrophilic such that water droplets on a front surface of coating 130 exhibit a contact angle of less than about 30°, more preferably less than about 20°, and most preferably less than about 10°. If the contact angle is greater than about 30°, the coating 130 exhibits insufficient hydrophilic properties to prevent distracting water beads from forming. Optical coating 130 should also exhibit self-cleaning properties whereby the hydrophilic properties may be restored following exposure to UV radiation. As explained in further detail below, optical coating 130 should also have certain color characteristics so as to be color neutral or complement any coloration of the mirror element to render the mirror color neutral. For these purposes, coating 130 may include a color suppression coating 131 including one or more optical layers 132 and 134.
- optical coating 130 includes at least four layers of alternating high and low refractive index. Specifically, as shown in Fig. 2, optical coating 130 includes, in sequence, a first layer 132 having a high refractive index, a second layer 134 having a low refractive index, a third layer 136 having a high refractive index, and a fourth layer 138 having a low refractive index.
- third layer 136 is made of a photocatalytic material
- fourth layer 138 is made of a material that will enhance the hydrophilic properties of the photocatalytic layer 136 by generating hydroxyl groups on its surface.
- Suitable hydrophilic enhancement materials include SiO 2 and Al 2 O 3 , with
- Suitable photocatalytic materials include TiO 2 , ZnO, ZnO 2 ,
- the thickness of the SiO 2 outer layer is less than about 800 A, more preferably less than 300 A, and most preferably less than 150 A. If the SiO 2 outer layer is too thick (e.g. , more than about 1000 A), the underlying photocatalytic layer will not be able to "clean" the SiO 2 hydrophilic outer layer, at least not within a short time period.
- the two additional layers are provided to reduce the undesirable reflectance levels at the front surface of reflective element 100 and to provide any necessary color compensation/suppression so as to provide the desired coloration of the mirror.
- layer 132 is made of a photocatalytic material and second layer 134 is made of a hydrophilic enhancement material so as to contribute to the hydrophilic and photocatalytic properties of the coating.
- layer 132 may be made of any one of the photocatalytic materials described above or mixtures thereof, and layer 134 may be made of any of the hydrophilic enhancement materials described above or mixtures thereof.
- layer 132 is made of TiO 2 and layer 134 is made of SiO 2 .
- An alternative technique to using a high index layer and low index layer between the glass and the layer that is primarily comprised of photocatalytic metal oxide (i.e. , layer 136) to obtain all of the desired properties while maintaining a minimum top layer thickness of primarily silica is to use a layer, or layers, of intermediate index.
- This layer(s) could be a single material such as tin oxide or a mixture of materials such as a blend of titania and silica.
- the materials that have been modeled as potentially useful are blends of titania and silica, which can be obtained through sol-gel deposition as well as other means, and tin oxide, indium tin oxide, and yttrium oxide.
- color suppression coating 131 may also include a layer 150 of an electrically conductive transparent material such as ITO.
- the index of refraction of a titania film obtained from a given coating system can vary substantially with the choice of coating conditions and could be chosen to give the lowest index possible while maintaining sufficient amounts of anatase or rutile form in the film and demonstrating adequate abrasion resistance and physical durability.
- the lower index obtained in this fashion would yield similar advantages to lowering the index by mixing titania with a lower index material.
- Materials used for transparent second surface conductors are typically materials whose index of refraction is about 1.9 or greater and have their color minimized by using half wave thickness multiples or by using the thinnest layer possible for the application or by the use of one of several "non-iridescent glass structures. " These non- iridescent structures will typically use either a high and low index layer under the high index conductive coating (see, for example, U.S. Patent No. 4,377,613 and U.S. Patent No. 4,419,386 by Roy Gordon), or an intermediate index layer (see U.S. Patent No. 4,308,316 by Roy Gordon) or graded index layer (see U.S. Patent No. 4,440,822 by
- Fluorine doped tin oxide conductors using a non-iridescent structure are commercially available from Libbey-Owens-Ford and are used as the second surface transparent conductors in most inside automotive electrochromic mirrors produced at the present time.
- the dark state color of devices using this second surface coating stack is superior to that of elements using optical half wave thickness indium tin oxide (ITO) when it is used as a second surface conductive coating.
- ITO optical half wave thickness indium tin oxide
- Hydrophilic and photocatalytic coating stacks with less than about 800 A silica top layer, such as 1000 A titania 500 A silica, would still impart unacceptable color and/or reflectivity when used as a first surface coating stack in conjunction with this non-iridescent second surface conductor and other non-iridescent second surface structures, per the previous paragraph, that are not designed to compensate for the color of hydrophilic coating stacks on the opposing surface. Techniques would still need to be applied per the present embodiment at the first surface to reduce C* of the system in the dark state if these coatings were used on the second surface.
- ITO layers typically used as second surface conductors are either very thin (approximately 200-250 A), which minimizes the optical effect of the material by making it as thin as possible while maintaining sheet resistances adequate for many display devices, or multiples of half wave optical thickness (about 1400 A), which minimizes the overall reflectivity of the coating.
- the addition of photocatalytic hydrophilic coating stacks on opposing surfaces per the previous paragraph would create unacceptable color and/or reflectivity in conjunction with the use of these layer thicknesses of ITO used as the second surface conductor.
- techniques would need to be applied per the present embodiment at the first surface to reduce the C* of the system in the dark state.
- the second surface-coating stack for modification of the first surface-coating stack to optimize the color and reflectivity of the system containing both first and second surface coatings, one can modify the second surface-coating stack to optimize the color of the system.
- the 1000 A titania 500 A silica stack discussed in several places within this document has a reddish-purple color due to having somewhat higher reflectance in both the violet and red portions of the spectrum than it has in the green.
- a second surface coating with green color such as % wave optical thickness ITO, will result in a lower C* value for the dark state system than a system with a more standard thickness of ITO of half wave optical thickness, which is not green in color.
- These second surface compensating color layers will add reflectance at relative reflectance minima in the first surface coating stack. If desired, these second surface coating stacks can add reflectance without a first surface coating present.
- the three quarter wave optical thickness ITO layer mentioned above is at a relative maximum for reflectance and when used on the second surface will result in an element with higher dark state reflectivity than a similarly constructed element with half wave optical thickness ITO on the second surface whether or not additional first surface coatings are present.
- Another method of color compensating the first surface is through pre-selecting the color of the electrochromic medium in the dark state in accordance with the teachings of commonly assigned U.S. Patent No. 6,020,987, entitled “ELECTROCHROMIC MEDIUM CAPABLE OF PRODUCING A PRE-SELECTED COLOR. " Again, by using first surface coatings of 1000 A titania followed by 500 A silica as an example, the following modification would assist in lowering the C* value of an electrochromic mirror when activated.
- the color of the electrochromic medium was selected so that it was less absorbing in the green region when activated, the higher reflection of green wavelengths of light from the third or fourth surface reflector of the element would help balance the reflection of the unit in the dark state.
- Combinations of the aforementioned concepts for the first, second surface, and electrochromic medium are also potentially advantageous for the design.
- the low end reflectance of an electro-optic mirror may be desirable to limit the low end reflectance of an electro-optic mirror to about 12 percent or greater to compensate for the reduced brightness of images reflected off of the convex or aspheric surface. Maintaining a tight tolerance on this increased low-end reflectance value is difficult to achieve by controlling the full dark absorption of the electro-optic media alone, which is accomplished by either reducing the applied voltage or altering the concentration of the electro-optic materials in the electro-optic medium. It is much more preferred to maintain and control the tolerance on this increased low-end reflectance with a first surface film that would have a higher refractive index and therefore higher first surface reflectance than glass alone.
- first surface film Maintaining uniformity of the increased low- end reflectance from batch to batch in manufacturing is much easier with a first surface film than with the electro-optic media.
- photocatalytic layers such as titanium dioxide have such a higher refractive index.
- the dark state reflectivity can be raised using first surface coatings that are non-photocatalytic in nature as well. For example, by using quarter wave optical thickness aluminum oxide as the only layer on the first surface, the dark state reflectance of an element can be raised by approximately three to four percent.
- optical properties for a deposited film vary depending on deposition conditions that include partial pressure of oxygen gas, temperature of the substrate speed of deposition, and the like.
- index of refraction for a particular set of parameters on a particular system will affect the optimum layer thicknesses for obtaining the optical properties being discussed.
- this invention it may be preferable to include a layer of material between the substrate, especially if it is soda lime glass, and the photocatalytic layer(s) to serve as a barrier against sodium leaching in particular. If this layer is close to the index of refraction of the substrate, such as silica on soda lime glass, it will not affect the optical properties of the system greatly and should not be considered as circumventing the spirit of the invention with regards to contrasting optical properties between layers.
