Patent Grant
10427606
The present invention relates to polymer-based film laminates and, more particularly, to automotive rearview mirrors incorporating laminates comprising polymer-based film structures having an optically anisotropic layer.
Mirror assemblies have proven to be a convenient location for providing drivers with useful information. For example, a video display disposed behind a mirror, but visible through a portion of the mirror, may supply the driver with a video image of the scene to the rear of the vehicle where the driver's view may otherwise be obstructed. Similarly, an information display may offer the driver such vehicle-telemetry information as vehicle speed, engine status, oil level and temperature, for example, or any other information of interest. Integration of backup or other displays behind the automotive rearview mirror is generally preferred over placing them adjacent to the mirror, thereby increasing the area of the overall mirror assembly and impairing the driver's view through the windshield.
Various types of displays incorporated within the rearview automotive mirror are known in the art, such as alphanumeric displays, graphical displays, video displays, and combinations thereof. These displays are discussed, for example, in U.S. Pat. No. 7,221,363, and in US Patent Publication No. 2008/0068520, each of which is incorporated herein in its entirety by reference. Displays that have been, or might be, used in automotive applications employ various principles such as vacuum fluorescence (VF), electromechanics (EM), light emitting or organic light emitting diodes (LED or OLED), plasma display panels (PDP), microelectromechanical systems (MEMS), electroluminescence (EL), projection (the projection systems include but are not limited to DLP and LCOS), or liquid crystal technology (used in liquid crystal displays, or LCDs), to name just a few. High-resolution LCDs capable of delivering color images, for example, may be mass-produced reliably and at low cost. LCDs are also noteworthy in that the liquid crystal medium changes its polarizing properties under the influence of the applied electric field and the light emanating from an LCD is polarized.
A particular challenge presented by display technology in an automotive context is that of providing the driver with sufficient luminance to see the display clearly, especially under daunting conditions of ambient light, while, at the same time, providing a clear and undistorted reflected view of the rear and peripheral scene to the driver. Since automotive reflectors serve a crucial safety function in identifying objects otherwise outside of the driver's field of view, they must critically preserve image quality.
Embodiments of the invention provide an image-forming optical reflector comprising a base element (such as an electrochromic element or a prism element) that reflects ambient light incident upon it, a light source, and a laminate that includes an anisotropic film disposed between the base element and the light source. In one embodiment, the image-forming reflector may include a variable reflectance mirror system for use in a rearview mirror assembly having a light source transmitting light of a first polarization through the mirror system. The mirror system may be a multi-zone mirror system. The anisotropic film may extend across the full field-of-view of the mirror system or, alternatively, it may extend substantially over only a transflective zone of the multi-zone system through which the light source transmits light towards a viewer. The film receives the light from the light source, transmitting a portion of this light that has a first polarization and reflecting a portion of this light that has a second polarization that is opposite to the first polarization. The mirror is substantially devoid of any extended distortion. In one embodiment, the mirror system is characterized by surface values SW and LW, derived as discussed below, which do not exceed 3, preferably do not exceed 2 and most preferably do not exceed 1. The anisotropic film may be laminated between a substrate and a superstrate, which may be releasably adhered to the film. The light source may be a part of the laminate and may act as the superstrate. Alternatively or in addition, the base element may be a part of the laminate and may act as the substrate. In a specific embodiment, the laminate may be a stand-alone component of the reflector. The light source may comprise a display subassembly, for example an LCD subassembly. In a specific embodiment, at least one of a reflectance-enhancing and an opacifying layer may be additionally employed adjacent to a surface of the substrate and superstrate. The opacifying layer may substantially cover a portion of the surface that is located outside the transflective portion of the mirror structure.
Additional embodiments of the invention provide an optical element for optimizing transmission of light through an image-forming optical reflector. In a specific embodiment, the optical element of the invention placed within the mirror system of the invention increases a contrast of light transmitted from a light source through the mirror system to a viewer. The optical element may comprise an optical substrate, having a surface, and a light-transmitting layered structure adhered to the surface, where the layered structure includes an anisotropic layer that transmits light of a first polarization and reflects light of a second polarization that is opposite to the first polarization. The anisotropic layer may be birefringent. Layers of the layered structure, including the anisotropic layer, may each have associated glass transition temperatures, and the layered structure may be characterized by a range of glass transition temperatures. In one embodiment, the layered structure is characterized by SW and LW that do not exceed 3 after the layered structure has been heated to soften at least a portion of the plastic film, which generally occurs at a temperature approaching or exceeding at least a lower glass-transition temperature from the range of glass transition temperatures associated with the layered structure. In another embodiment, after having been heated to such softening temperature under uniform (and, preferably, substantially omnidirectional) pressure, the layered structure is substantially devoid of any extended distortion. In one embodiment, the optical element may be a laminate integrating at least a substrate and the anisotropic layer. In another embodiment, the optical element may additionally comprise a light-transmitting optical superstrate disposed over the layered structure where the optical superstrate may or may not be releasably coupled to the layered structure. The optical element is substantially devoid of any extended distortion and may be characterized by values SW and LW that do not exceed 3, preferably do not exceed 2 and most preferably do not exceed 1. In a specific embodiment, the optical reflector may be an image-forming reflector, for example a rearview automotive mirror.