- a heating element 122 may optionally be provided on the fourth surface 114b of reflective element 100.
- one of the transparent front surface films could be formed of an electrically conductive material and hence function as a heater.
- a second embodiment of the invention is shown in Fig. 3.
- electrochromic mirror 100 has a similar construction to that shown in Fig. 2.
- Optical coating 130 differs in that it includes a transparent electrically conductive coating 150 that underlies hydrophilic layer 136. Suitable transparent conductors include ITO, ZnO, and SnO 2 (fluorine doped).
- each of these transparent conductors has a refractive index between that of the glass (1.45) of element 112 and the ⁇ O2 ( ⁇ 2.3) of layer 136, they make an excellent optical sublayer by reducing color and reflectivity as a result of applying the hydrophilic layer 136.
- An additional advantage resulting from the use of a transparent conductor 150 on the front surface of mirror element 100 is that an electric current may be passed through layer 150 such that layer 150 functions as a heater. Because hydrophilic coatings tend to spread water out into a thin film over the surface of the mirror, the water tends to freeze more quickly and impair vision. Thus, transparent conductive layer 150 can double both as a heater and a color/reflection suppression layer.
- the provision of a heater layer 150 on the front surface of the mirror provides several advantages. First, it removes the need to provide a costly heater to the back of the mirror. Additionally, heater 150 provides heat at the front surface of the mirror where the heat is needed most to clear the mirror of frost. Current heaters applied to the back of the mirror must heat through the whole mirror mass to reach the frost film on the front surface.
- a pair of buss clips 152 and 154 may be secured at the top and bottom of mirror 100 or on opposite sides so as to not interfere with the buss clips that are otherwise used to apply a voltage across electrochromic medium 124 via conductors 118 and 120.
- a common buss clip 160 may be provided to electrically couple electrode 118 and one edge of heater layer 150 to ground while separate electrical buss connections 162 and 164 are provided to respectively couple the other side of heater layer 150 and electrode 120 to a positive voltage potential.
- L*a*b* chart L* defines lightness, a* denotes the red/green value, and b* denotes the yellow/blue value.
- Each of the electrochromic media has an absorption spectra at each particular voltage that may be converted to a three-number designation, their L*a*b* values.
- *a*b* values To calculate a set of color coordinates, such as *a*b* values, from the spectral transmission or reflectance, two additional items are required.
- One is the spectral power distribution of the source or illuminant.
- the present disclosure uses CIE Standard Illuminant D ⁇ s.
- the second item needed is the spectral response of the observer.
- the present disclosure uses the 2-degree CIE standard observer.
- the illuminant/observer combination used is represented as D ⁇ 5/2 degree.
- Many of the examples below refer to a value Y from the 1931 CIE Standard since it corresponds more closely to the reflectance than L*.
- the value C* which is also described below, is equal to the square root of (a*) 2 +(b*) 2 , and hence, provides a measure for quantifying color neutrality.
- the C* value of the mirror should be less than 25.
- the C* value is less than 20, more preferably is less than 15, and even more preferably is less than about 10.
- EXAMPLE 1 Two identical electrochromic mirrors were constructed having a rear element made with 2.2 mm thick glass with a layer of chrome applied to the front surface of the rear element and a layer of rhodium applied on top of the layer of chrome using vacuum deposition. Both mirrors included a front transparent element made of 1.1 mm thick glass, which was coated on its rear surface with a transparent conductive ITO coating of Vi wave optical thickness. The front surfaces of the front transparent elements were covered by a coating that included a first layer of 200 A thick TiO 2 , a second layer of
- the elements were filled with an electrochromic solution including propylene carbonate containing 3 percent by weight polymethylmethacrylate, 30 Mm Tinuvin P (UV absorber), 38 Mm N,N'-dioctyl-4, 4'bipyridinium bis(tetrafluoroborate), 27 Mm 5,10-dihydrodimethylphenazine and the ports were then plugged with a UV curable adhesive. Electrical contact buss clips were electrically coupled to the transparent conductors.
- an electrochromic solution including propylene carbonate containing 3 percent by weight polymethylmethacrylate, 30 Mm Tinuvin P (UV absorber), 38 Mm N,N'-dioctyl-4, 4'bipyridinium bis(tetrafluoroborate), 27 Mm 5,10-dihydrodimethylphenazine and the ports were then plugged with a UV curable adhesive. Electrical contact buss clips were electrically coupled to the transparent conductors.
- the average contact angle that a drop of water formed on the surfaces of the electrochromic mirrors after it was cleaned was 7°.
- two similar electrochromic mirrors were constructed, but without any first surface coating. These two mirrors had identical construction.
- the electrochromic mirrors having the inventive hydrophilic coating unexpectedly and surprisingly had better color neutrality than similarly constructed electrochromic mirrors not having such a hydrophilic coating. Additionally, the comparison shows that the addition of the hydrophilic coating does not appreciably increase the low-end reflectance of the mirrors.
- EXAMPLE 2 An electrochromic mirror was constructed in accordance with the description of Example 1 with the exception that a different first surface coating stack was deposited.
- the first surface stack consisted of a first layer of ITO having a thickness of approximately 700 A, a second layer of ⁇ O2 having thickness of 2400 A, and a third layer of SiO 2 having a thickness of approximately 100 A.
- the physical thickness of the ITO layer corresponds to approximately V ⁇ wave optical thickness at 500 run and the physical thickness of the ⁇ O2 layer corresponds to approximately 1 wave optical thickness at 550 nm.
- the proportion of anatase titania to rutile titania in the TiO ⁇ layer was determined to be about 89 percent anatase form and 11 percent rutile form from X- ray diffraction analysis of a similar piece taken from glass run in the same timeframe under similar coating parameters.
- the contact angle of a water droplet on the surface of this electrochromic mirror after cleaning was 4°.
- This example illustrates the suitability of an ITO color suppression layer 150 underlying the hydrophilic layers 136 and 138.
- EXAMPLE 3 An electrochromic mirror was modeled using commercially available thin film modeling software.
- the modeling software was FILMSTAR available from FTG Software Associates, Princeton, New Jersey.
- the electrochromic mirror that was modeled had the same constructions as in Examples 1 and 2 above except for the construction of the optical coating applied to the front surface of the mirror. Additionally, the mirror was only modeled in a dark state assuming the completely absorbing electrochromic fluid of index 1.43.
- the optical coating stack consisted of a first layer of SnOi having a thickness of 720 A and a refractive index of 1.90 at 550 nm, a second layer of dense TiO ⁇ having a thickness of 1552 A and a refractive index of about 2.43 at 550 nm, a third layer of a material with an index of about 2.31 at 550 nm and a wavelength-dependent refractive index similar to Ti ⁇ 2 applied at a thickness of 538 A, and a fourth layer of Si ⁇ 2 having a refractive index of 1.46 at 550 nm and a thickness of 100 A.
- the electrochromic mirror had the following averaged values:
- the material with an index of 2.31 constituting the third layer may be attained in several ways, including the following which could be used in combination or singularly: (1) reducing the density of the titania in the layer, (2) changing the ratio of anatase to rutile titania in the layer, and/or (3) creating a mixed oxide of titania and at least one other metal oxide with lower refractive index, such as AhO 3 , SiO 2 or SnO 2 among others.
- the electrochromic materials used in Examples 1 and 2 above do not become a perfectly absorbing layer upon application of voltage, and therefore, the model based on a completely absorbing electrochromic layer will tend to be slightly lower in predicted luminous reflectance Y than the actual device.
- EXAMPLE 4 An electrochromic mirror was modeled having the exact same parameters as in Example 3, but replacing the 1552 A-thick second layer of Ti ⁇ 2 of index 2.43 at 550 nm and the 538 A-thick third layer of index 2.31 at 550 nm, with a single layer of 2100 A- thick material having a refractive index of 2.31 at 550 nm.
- L* 43.34
- Example 3 yield a unit with lower Y than an equal thickness of material with refractive index of 2.31 in the same stack. Nevertheless, the color neutrality value C* is lower in the fourth example.
- first surface coating stack a first layer of Ta ⁇ Os having a thickness of 161 A and a refractive index of about 2.13 at 550 nm; a second layer of AhO 3 having a thickness of 442 A and a refractive index of about 1.67 at 550 nm; a third layer of Ti ⁇ 2 having a thickness of 541 A and a refractive index of about 2.43 at 550 nm; a fourth layer of ⁇ O2 or ⁇ O2 mixed with another oxide and having a thickness of 554 A and a refractive index of about 2.31 at 550 nm; and a fifth layer of SiO 2 having a thickness of 100 A and a refractive index of about 1.46 at 550 nm.
- An electrochromic mirror was constructed in the same manner as described above with respect to Example 1 except that a different first surface coating stack was deposited.
- This first surface stack consisted of a first layer of ⁇ O2 having a thickness of approximately 1000 A and a second layer of Si ⁇ 2 having a thickness of 200 A. In a high reflectance state, the following averaged values were measured:
- the present invention thus provides a hydrophilic coating that not only is suitable for an electrochromic device, but actually improves the color neutrality of the device.
- the third sample included a bottom layer of ITO having a thickness of 700 A, a middle layer of ⁇ O2 having a thickness of 2400 A, and a top layer of Si ⁇ 2 having a thickness of 100 A.
- the fourth sample had a bottom layer of ⁇ O2 having a thickness of 2400 A and a top layer of Si ⁇ 2 having a thickness of 300 A. These samples were all produced via sputter deposition on the same day. In sample 3, however, the ITO was pre-deposited. X-ray diffraction analysis showed a crystal structure of the ⁇ O2 layer as including 74 percent anatase TiCh and 26 percent rutile ⁇ O2. All samples were formed on soda lime glass substrates. The results of the test are illustrated below in Table 1.
- any top layer of SiO 2 should be kept relatively thin to allow the photocatalytic effect of the underlying TiO ⁇ layer to be effective. It is also apparent that increasing the thickness of the TiO 2 layer increases the photocatalytic rate.
- these coatings can also be applied by conventional sol-gel techniques. In this approach, the glass is coated with a metal alkoxide made from precursors such as tetra isopropyl titanate, tetra ethyl ortho silicate, or the like.
- metal alkoxides can be blended or mixed in various proportions and coated onto glass usually from an alcohol solution after being partially hydrolyzed and condensed to increase the molecular weight by forming metal oxygen metal bonds.
- These coating solutions of metal alkoxides can be applied to glass substrates by a number of means such as dip coating, spin coating, or spray coating. These coatings are then fired to convert the metal alkoxide to a metal oxide typically at temperatures above 450°C. Very uniform and durable thin film can be formed using this method. Since a vacuum process is not involved, these films are relatively inexpensive to produce. Multiple films with different compositions can be built up prior to firing by coating and drying between applications.
- This approach can be very useful to produce inexpensive hydrophilic coatings on glass for mirrors, especially convex or aspheric mirrors that are made from bent glass.
- the glass In order to bend the glass, the glass must be heated to temperatures above 550°C. If the sol-gel coatings are applied to the flat glass substrate before bending (typically on what will be the convex surface of the finished mirror), the coatings will fire to a durable metal oxide during the bending process.
- a hydrophilic coating can be applied to bent glass substrates for little additional cost. Since the majority of outside mirrors used in the world today are made from bent glass, this approach has major cost. benefits.
- the coatings could be applied by this sol-gel process with the remainder of the coating(s) applied by a vacuum process, such as sputtering or E-beam deposition.
- the first high index layer and low index layer of, for instance, TiO 2 and SiO 2> could be applied by a sol-gel technique and then the top TiO 2 and SiO 2 layer applied by sputtering. This would simplify the requirements of the coating equipment and yield cost savings.
- a sol-gel formed silica or doped silica layer for instance phosphorous doped silica, is effective in reducing sodium migration.
- This barrier underlayer can be applied using a sol-gel process.
- This silica layer could be applied first to the base glass or incorporated into the hydrophilic stack between the photocatalytic layer and the glass.
- the present invention is applicable to any electrochromic element including architectural windows and skylights, automobile windows, rearview mirrors, and sunroofs. With respect to rearview mirrors, the present invention is primarily intended for outside mirrors due to the increased likelihood that they will become foggy or covered with mist. Inside and outside rearview mirrors may be slightly different in configuration.
- the shape of the front glass element of an inside mirror is generally longer and narrower than outside mirrors.
- an inside mirror generally, when fully cleared, should have a reflectance value of about 70 percent to about 85 percent or higher, whereas the outside mirrors often have a reflectance of about 50 percent to about 65 percent. Also, in the United States
- the passenger-side mirror typically has a non-planar spherically bent or convex shape, whereas the driver-side mirror Ilia and inside mirror 110 presently must be flat.
- the driver-side mirror Ilia is commonly flat or aspheric, whereas the passenger-side mirror 111b has a convex shape.
- both outside mirrors have a non-planar convex shape.
- the transparent conductive layer applied to the rear surface of a non-planar front element is typically not made of fluorine-doped tin oxide, which is commonly used in planar mirrors, because the tin oxide coating can complicate the bending process and it is not commercially available on glass thinner than
- Such bent mirrors typically utilize a layer of ITO as the front transparent conductor.
- ITO is slightly colored and adversely introduces blue coloration into the reflected image as viewed by the driver.
- the color introduced by an ITO layer applied to the second surface of the element may be neutralized by utilizing an optical coating on the first surface of the electrochromic element.
- a glass element coated with a half wave thick ITO layer was constructed as was a glass element coated with a half wave thick ITO layer on one side and the hydrophilic coating described in the above Example 1 on the other side.
- the hydrophilic coating serves as a color suppression coating by noticeably improving the coloration of a glass element coated with ITO. Because outside rearview mirrors are often bent and include ITO as a transparent conductor, the ability to improve the color of the front coated element by adding a color suppression coating to the opposite side of the bent glass provides many manufacturing advantages.
- the first transparent electrode 118 coating can also be rendered more color neutral by incorporating thicker layers of first high then low refractive index of the appropriate thicknesses or an underlayer with an intermediate refractive index of the appropriate thickness.
- half wave and full wave ITO films can be made more color neutral by a one-quarter wave underlayer of intermediate refractive index aluminum oxide (AbO,).
- AbO intermediate refractive index aluminum oxide Table 2 below lists the measured reflected color values of one- half and full wave ITO films with and without a one-quarter wave thick underlayer of AI2O3 on glass. Both films were applied to the glass substrate by reactive magnetron sputtering.
- light attenuating devices such as scattered particle displays (such as those discussed in U.S. Patent Nos. 5,650,872, 5,325,220, 4,131,334, and 4,078,856) or liquid crystal displays (such as those discussed in U.S. Patent Nos. 5,673,150, 4,878,743, 4,813,768, 4,693,558, 4,671,615, and 4,660,937), can also benefit from the application of these principles.
- the light attenuating layer is between two pieces of glass or plastic, the same basic constraints and solutions to those constraints will apply.
- the color and reflectivity of a first surface hydrophilic layer or layer stack can impart substantial color and reflectivity to the device in the darkened state even when this first surface layer stack does not appreciably affect the bright state characteristics.
- Adjustments to the first surface layer stack similar to those discussed for an electrochromic device will, therefore, affect the color and/or reflectivity of the darkened device advantageously. The same will apply to adjustments made to the second surface of the device or to the color of the darkening layer itself.
- Fig. 5 shows an example of a variable transmittance window 200.
- the window includes an inner glass pane or other transparent element 204, an outer glass pane or other transparent element 202, and a window frame 206 that holds glass panes 202 and 204 in parallel spaced-apart relation.
- a variable transmittance element is positioned between glass panes 202 and 204 and may take the form of an electrochromic mirror with the exception that the reflective layer of the mirror is removed.
- the element may include a pair of spaced-apart transparent substrates 112 and 114 joined together by a seal 116 to define a chamber in which an electrochromic medium is dispensed. It will be appreciated by those skilled in the art that the structure of window 200 is shown for purposes of example only and that the frame and relation of the components to one another may vary.
- outer pane 202 may have an optical coating disposed on its outer surface.
- this coating may include a first layer 150 having a refractive index intermediate that of glass pane 202 and a second layer 136 made of a photocatalytic material, such as titanium dioxide.
- a third layer 137 may optionally be disposed over layer 136 and may comprise a photocatalytic material such as titanium dioxide.
- a layer would be modified to have a lower refractive index than layer 136.
- the coating may further include an optional hydrophilic layer 138 made of a material such as Si ⁇ 2. In general, any of the hydrophilic coatings discussed above may be utilized. It should be noted that color suppression and obtaining a neutral color of the window as a whole may or may not be a design constraint.
- any color suppression layer may be selected so as to enhance a particular color.
- any color suppression layer may be selected so as to enhance a particular color.
- increasing the thickness of the high index functional coating increases the strength of the photocatalytic effect. This is evidenced by a comparison of samples 1 and 2 in Table 1 above.