In accordance with another embodiment of the invention, a method is provided for fabricating a laminate containing an APBF for use in a rearview mirror assembly. The method includes disposing a film structure characterized by a predetermined water content and having a layer with anisotropic optical properties on a substrate to form a composite. The method further includes applying heat and pressure at controlled humidity levels and, optionally, vacuum to the composite under conditions causing formation of a laminate that comprises a part of the image-forming and image-preserving reflector characterized by SW and LW values that are less than 3, preferably less than 2, and most preferably less than 1. According to one embodiment of the invention it is preferred that the water content of the APBF prior to lamination be less than about 0.6 weight-%, more preferably less than about 0.4 weight-%, even more preferably less than 0.2 weight-%, and most preferably less than about 0.1 weight-%. The temperature selected to laminate the composite may be within a range from about 50° C. to about 160° C., preferably between about 80° C. to about 150° C., and most preferably between about 90° C. to about 110° C. The pressure chosen for lamination is preferably substantially omnidirectional and may be between about 25 psi to about 2,500 psi, preferably from about 50 psi to about 500 psi, and most preferably from about 100 psi to about 400 psi. The film structure may be optionally stretched during the lamination process to assure adequate flatness of the film. In one embodiment, the fabricated laminate may be additionally annealed to enhance the strength of the lamination bond. In one embodiment, the layer with anisotropic properties transmits light having a first polarization and reflects light having a second polarization that is opposite to the first polarization, and the laminate is characterized by SW and LW values less than 3, preferably less than 2, and most preferably less than 1. In another embodiment, the laminate is substantially devoid of any extended distortion and the optical reflector comprising such laminate forms an image satisfying automotive industry standards.
In accordance with another embodiment, a switchable mirror system (SMS) for use in a vehicular rearview assembly equipped with a light source transmitting light from within the rearview assembly through said SMS to a field-of-view (FOV) outside the assembly is provided. The SMS includes at least two electro-optic (EO) cells defined by at least three sequentially disposed spaced-apart glass substrates, a first EO-cell corresponding to an outside portion of the rearview assembly and a second EO-cell disposed between the first EO-cell and the light source. The first EO-cell is adapted to be a switchable linear absorptive polarizer that attenuates light reflected from the second EO-cell, and does not substantially attenuate light transmitted from the light source through the second EO-cell. Further, the SMS has a reflectance value that is gradually variable in response to changes in voltages applied to the first EO-cell, and as measured in said FOV in ambient light. In addition, the thicknesses of said at least three substrates are chosen to provide for a net weight of said SMS per unit area of less than 2.0 grams per cm2.
In accordance with a further embodiment, a switchable mirror system (SMS) for use in a vehicular rearview assembly equipped with a light source transmitting light from within the rearview assembly through said SMS to a field-of-view (FOV) outside the assembly is provided. The SMS includes: a first electro-optic (EO) cell defined by two sequentially disposed spaced-apart substrates that corresponds to an outside portion of the rearview assembly; and a linear reflective polarizer disposed between the light source and the first EO-cell. The first EO-cell is adapted to be a switchable linear absorptive polarizer that attenuates light reflected from the reflective polarizer and does not substantially attenuate light transmitted from the light source through the first EO-cell. In addition, the SMS has a reflectance value that is gradually variable in response to changes in voltages applied to the first EO cell, and as measured in said FOV in ambient light.
The foregoing features of the invention will be more readily understood by reference to the following detailed description, taken with reference to the accompanying, drawn not to scale, drawings where like features and elements are denoted by like numbers and labels, and in which:
As used in this description and the accompanying claims, the following terms shall have the meanings indicated, unless the context requires otherwise:
A “laminate” refers generally to a compound material fabricated through the union of two or more components, while a term “lamination” refers to a process of fabricating such a material. Within the meaning of the term “laminate,” the individual components may share a material composition, or not, and may undergo distinct forms of processing such as directional stretching, embossing, or coating. Examples of laminates using different materials include the application of a plastic film to a supporting material such as glass, or sealing a plastic layer between two supporting layers, where the supporting layers may include glass, plastic, or any other suitable material.