- dopants may also increase photocatalytic activity and possibly allow the thickness of the layer to otherwise be decreased while maintaining a particular level of photocatalism.
- Such dopants may include platinum, group metals copper, nickel, lanthanum, cobalt, and Sn ⁇ 2.
- a lower index of refraction for the outermost layer is desirable to reduce the reflectivity of the coating. This can be accomplished by lowering the density of the outermost layer, however, this may decrease the scratch resistance.
- the TiO ⁇ layer may be blended with silica, alumina, tin oxide, zinc oxide, zirconia, and praseodymium oxide to lower the index of that layer. In designs such as that described in Example 3, it may be possible to keep the majority of the material having the intermediate refractive index (i.e. , the SnO ⁇ layer) or blending with another material having some photocatalytic activity and thereby increase the photocatalytic activity of the entire stack. For example,
- SnO ⁇ may be used alone or in a mixture with another oxide.
- the thicker the SiO 2 top layer the easier it is to attain relatively low C* and Y, but there may be a substantial and undesirable insulative effect with respect to the photocatalism of the stack when the SiO ⁇ top layer is too thick.
- the above description is considered that of the preferred embodiments only.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00946851A EP1206726A4 (en) | 1999-06-25 | 2000-06-23 | An electro-optic device having a self-cleaning hydrophilic coating |
MXPA01012298A MXPA01012298A (en) | 1999-06-25 | 2000-06-23 | An electro-optic device having a self-cleaning hydrophilic coating. |
CA002378056A CA2378056A1 (en) | 1999-06-25 | 2000-06-23 | An electro-optic device having a self-cleaning hydrophilic coating |
JP2001507140A JP3746004B2 (en) | 1999-06-25 | 2000-06-23 | Electro-optical device with self-cleaning hydrophilic coating |
AU60547/00A AU6054700A (en) | 1999-06-25 | 2000-06-23 | An electro-optic device having a self-cleaning hydrophilic coating |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14108099P | 1999-06-25 | 1999-06-25 | |
US60/141,080 | 1999-06-25 | ||
US09/435,266 US6193378B1 (en) | 1999-06-25 | 1999-11-05 | Electrochromic device having a self-cleaning hydrophilic coating |
US09/435,266 | 1999-11-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001001192A1 true WO2001001192A1 (en) | 2001-01-04 |
Family
ID=26838775
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2000/017402 WO2001001192A1 (en) | 1999-06-25 | 2000-06-23 | An electro-optic device having a self-cleaning hydrophilic coating |
Country Status (8)
Country | Link |
---|---|
US (3) | US6193378B1 (en) |
EP (1) | EP1206726A4 (en) |
JP (2) | JP3746004B2 (en) |
KR (1) | KR100667417B1 (en) |
AU (1) | AU6054700A (en) |
CA (1) | CA2378056A1 (en) |
MX (1) | MXPA01012298A (en) |
WO (1) | WO2001001192A1 (en) |
Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005082015A2 (en) | 2004-02-27 | 2005-09-09 | Gentex Corporation | Vehicular rearview mirror elements and assemblies incorporating these elements |
EP1678530A2 (en) * | 2003-10-30 | 2006-07-12 | Gentex Corporation | Electrochromic device having a self-cleaning hydrophilic coating with an acid resistant under layer |
US7602542B2 (en) | 2002-09-30 | 2009-10-13 | Gentex Corporation | Vehicular rearview mirror elements and assemblies incorporating these elements |
US7719750B2 (en) | 2002-09-30 | 2010-05-18 | Gentex Corporation | Vehicular rearview mirror elements and assemblies incorporating these elements |
US8004741B2 (en) | 2004-02-27 | 2011-08-23 | Gentex Corporation | Vehicular rearview mirror elements and assemblies incorporating these elements |
US8169684B2 (en) | 2002-09-30 | 2012-05-01 | Gentex Corporation | Vehicular rearview mirror elements and assemblies incorporating these elements |
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 |
US8922867B2 (en) | 2009-04-23 | 2014-12-30 | Magna Mirrors Of America, Inc. | Frameless interior rearview mirror assembly |
US8976439B2 (en) | 2009-04-23 | 2015-03-10 | Magna Mirrors Of America, Inc. | Mirror assembly 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 |
US9019091B2 (en) | 1999-11-24 | 2015-04-28 | Donnelly Corporation | Interior rearview mirror system |
US9056584B2 (en) | 2010-07-08 | 2015-06-16 | Gentex Corporation | Rearview assembly for a 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 |
US9134585B2 (en) | 2002-09-30 | 2015-09-15 | Gentex Corporation | Automotive rearview mirror with capacitive switches |
US9278654B2 (en) | 1999-11-24 | 2016-03-08 | Donnelly Corporation | Interior rearview mirror system for vehicle |
US9316347B2 (en) | 2012-01-24 | 2016-04-19 | Gentex Corporation | Rearview assembly with interchangeable rearward viewing device |
US9346403B2 (en) | 2009-10-07 | 2016-05-24 | Magna Mirrors Of America, Inc. | Rearview mirror assembly |
US9352623B2 (en) | 2001-01-23 | 2016-05-31 | Magna Electronics Inc. | Trailer hitching aid system for vehicle |
US10112538B2 (en) | 2013-04-22 | 2018-10-30 | Magna Mirrors Of America, Inc. | Rearview mirror assembly for vehicle |
US10175477B2 (en) | 2008-03-31 | 2019-01-08 | Magna Mirrors Of America, Inc. | Display system for vehicle |
US10261648B2 (en) | 2009-10-07 | 2019-04-16 | Magna Mirrors Of America, Inc. | Exterior rearview mirror assembly |
US11325533B2 (en) | 2009-04-23 | 2022-05-10 | Magna Mirrors Of America, Inc. | Frameless interior rearview mirror assembly |
US11498486B2 (en) | 2009-10-07 | 2022-11-15 | Magna Mirrors Of America, Inc. | Vehicular exterior rearview mirror assembly |
Families Citing this family (113)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6830785B1 (en) * | 1995-03-20 | 2004-12-14 | Toto Ltd. | Method for photocatalytically rendering a surface of a substrate superhydrophilic, a substrate with a superhydrophilic photocatalytic surface, and method of making thereof |
US8060308B2 (en) * | 1997-10-22 | 2011-11-15 | Intelligent Technologies International, Inc. | Weather monitoring techniques |
US6816297B1 (en) * | 1999-06-25 | 2004-11-09 | Gentex Corporation | Electrochromic mirror having a self-cleaning hydrophilic coating |
US20060158735A1 (en) * | 2004-02-20 | 2006-07-20 | Tonar William L | Electro-optic device having a self-cleaning hydrophilic coating |
JP3701826B2 (en) * | 1999-11-12 | 2005-10-05 | 株式会社村上開明堂 | Colored anti-fog mirror |
US7021421B2 (en) * | 2000-06-07 | 2006-04-04 | Showa Denko Kabushiki Kaisha | Transparent noise-barrier wall |
US6409354B1 (en) * | 2000-08-23 | 2002-06-25 | Vtec Technologies, Inc. | Transparent plastic or polymer based mirror apparatus and method for making the same |
JP2002286904A (en) * | 2001-03-27 | 2002-10-03 | Seiko Epson Corp | Optical parts and projector using the same |
CN1401085A (en) * | 2001-06-11 | 2003-03-05 | 株式会社村上开明堂 | Antiforging element and method for forming same |
WO2003053577A1 (en) * | 2001-12-21 | 2003-07-03 | Nippon Sheet Glass Co., Ltd. | Member having photocatalytic function and method for manufacture thereof |
WO2003056386A1 (en) * | 2001-12-25 | 2003-07-10 | Murakami Corporation | Antiglare, anticlouding element |
JP2003287601A (en) * | 2002-03-27 | 2003-10-10 | Murakami Corp | Composite material |
DE10218820B4 (en) * | 2002-04-26 | 2006-05-11 | Fritz Reupsch | Exterior mirrors for motor vehicles |
CA2435164A1 (en) * | 2002-07-15 | 2004-01-15 | Magna Donnelly Mirrors North America L.L.C. | Resizeable mirror heating element and vehicular mirror assembly incorporating the same |
US7613741B2 (en) * | 2002-08-01 | 2009-11-03 | Oracle International Corporation | Utilizing rules in a distributed information sharing system |
MXPA05001880A (en) | 2002-08-21 | 2005-06-03 | Gentex Corp | Image acquisition and processing methods for automatic vehicular exterior lighting control. |
US9346402B2 (en) | 2002-09-30 | 2016-05-24 | Gentex Corporation | Vehicular rearview mirror elements and assemblies incorporating these elements |
US7370982B2 (en) | 2002-10-02 | 2008-05-13 | Gentex Corporation | Environmentally improved rearview mirror assemblies |
US7132625B2 (en) * | 2002-10-03 | 2006-11-07 | Ppg Industries Ohio, Inc. | Heatable article having a configured heating member |
US20050024705A1 (en) * | 2002-11-04 | 2005-02-03 | William Freeman | Photopolymerizable electrolyte layers for electrochromic windows |
ES2550534T3 (en) | 2002-11-05 | 2015-11-10 | Magna Mirrors Of America, Inc. | Electro-optic reflector element set |
US7965336B2 (en) | 2002-11-14 | 2011-06-21 | Donnelly Corporation | Imaging system for vehicle |
US7300166B2 (en) * | 2003-03-05 | 2007-11-27 | Electrochromix, Inc. | Electrochromic mirrors and other electrooptic devices |
EP1620763B1 (en) | 2003-05-06 | 2012-07-25 | Gentex Corporation | Vehicular rearview mirror |
CN1767777A (en) * | 2003-05-14 | 2006-05-03 | 株式会社村上开明堂 | Anti-fog mirror |
US20050286132A1 (en) * | 2003-10-30 | 2005-12-29 | Tonar William L | Electrochromic device having a self-cleaning hydrophilic coating with a controlled surface morphology |
EP1713736B1 (en) * | 2003-12-22 | 2016-04-27 | Cardinal CG Company | Graded photocatalytic coatings and methods of making such coatings |
JP2008505842A (en) * | 2004-07-12 | 2008-02-28 | 日本板硝子株式会社 | Low maintenance coating |
US8545030B2 (en) | 2004-07-12 | 2013-10-01 | Gentex Corporation | Rearview mirror assemblies with anisotropic polymer laminates |
EP1797017B1 (en) * | 2004-10-04 | 2010-11-24 | Cardinal CG Company | Thin film coating and temporary protection technology, insulating glazing units, and associated methods |
JP2006120356A (en) * | 2004-10-19 | 2006-05-11 | Fujitsu Hitachi Plasma Display Ltd | Plasma display panel and its manufacturing method |
JP4408438B2 (en) * | 2004-11-12 | 2010-02-03 | 株式会社村上開明堂 | Anti-fogging element and outer mirror |
CA2586842C (en) * | 2004-11-15 | 2013-01-08 | Cardinal Cg Company | Methods and equipment for depositing coatings having sequenced structures |
US7855821B2 (en) * | 2004-11-15 | 2010-12-21 | Gentex Corporation | Electrochromic compounds and associated media and devices |
JP4806416B2 (en) * | 2004-11-15 | 2011-11-02 | ジェンテックス コーポレイション | Electrochromic compounds and related media and devices |
US7923114B2 (en) * | 2004-12-03 | 2011-04-12 | Cardinal Cg Company | Hydrophilic coatings, methods for depositing hydrophilic coatings, and improved deposition technology for thin films |
US8092660B2 (en) * | 2004-12-03 | 2012-01-10 | Cardinal Cg Company | Methods and equipment for depositing hydrophilic coatings, and deposition technologies for thin films |
EP1852402A1 (en) * | 2004-12-06 | 2007-11-07 | Nippon Sheet Glass Company Limited | Glass member having photocatalytic function and heat ray reflective function, and double layer glass employing it |
DE102005015903B4 (en) * | 2005-04-06 | 2007-11-29 | Bayer Materialscience Ag | headlights |
US8344238B2 (en) * | 2005-07-19 | 2013-01-01 | Solyndra Llc | Self-cleaning protective coatings for use with photovoltaic cells |
US20090244361A1 (en) * | 2005-10-28 | 2009-10-01 | Magna Electronics Inc. | Camera module for vehicle vision system |
EP2426552A1 (en) | 2006-03-03 | 2012-03-07 | Gentex Corporation | Electro-optic elements incorporating improved thin-film coatings |
KR101275450B1 (en) * | 2006-03-03 | 2013-06-17 | 젠텍스 코포레이션 | Improved thin-film coatings, electro-optic elements and assemblies incorporating these elements |
EP2378350B1 (en) | 2006-03-09 | 2013-12-11 | Gentex Corporation | Vehicle rearview assembly including a high intensity display |
US7190505B1 (en) | 2006-03-28 | 2007-03-13 | Gentex Corporation | Electrochromic device having an improved fill port plug |
WO2007121215A1 (en) * | 2006-04-11 | 2007-10-25 | Cardinal Cg Company | Photocatalytic coatings having improved low-maintenance properties |
US7989094B2 (en) | 2006-04-19 | 2011-08-02 | Cardinal Cg Company | Opposed functional coatings having comparable single surface reflectances |
US7414770B2 (en) * | 2006-05-03 | 2008-08-19 | Gentex Corporation | Contollably dissolving spacing member and associated electrochromic device and method for manufacturing the same |
CN101472851A (en) * | 2006-06-16 | 2009-07-01 | 旭硝子欧洲平板玻璃股份有限公司 | Mirror |
US20080011599A1 (en) | 2006-07-12 | 2008-01-17 | Brabender Dennis M | Sputtering apparatus including novel target mounting and/or control |
FR2912977B1 (en) * | 2007-02-27 | 2009-04-10 | Renault Sas | BODY COMPONENT OF AN AUTOMOTIVE VEHICLE WITH A REFLECTIVE OR TRANSPARENT SURFACE WITH IMPROVED VISIBILITY IN THE PRESENCE OF DROPLETS |
US9274394B2 (en) * | 2007-03-05 | 2016-03-01 | Gentex Corporation | Multi-zone mirrors |
KR20080110090A (en) * | 2007-06-14 | 2008-12-18 | 삼성전자주식회사 | Refractive index decrement film, polarizing member using the same, and display device using the same |
US7820296B2 (en) | 2007-09-14 | 2010-10-26 | Cardinal Cg Company | Low-maintenance coating technology |
US8848158B2 (en) | 2008-07-01 | 2014-09-30 | Gentex Corporation | Liquid crystal display device and associated liquid crystal media for use in the same |
US7803285B2 (en) * | 2008-07-01 | 2010-09-28 | Gentex Corporation | Liquid crystal display device and associated liquid crystal media for use in the same |
US20100073754A1 (en) * | 2008-09-24 | 2010-03-25 | Gentex Corporation | Ultraviolet light stabilizing compounds and associated media and devices |
US8482664B2 (en) | 2008-10-16 | 2013-07-09 | Magna Electronics Inc. | Compact camera and cable system for vehicular applications |
EP2394426A4 (en) | 2009-02-06 | 2013-02-20 | Magna Electronics Inc | Improvements to camera for vehicle |
EP2411856B1 (en) | 2009-03-25 | 2018-08-01 | Magna Electronics Inc. | Vehicular camera and lens assembly |
WO2012051294A2 (en) | 2010-10-12 | 2012-04-19 | Gentex Corporation | Clear bezel |
KR101063745B1 (en) * | 2010-11-05 | 2011-09-08 | (주) 태양기전 | Glass and coating method |
US10350647B2 (en) | 2011-03-10 | 2019-07-16 | Dlhbowles, Inc. | Integrated automotive system, nozzle assembly and remote control method for cleaning an image sensor's exterior or objective lens surface |
WO2012138455A1 (en) * | 2011-03-10 | 2012-10-11 | Bowles Fluidics Corporation | Integrated automotive system, nozzle assembly and remote control method for cleaning an image sensor's lens |
WO2012145501A1 (en) | 2011-04-20 | 2012-10-26 | Magna Electronics Inc. | Angular filter for vehicle mounted camera |
US9871971B2 (en) | 2011-08-02 | 2018-01-16 | Magma Electronics Inc. | Vehicle vision system with light baffling system |
US9596387B2 (en) | 2011-08-02 | 2017-03-14 | Magna Electronics Inc. | Vehicular camera system |
US8885240B2 (en) | 2011-08-04 | 2014-11-11 | Gentex Corporation | Rearview assembly for a vehicle |
US8736943B2 (en) | 2012-01-17 | 2014-05-27 | Gentex Corporation | Variable transmission electrochromic window and associated aircraft window system |
US8879139B2 (en) | 2012-04-24 | 2014-11-04 | Gentex Corporation | Display mirror assembly |