An “image-forming” or “image-preserving” reflector is a reflector forming an essentially undistorted image in specularly reflected light. In imaging, optical distortion is understood as a deviation from rectilinear projection. For example, an undistorted image of a straight line formed in a flat reflector is a straight line. For the purposes of this invention, “image-forming” and “image-preserving” include projections that may incorporate pre-determined distortions introduced by design into an otherwise undistorted image. For example, an image-forming reflector designed to be non-flat (such as a convex or an aspheric reflector) produces substantially no deviations from the curvilinear image resulting from the design curvature of the reflector.
“Transflective” refers to an optical configuration that reflects at least a portion of light incident from at least one side, and transmits at least a portion of light incident from at least one side.
An “isolated defect” in an optical element is defined as a deformation feature that may be surrounded with a complete annulus within which there is no excursion from the mean figure of the surface perceptible to an ordinary user. Such highly localized defects, moreover, are characterized by high spatial frequency when described in a Fourier domain. For example, a particle of dust trapped within a laminate might form an isolated defect, in which case this deformation is limited to the region encompassing and surrounding a dust particle. Another example of an isolated defect in a laminate may be provided by a lamination interface singularity (i.e., a singularity at an interface between the laminated components) such as a scratch. Isolated defects are sometimes defined by the rate of change in the local slope of a surface measured with a deflectometry-based technique developed by an automotive consortium and discussed by Fernholtz et al. at www.speautomotive.com/SPEA_CD/SPEA2007/pdf/d/enabling_part1_paper4_femholz_ford.pdf.
By way of distinction, however, the terms “extended defect” and “extended distortion” refer to a deformation of the surface of an optical element, such that there exists no complete annulus, surrounding the deformation, which annulus contains imperceptible excursion from the mean figure of the surface. An extended defect in an optical element may include such features as singular elongated scratches, creases and the like as well as groups of similar defects. Extended distortion in a reflecting surface may manifest itself by and be recognized through a measured rate of change of curvature of the surface, or, equivalently, a local change in optical power of the reflecting surface.
An optical element is said to be “substantially devoid of extended distortions” if the element, in its intended use, is substantially free of extended distortions as visually perceived by an ordinary observer. For example, an image-preserving reflector including a laminate, which has extended distortions that reduce the quality of the image formed by the reflector and that can be visually perceived by an ordinary viewer, is not “substantially devoid of extended distortion.” A stippled surface referred to as “orange-peel” provides an example of surface having extended distortion. Visual requirements for automotive image-forming reflectors, including rearview mirror assemblies and those with back-up displays, are based on the intended use where images of relatively distant objects, viewed in reflection, are moving across the field of view of the reflectors in a generally horizontal direction when the vehicles is in motion. Therefore, a reflector producing an acceptable image for a closer and stationary object (such as a decorative room mirror, for example), may not yield an acceptable image for an automotive application. Verification of whether various laminate-containing automotive image-forming reflector assemblies form images that satisfy the visual requirements may be carried out with different tests such as, for example, a test for visual distortion evaluation of a flat mirror as described in the DaimlerChrysler Corporation standard no. MS-3612 (referred to hereinafter as visual evaluation test). If, as required by this standard, an ordinary observer located at about 36 inches away from the reflector, does not see blurring or fuzziness in the image of a 1 inch grid, consisting of intersecting straight horizontal and vertical lines and placed at about 15 ft in front of the planar reflector, such reflector will be perceived as substantially devoid of extended distortions in its intended use. When performing a visual evaluation test, the observer will often move his head relative to the mirror to assure that a slightly discernible distortion of the image of the grid does not become objectionable for the purposes of the mirror use. Such dynamic evaluation is not required by the MS-3612 standard. It is understood, however, that other standards may be applied in determining the fitness of the image-preserving automotive reflector for its intended purpose.
A “first polarization” and a “second polarization opposite the first polarization” generally refer to two different polarizations. In a particular case, the first and the second polarizations may be orthogonal polarizations (such as two linear polarizations represented by mutually perpendicular vectors, or left and right circular or elliptical polarizations).
A “light source” generally refers to a device serving as a source of illumination inclusive of optical elements that may gate or shape the illumination. Thus, for example, an LCD or any other display illuminated with the light from a light emitter is included within the meaning of a “light source”. A light source may be used, e.g., for display of information, video images, or for illumination of an object.