WO2014032042A1 (en) | 2012-08-24 | 2014-02-27 | Gentex Corporation | Shaped rearview mirror assembly |
JP5865237B2 (en) * | 2012-11-21 | 2016-02-17 | 株式会社村上開明堂 | Hydrophilic member and method for producing the same |
US9327648B2 (en) | 2013-01-04 | 2016-05-03 | Gentex Corporation | Rearview assembly with exposed carrier plate |
US9488892B2 (en) | 2013-01-09 | 2016-11-08 | Gentex Corporation | Printed appliqué and method thereof |
US9434311B2 (en) | 2013-03-15 | 2016-09-06 | Gentex Corporation | Low reflectance glare optic |
EP2996818B1 (en) | 2013-05-17 | 2018-07-25 | 3M Innovative Properties Company | Method of making easy-clean surface |
EP2845773B1 (en) | 2013-09-10 | 2021-09-08 | dlhBowles Inc. | Integrated automotive system, pop-up nozzle assembly and remote control method for cleaning a wide-angle image sensor's exterior surface |
AU2014326772B2 (en) | 2013-09-24 | 2017-07-20 | Gentex Corporation | Display mirror assembly |
US9451138B2 (en) | 2013-11-07 | 2016-09-20 | Magna Electronics Inc. | Camera for vehicle vision system |
US9454054B2 (en) | 2013-11-18 | 2016-09-27 | Magna Mirrors Of America, Inc. | Electro-optic mirror element and process of making same |
US9749509B2 (en) | 2014-03-13 | 2017-08-29 | Magna Electronics Inc. | Camera with lens for vehicle vision system |
CN106660525B (en) | 2014-04-11 | 2020-06-02 | Dlh鲍尔斯公司 | Compact low-profile nozzle assembly and remotely controlled image sensor cleaning system |
EP3131785B1 (en) | 2014-04-16 | 2019-02-13 | dlhBowles Inc. | Integrated multi image sensor and lens washing nozzle assembly and method for simultaneously cleaning multiple image sensors |
WO2016044746A1 (en) | 2014-09-19 | 2016-03-24 | Gentex Corporation | Rearview assembly |
JP6504382B2 (en) * | 2014-10-24 | 2019-04-24 | パナソニックIpマネジメント株式会社 | Display control apparatus, display system, display control method, display control program, and projection apparatus |
WO2016073848A1 (en) | 2014-11-07 | 2016-05-12 | Gentex Corporation | Full display mirror actuator |
EP3218227B1 (en) | 2014-11-13 | 2018-10-24 | Gentex Corporation | Rearview mirror system with a display |
KR101997815B1 (en) | 2014-12-03 | 2019-07-08 | 젠텍스 코포레이션 | Display mirror assembly |
USD746744S1 (en) | 2014-12-05 | 2016-01-05 | Gentex Corporation | Rearview device |
JP2018513810A (en) | 2015-04-20 | 2018-05-31 | ジェンテックス コーポレイション | Rear view assembly with decoration |
EP3297870B1 (en) | 2015-05-18 | 2020-02-05 | Gentex Corporation | Full display rearview device |
JP6255541B2 (en) * | 2015-09-29 | 2017-12-27 | 富士フイルム株式会社 | Hydrophilic multilayer film, method for producing the same, and imaging system |
EP3368375B1 (en) | 2015-10-30 | 2020-03-04 | Gentex Corporation | Rearview device |
CN108349435B (en) | 2015-10-30 | 2021-06-15 | 金泰克斯公司 | Switching board |
US10250004B2 (en) | 2015-11-05 | 2019-04-02 | Magna Electronics Inc. | Method of forming a connector for an electrical cable for electrically connecting to a camera of a vehicle |
US10560613B2 (en) | 2015-11-05 | 2020-02-11 | Magna Electronics Inc. | Vehicle camera with modular construction |
US10351072B2 (en) | 2015-11-05 | 2019-07-16 | Magna Electronics Inc. | Vehicle camera with modular construction |
US10230875B2 (en) | 2016-04-14 | 2019-03-12 | Magna Electronics Inc. | Camera for vehicle vision system |
USD845851S1 (en) | 2016-03-31 | 2019-04-16 | Gentex Corporation | Rearview device |
US10142532B2 (en) | 2016-04-08 | 2018-11-27 | Magna Electronics Inc. | Camera for vehicle vision system |
USD817238S1 (en) | 2016-04-29 | 2018-05-08 | Gentex Corporation | Rearview device |
US10025138B2 (en) | 2016-06-06 | 2018-07-17 | Gentex Corporation | Illuminating display with light gathering structure |
US10237456B2 (en) | 2016-08-22 | 2019-03-19 | Magna Electronics Inc. | Vehicle camera assembly process |
WO2018093985A1 (en) | 2016-11-17 | 2018-05-24 | Cardinal Cg Company | Static-dissipative coating technology |
USD809984S1 (en) | 2016-12-07 | 2018-02-13 | Gentex Corporation | Rearview assembly |
USD854473S1 (en) | 2016-12-16 | 2019-07-23 | Gentex Corporation | Rearview assembly |
US10429641B2 (en) * | 2017-05-31 | 2019-10-01 | GM Global Technology Operations LLC | Light-enhanced self-cleaning film system and method of forming same |
US11305297B2 (en) | 2017-06-05 | 2022-04-19 | Dlhbowles, Inc. | Compact low flow rate fluidic nozzle for spraying and cleaning applications having a reverse mushroom insert geometry |
KR102616292B1 (en) * | 2019-04-24 | 2023-12-21 | 주식회사 라이드로 | Optical apparatus with window cleaning machanism |
CN111139478B (en) * | 2019-12-06 | 2021-02-26 | 清华大学 | MoS2Use of ZnO heterostructure as reversible light-controlled wetting material and method of use |
FR3105460B1 (en) * | 2019-12-24 | 2023-01-20 | Saint Gobain | Optical system with electrochemical functional device having electrically controllable optical and/or energetic properties and chromatic control coating in reflection, related methods. |
US11365855B1 (en) | 2021-06-03 | 2022-06-21 | Adesso Inc. | Lighting assembly having motion effects |
US11789329B2 (en) * | 2021-10-01 | 2023-10-17 | Redoxlens Co., Ltd. | Electrochromic device capable of creating color-changing pattern |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4293901A (en) * | 1979-12-17 | 1981-10-06 | Esquire, Inc. | Reflector system having sharp light cutoff characteristics |
US4375318A (en) * | 1979-08-30 | 1983-03-01 | American Cyanamid Company | Electrochromic cells with improved electrolyte system |
US5216536A (en) * | 1991-11-26 | 1993-06-01 | Donnelly Corporation | Encapsulated electrochromic device and method for making same |
US5688855A (en) * | 1995-05-01 | 1997-11-18 | S.K.Y. Polymers, Inc. | Thin film hydrophilic coatings |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4330604A (en) * | 1980-08-04 | 1982-05-18 | Hughes Aircraft Company | Fabrication of holograms on plastic substrates |
JPS635301A (en) | 1986-06-25 | 1988-01-11 | Matsushita Electric Works Ltd | Reflecting mirror |
JPS63100042A (en) | 1986-10-14 | 1988-05-02 | Nippon Sheet Glass Co Ltd | Glass article difficult-to be dirtied |
FR2691550B1 (en) * | 1992-05-21 | 1995-04-21 | Saint Gobain Vitrage Int | Architectural electrochromic glazing. |
US5909314A (en) * | 1994-02-15 | 1999-06-01 | Dai Nippon Printing Co., Ltd. | Optical functional materials and process for producing the same |
US5790298A (en) * | 1994-05-03 | 1998-08-04 | Gentex Corporation | Method of forming optically transparent seal and seal formed by said method |
JPH0811631A (en) | 1994-06-29 | 1996-01-16 | Murakami Kaimeidou:Kk | Mirror for vehicle |
DE29623901U1 (en) | 1995-03-20 | 2000-07-06 | Toto Ltd | Substrate with a superhydrophilic photocatalytic surface |
FR2738813B1 (en) * | 1995-09-15 | 1997-10-17 | Saint Gobain Vitrage | SUBSTRATE WITH PHOTO-CATALYTIC COATING |
EP0850203B2 (en) * | 1995-09-15 | 2012-01-04 | Rhodia Chimie | Titanium dioxide-based photocatalytic coating substrate, and titanium dioxide-based organic dispersions |
JP2901550B2 (en) | 1996-07-26 | 1999-06-07 | 株式会社村上開明堂 | Anti-fog element |
DE19736925A1 (en) | 1996-08-26 | 1998-03-05 | Central Glass Co Ltd | Hydrophilic film and method for producing the same on a substrate |
JP3598752B2 (en) * | 1996-10-04 | 2004-12-08 | セイコーエプソン株式会社 | Projection display device |
US6166848A (en) * | 1997-04-02 | 2000-12-26 | Gentex Corporation | Electrochromic rearview mirror incorporating a third surface metal reflector and a display/signal light |