A “stand-alone” element of a mirror assembly is an element that, upon being fabricated, does not include any elements of the mirror assembly that serve purposes other than the purpose of the stand-alone element. No component of a stand-alone laminate of the mirror assembly may be a structural element of any other subset of the mirror assembly. A stand-alone laminate, when fabricated, can be inserted into the mirror assembly and removed from it without disturbing the performance of the remaining elements of the assembly. In comparison, a laminate may integrate another element of the mirror assembly: e.g., a substrate for a mirror component may be simultaneously utilized as a substrate for the laminate, thus becoming one of the compound material components of the laminate.
In reference to an optical component, being “opaque” implies having transmittance low enough to substantially conceal mirror assembly components located behind the optical component. “Opacification”, in turn, refers to an act or process of rendering an optical component substantially opaque.
A “depolarizer” is an optical structure that effectively changes a state of polarization of polarized light transmitted or reflected by the depolarizer into a different polarization state such that differences between the fundamental polarization components of incident polarized light are reduced after passing through or reflecting from said polarizer. One example of a depolarizer for present purposes would be an ideal depolarizer that scrambles the polarization of light and outputs randomly polarized light whatever the input. A practical depolarizer of this type typically produces pseudo-random output polarization. For example, an element that randomizes the phase difference between the s and p components of incident linearly polarized light passing through such element provides one example of a depolarizer. Another example of a depolarizer for present purposes would be a phase retarder converting linearly polarized light into elliptically polarized light such as, e.g., light polarized circularly, or into randomly polarized light. The addition of a depolarizer to the mirror assembly may result in a more uniform distribution of intensity with a tilt angle in both reflectance and transmittance when a viewer wears polarizing sunglasses. In addition, the presence of such depolarizer minimizes certain artifacts that appear in reflected and transmitted images.
The following disclosure describes embodiments of the invention with reference to the corresponding drawings, in which like numbers represent the same or similar elements wherever possible. In the drawings, the depicted structural elements are not to scale and certain components are enlarged relative to the other components for purposes of emphasis and understanding. References throughout this specification to “one embodiment,” “an embodiment,” or similar language mean that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases “in one embodiment,” “in an embodiment,” and similar language throughout this specification may, but do not necessarily, all refer to the same embodiment.
The described features, structures, or characteristics of the invention may be combined in any suitable manner in one or more embodiments. For example, to simplify a particular drawing of an electro-optical device of the invention not all thin-film coatings, electrical interconnections, elements of structural support (such as housing, for example), or auxiliary devices (such as sensors, for example) may be shown in a single drawing. It is understood, however, that such coatings, interconnections, structural support elements, or auxiliary devices are implied as they may be required for proper operation of the particular embodiment. In the following description, numerous specific details are recited to provide a thorough understanding of embodiments of the invention. One skilled in the relevant art will recognize, however, that the invention may be practiced without one or more of the specific details, or with other methods, components, or materials.
Types of rearview mirror assemblies that contain a display and to which embodiments of the present invention may advantageously be applied include, without limitation, mirrors comprising transflective elements (i.e. elements that are partially transmissive and partially reflective), reflective elements including prismatic reflective elements, and electrochromic mirrors. Transflective optics may be, without limitation, partially transmissive, multichroic, polarization-sensitive, or directionally transmissive. Various rearview mirror structures and related methods of fabrication have been addressed, for example, in U.S. Pat. Nos. 5,818,625, 6,166,848, 6,356,376, 6,700,692, 7,009,751, 7,042,616, 7,221,363, 7,502,156 and U.S. Patent Publication No. 2008/0068520, 2008/0030836, and 2008/0302657, and U.S. patent application Ser. No. 12/570,585 filed on Sep. 30, 2009 and Ser. No. 12/367,143, filed on Feb. 6, 2009, each of which is incorporated herein in its entirety by reference in its entirety. These patent documents are collectively referred to herein as “Our Prior Applications.” Displays and transflective optics may be incorporated in various vehicle locations, not only in rearview mirrors (interior or exterior to the vehicle) and sideview mirrors, such as sun visors, instrument panels, dashboards, overhead consoles and the like. The rearview mirror assemblies may comprise surfaces of various geometries such as, by way of non-limiting example, planar, cylindrical, convex, aspheric, prismatic, other complex surfaces, or combinations thereof. As schematically illustrated in
Embodiments of the invention may be incorporated in a rearview mirror assembly that may include a glare light sensor and an ambient light sensor, which are described in commonly assigned U.S. Pat. Nos. 6,359,274 and 6,402,328. The disclosure of each of these patents is incorporated herein by reference in its entirety. The electrical output signal from either or both of these sensors may be used as inputs to a controller on a circuit board of the assembly that controls the intensity of display backlighting. The details of various control circuits for use herewith are described in commonly assigned U.S. Pat. Nos. 5,956,012; 6,084,700; 6,222,177; 6,224,716; 6,247,819; 6,249,369; 6,392,783; and 6,402,328, the disclosures of which are incorporated in their entireties herein by reference. These systems may be integrated, at least in part, in a common control with information displays and/or may share components with the information displays. In addition, the status of these systems and/or the devices controlled thereby may be displayed on the associated information displays.