JP3781888B2 (en) | 1998-02-13 | 2006-05-31 | 日産自動車株式会社 | Hydrophilic substrate and method for producing the same |
US6171702B1 (en) * | 1998-07-17 | 2001-01-09 | Xerox Corporation | Coated substrates |
JP2000155344A (en) | 1998-11-20 | 2000-06-06 | Murakami Corp | Electrochromic element |
-
1999
- 1999-11-05 US US09/435,266 patent/US6193378B1/en not_active Expired - Lifetime
-
2000
- 2000-06-23 JP JP2001507140A patent/JP3746004B2/en not_active Expired - Fee Related
- 2000-06-23 MX MXPA01012298A patent/MXPA01012298A/en active IP Right Grant
- 2000-06-23 CA CA002378056A patent/CA2378056A1/en not_active Abandoned
- 2000-06-23 AU AU60547/00A patent/AU6054700A/en not_active Abandoned
- 2000-06-23 KR KR1020017016378A patent/KR100667417B1/en not_active IP Right Cessation
- 2000-06-23 EP EP00946851A patent/EP1206726A4/en not_active Ceased
- 2000-06-23 WO PCT/US2000/017402 patent/WO2001001192A1/en not_active Application Discontinuation
-
2001
- 2001-01-19 US US09/765,986 patent/US6447123B2/en not_active Expired - Lifetime
-
2002
- 2002-09-09 US US10/238,015 patent/US6789906B2/en not_active Expired - Fee Related
-
2005
- 2005-08-16 JP JP2005235842A patent/JP4299818B2/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4375318A (en) * | 1979-08-30 | 1983-03-01 | American Cyanamid Company | Electrochromic cells with improved electrolyte system |
US4293901A (en) * | 1979-12-17 | 1981-10-06 | Esquire, Inc. | Reflector system having sharp light cutoff characteristics |
US5216536A (en) * | 1991-11-26 | 1993-06-01 | Donnelly Corporation | Encapsulated electrochromic device and method for making same |
US5688855A (en) * | 1995-05-01 | 1997-11-18 | S.K.Y. Polymers, Inc. | Thin film hydrophilic coatings |
Non-Patent Citations (1)
Title |
---|
See also references of EP1206726A4 * |
Cited By (83)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9481306B2 (en) | 1998-04-08 | 2016-11-01 | Donnelly Corporation | Automotive communication system |
US8884788B2 (en) | 1998-04-08 | 2014-11-11 | Donnelly Corporation | Automotive communication system |
US9221399B2 (en) | 1998-04-08 | 2015-12-29 | Magna Mirrors Of America, Inc. | Automotive communication system |
US9019091B2 (en) | 1999-11-24 | 2015-04-28 | Donnelly Corporation | Interior rearview mirror system |
US10144355B2 (en) | 1999-11-24 | 2018-12-04 | Donnelly Corporation | Interior rearview mirror system for vehicle |
US9278654B2 (en) | 1999-11-24 | 2016-03-08 | Donnelly Corporation | Interior rearview mirror system for vehicle |
US9376061B2 (en) | 1999-11-24 | 2016-06-28 | Donnelly Corporation | Accessory system of a vehicle |
US10053013B2 (en) | 2000-03-02 | 2018-08-21 | Magna Electronics Inc. | Vision system for vehicle |
US9315151B2 (en) | 2000-03-02 | 2016-04-19 | Magna Electronics Inc. | Driver assist system for vehicle |
US10239457B2 (en) | 2000-03-02 | 2019-03-26 | Magna Electronics Inc. | Vehicular vision system |
US9019090B2 (en) | 2000-03-02 | 2015-04-28 | Magna Electronics Inc. | Vision system for vehicle |
US9809168B2 (en) | 2000-03-02 | 2017-11-07 | Magna Electronics Inc. | Driver assist system for vehicle |
US9809171B2 (en) | 2000-03-02 | 2017-11-07 | Magna Electronics Inc. | Vision system for vehicle |
US10179545B2 (en) | 2000-03-02 | 2019-01-15 | Magna Electronics Inc. | Park-aid system for vehicle |
US9783114B2 (en) | 2000-03-02 | 2017-10-10 | Donnelly Corporation | Vehicular video mirror system |
US9014966B2 (en) | 2000-03-02 | 2015-04-21 | Magna Electronics Inc. | Driver assist system for vehicle |
US8908039B2 (en) | 2000-03-02 | 2014-12-09 | Donnelly Corporation | Vehicular video mirror system |
US10131280B2 (en) | 2000-03-02 | 2018-11-20 | Donnelly Corporation | Vehicular video mirror system |
US10272839B2 (en) | 2001-01-23 | 2019-04-30 | Magna Electronics Inc. | Rear seat occupant monitoring system for vehicle |
US9352623B2 (en) | 2001-01-23 | 2016-05-31 | Magna Electronics Inc. | Trailer hitching aid system for vehicle |
US9694749B2 (en) | 2001-01-23 | 2017-07-04 | Magna Electronics Inc. | Trailer hitching aid system for vehicle |
US10363875B2 (en) | 2002-09-20 | 2019-07-30 | Donnelly Corportion | Vehicular exterior electrically variable reflectance mirror reflective element assembly |
US10029616B2 (en) | 2002-09-20 | 2018-07-24 | Donnelly Corporation | Rearview mirror assembly for vehicle |
US9878670B2 (en) | 2002-09-20 | 2018-01-30 | Donnelly Corporation | Variable reflectance mirror reflective element for exterior mirror assembly |
US10538202B2 (en) | 2002-09-20 | 2020-01-21 | Donnelly Corporation | Method of manufacturing variable reflectance mirror reflective element for exterior mirror assembly |
US9545883B2 (en) | 2002-09-20 | 2017-01-17 | Donnelly Corporation | Exterior rearview mirror assembly |
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 |
US10661716B2 (en) | 2002-09-20 | 2020-05-26 | Donnelly Corporation | Vehicular exterior electrically variable reflectance mirror reflective element assembly |
US9341914B2 (en) | 2002-09-20 | 2016-05-17 | Donnelly Corporation | Variable reflectance mirror reflective element for exterior mirror assembly |
US8559092B2 (en) | 2002-09-30 | 2013-10-15 | Gentex Corporation | Vehicular rearview mirror elements and assemblies incorporating these elements |
US8169684B2 (en) | 2002-09-30 | 2012-05-01 | Gentex Corporation | Vehicular rearview mirror elements and assemblies incorporating these elements |
US8614847B2 (en) | 2002-09-30 | 2013-12-24 | Gentex Corporation | Vehicular rearview mirror elements and assemblies incorporating these elements |
US8730551B2 (en) | 2002-09-30 | 2014-05-20 | Gentex Corporation | Vehicular rearview mirror elements and assemblies incorporating these elements |
US7719750B2 (en) | 2002-09-30 | 2010-05-18 | Gentex Corporation | Vehicular rearview mirror elements and assemblies incorporating these elements |
US8614846B2 (en) | 2002-09-30 | 2013-12-24 | Gentex Corporation | Vehicular rearview mirror elements and assemblies incorporating these elements |
US8614845B2 (en) | 2002-09-30 | 2013-12-24 | Gentex Corporation | Vehicular rearview mirror elements and assemblies incorporating these elements |
US7602542B2 (en) | 2002-09-30 | 2009-10-13 | Gentex Corporation | Vehicular rearview mirror elements and assemblies incorporating these elements |
US8638488B2 (en) | 2002-09-30 | 2014-01-28 | Gentex Corporation | Vehicular rearview mirror elements and assemblies incorporating these elements |
US9134585B2 (en) | 2002-09-30 | 2015-09-15 | Gentex Corporation | Automotive rearview mirror with capacitive switches |
EP1678530A4 (en) * | 2003-10-30 | 2008-02-20 | Gentex Corp | Electrochromic device having a self-cleaning hydrophilic coating with an acid resistant under layer |
EP1678530A2 (en) * | 2003-10-30 | 2006-07-12 | Gentex Corporation | Electrochromic device having a self-cleaning hydrophilic coating with an acid resistant under layer |
WO2005082015A2 (en) | 2004-02-27 | 2005-09-09 | Gentex Corporation | Vehicular rearview mirror elements and assemblies incorporating these elements |
EP1766469A4 (en) * | 2004-02-27 | 2009-05-20 | Gentex Corp | Vehicular rearview mirror elements and assemblies incorporating these elements |
EP1766469A2 (en) * | 2004-02-27 | 2007-03-28 | Gentex Corporation | Vehicular rearview mirror elements and assemblies incorporating these elements |
US8004741B2 (en) | 2004-02-27 | 2011-08-23 | Gentex Corporation | Vehicular rearview mirror elements and assemblies incorporating these elements |
US7978393B2 (en) | 2004-02-27 | 2011-07-12 | Gentex Corporation | Vehicular rearview mirror elements and assemblies incorporating these elements |
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 |
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 |
US11285879B2 (en) | 2005-09-14 | 2022-03-29 | Magna Mirrors Of America, Inc. | Vehicular exterior rearview mirror assembly with blind spot indicator element |
US9045091B2 (en) | 2005-09-14 | 2015-06-02 | Donnelly Corporation | Mirror reflective element sub-assembly for exterior rearview mirror of a vehicle |
US10308186B2 (en) | 2005-09-14 | 2019-06-04 | Magna Mirrors Of America, Inc. | Vehicular exterior rearview mirror assembly with blind spot indicator |
US10829053B2 (en) | 2005-09-14 | 2020-11-10 | Magna Mirrors Of America, Inc. | Vehicular exterior rearview mirror assembly with blind spot indicator |
US8833987B2 (en) | 2005-09-14 | 2014-09-16 | Donnelly Corporation | Mirror reflective element sub-assembly for exterior rearview mirror of a vehicle |
US10150417B2 (en) | 2005-09-14 | 2018-12-11 | Magna Mirrors Of America, Inc. | Mirror reflective element sub-assembly for exterior rearview mirror of a vehicle |
US11072288B2 (en) | 2005-09-14 | 2021-07-27 | Magna Mirrors Of America, Inc. | Vehicular exterior rearview mirror assembly with blind spot indicator element |
US11124121B2 (en) | 2005-11-01 | 2021-09-21 | Magna Electronics Inc. | Vehicular vision system |
US10175477B2 (en) | 2008-03-31 | 2019-01-08 | Magna Mirrors Of America, Inc. | Display system for vehicle |
US8922867B2 (en) | 2009-04-23 | 2014-12-30 | Magna Mirrors Of America, Inc. | Frameless interior rearview mirror assembly |
US9481303B2 (en) | 2009-04-23 | 2016-11-01 | Magna Mirrors Of America, Inc. | Method of making a mirror substrate for an interior rearview mirror assembly for a vehicle |
US10189407B2 (en) | 2009-04-23 | 2019-01-29 | Magna Mirrors Of America, Inc. | Method of making a mirror substrate for an interior rearview mirror assembly for a vehicle |
US11738686B2 (en) | 2009-04-23 | 2023-08-29 | Magna Mirrors Of America, Inc. | Frameless interior rearview mirror assembly |
US10124732B2 (en) | 2009-04-23 | 2018-11-13 | Magna Mirrors Of America, Inc. | Frameless interior rearview mirror assembly |
US11577648B2 (en) | 2009-04-23 | 2023-02-14 | Magna Mirrors Of America, Inc. | Frameless interior rearview mirror assembly |
US11472340B2 (en) | 2009-04-23 | 2022-10-18 | Magna Mirrors Of America, Inc. | Method of making a mirror substrate for a vehicular rearview mirror assembly |
US11325533B2 (en) | 2009-04-23 | 2022-05-10 | Magna Mirrors Of America, Inc. | Frameless interior rearview mirror assembly |
US9637055B2 (en) | 2009-04-23 | 2017-05-02 | Magna Mirrors Of America, Inc. | Frameless interior rearview mirror assembly |
US8976439B2 (en) | 2009-04-23 | 2015-03-10 | Magna Mirrors Of America, Inc. | Mirror assembly for vehicle |
US10632921B2 (en) | 2009-04-23 | 2020-04-28 | Magna Mirrors Of America, Inc. | Interior rearview mirror assembly for a vehicle |
US10647258B2 (en) | 2009-04-23 | 2020-05-12 | Magna Mirrors Of America, Inc. | Frameless interior rearview mirror assembly |
US9346403B2 (en) | 2009-10-07 | 2016-05-24 | Magna Mirrors Of America, Inc. | Rearview mirror assembly |
US10906467B2 (en) | 2009-10-07 | 2021-02-02 | Magna Mirrors Of America, Inc. | Exterior rearview mirror assembly |
US11498486B2 (en) | 2009-10-07 | 2022-11-15 | Magna Mirrors Of America, Inc. | Vehicular exterior rearview mirror assembly |
US11697373B2 (en) | 2009-10-07 | 2023-07-11 | Magna Mirrors Of America, Inc. | Vehicular exterior rearview mirror assembly |
US10261648B2 (en) | 2009-10-07 | 2019-04-16 | Magna Mirrors Of America, Inc. | Exterior rearview mirror assembly |
US10191348B2 (en) | 2010-07-08 | 2019-01-29 | Gentex Corporation | Electro-optic element |
US9056584B2 (en) | 2010-07-08 | 2015-06-16 | Gentex Corporation | Rearview assembly for a vehicle |
US9701248B2 (en) | 2010-07-08 | 2017-07-11 | Gentex Corporation | Rearview assembly for a vehicle |
US10345672B2 (en) | 2010-07-08 | 2019-07-09 | Gentex Corporation | Electro-optic element |
US9316347B2 (en) | 2012-01-24 | 2016-04-19 | Gentex Corporation | Rearview assembly with interchangeable rearward viewing device |
US10589684B2 (en) | 2013-04-22 | 2020-03-17 | Magna Mirrors Of America, Inc. | Rearview mirror assembly for vehicle |
US11479178B2 (en) | 2013-04-22 | 2022-10-25 | Magna Mirrors Of America, Inc. | Interior rearview mirror assembly for vehicle |
US10112538B2 (en) | 2013-04-22 | 2018-10-30 | Magna Mirrors Of America, Inc. | Rearview mirror assembly for vehicle |
Also Published As
Publication number | Publication date |
---|---|
US6193378B1 (en) | 2001-02-27 |
US20010021066A1 (en) | 2001-09-13 |
EP1206726A4 (en) | 2003-07-23 |
MXPA01012298A (en) | 2002-08-12 |
JP2006016001A (en) | 2006-01-19 |
EP1206726A1 (en) | 2002-05-22 |
KR20020019099A (en) | 2002-03-09 |
US6447123B2 (en) | 2002-09-10 |
US20030048538A1 (en) | 2003-03-13 |
JP3746004B2 (en) | 2006-02-15 |
AU6054700A (en) | 2001-01-31 |
US6789906B2 (en) | 2004-09-14 |
JP2003503264A (en) | 2003-01-28 |
CA2378056A1 (en) | 2001-01-04 |
KR100667417B1 (en) | 2007-01-10 |
JP4299818B2 (en) | 2009-07-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6816297B1 (en) | Electrochromic mirror having a self-cleaning hydrophilic coating | |
US6447123B2 (en) | Electrochromic device having a self-cleaning hydrophilic coating | |
US20050286132A1 (en) | Electrochromic device having a self-cleaning hydrophilic coating with a controlled surface morphology | |
US20080123190A1 (en) | Electro-optic device having a self-cleaning hydrophilic coating | |
CN101322069B (en) | Transparent electrode for an electrochromic switchable cell | |
US8264761B2 (en) | Vehicle rearview mirror with spotter mirror | |
US8643931B2 (en) | Vehicle rearview mirror with spotter mirror | |
CA2611371C (en) | Transparent electrode for an electrochromic switchable cell | |
Lynam | Smart windows for automobiles | |
EP0728618A2 (en) | Dimmable rearview mirror for motor vehicles | |
JPH10114007A (en) | Glazing with variable optical and/or energetic properties | |
KR20090034948A (en) | Electrochemical and/or electrocontrolable device, of the glazing type, having variable optical and/or energetic properties | |
JP2002520654A (en) | Glazing with electrically controllable optical / energy properties | |
EP1678530B1 (en) | Electrochromic device having a self-cleaning hydrophilic coating with an acid resistant under layer | |
JP2004309628A (en) | Reflector | |
EP1738958A2 (en) | An electro-optic device having a self-cleaning hydrophilic coating |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: PA/a/2001/012298 Country of ref document: MX |
|
ENP | Entry into the national phase |
Ref document number: 2001 507140 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2378056 Country of ref document: CA Ref document number: 1020017016378 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2000946851 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWP | Wipo information: published in national office |
Ref document number: 2000946851 Country of ref document: EP |
|
WWR | Wipo information: refused in national office |
Ref document number: 2000946851 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 2000946851 Country of ref document: EP |