As schematically shown in examples of
Generally, a mirror assembly incorporating embodiments of the invention may include, within the housing of the assembly, an EC-mirror element or a prismatic tilt mirror element, a light source such as that including an information display behind the mirror element, and various auxiliary components such as a voice activated system, a microphone, a compass system, a digital sound processing system, a telemetry system, a sensor such as a moisture sensor or a light sensor, for example, a loran system, a GPS, a vehicle vision system, and camera, a climate control system, a turn signal, a security system, an adaptive cruise control system, garage door openers, BlueTooth modules and map lights. Detailed description of embodiments of mirror elements and system configured within automotive rearview mirror assemblies is provided in Our Prior Applications.
In further reference to
For example, some automotive industry standards require only about 40 percent reflectance for inside rearview mirror assemblies and about 35 percent reflectance for outside rearview mirror assemblies. With the use of such mirror assemblies, the contrast of the illumination from a display, as perceived by the driver through a mirror system against a background of ambient light reflected by the mirror system, remains quite low, particularly when the ambient light is plentiful such as on a bright sunny day. For example, a commonly-assigned U.S. patent application Ser. No. 12/370,909 filed Feb. 13, 2009 and now published as U.S. 2009/0207513, which is further referred to herein as “Multi-Zone Mirror Application” and the entire disclosure of which is incorporated herein by reference, provides a discussion of the display contrast in a multi-zone mirror system having both opaque and transflective areas. The contrast is defined as the ratio of the intensity of display-generated light reaching the viewer and the intensity of ambient light reflected by the mirror system. As shown in Table 1 below, for a mirror system having a transflective area with absorbance of about 10% and an assumed 4,000 cd/m2 raw display signal luminance and 1,000 cd/m2 ambient light luminance, the contrast of the display increases rapidly as the reflectance of the transflective area of the mirror system decreases. Embodiments of the present invention, used in rearview mirror assemblies including a display device, may provide for the display contrast that is greater than 1, preferably greater than 2, more preferably greater than 3, and most preferably greater than 4. The use of laminates comprising polymer-based films (such as an APBF) or other reflective polarizers in automotive rearview mirror assemblies may facilitate transmitting an optimized amount of light from the light source through the mirror assembly to the driver. For example, by aligning the polarization axis of the APBF with the polarization vector of generally linearly polarized light delivered from a typical LCD located behind the mirror system, the losses of light from the display upon passing through the APBF may be minimized. Consequently, the overall amount of light transmitted from the display through the mirror towards the driver tends to be increased. Teachings of such a concept employing an optically anisotropic polarizer (whether a conventional wire-grid or a laminated foil made of multiple layers of plastic film at least one of which is optically anisotropic, e.g. wherein some or all of the film layers have internal molecular orientation that induces a directional difference in refractive index) are presented in U.S. Pat. No. 7,502,156. For example, a wire-grid polarizer, oriented within the mirror assembly so as to transmit a substantial majority of the linearly polarized light generated by a TFT LCD display located behind the mirror assembly, would reflect up to about a half of unpolarized ambient light incident upon the front of the mirror assembly and, therefore, provide for high visual contrast of the display on the ambient background. Examples of use of reflective polarizers in mirror/display devices are discussed in WO 2005/050267, WO 2005/024500, and WO 2003/079318, each of which is incorporated herein by reference in its entirety.
Various APBFs so far have been employed in energy efficient displays such as computer displays. Non-limiting examples of APBFs are provided by a multilayered polymer film comprising a body of alternating layers of a crystalline-based polymer and another selected polymer, or by micro-structured film-based polarizers such as brightness enhancement films, or by dual brightness enhancement films (DBEF-E, and DBEF-Q, APF 25, APF 35, APF 50, for example), all by 3M, Inc. (see, e.g., WO 95/17303, U.S. Pat. No. 5,422,756), or by multilayered films containing alternating polymeric layers stretched in chosen directions. See Steve Jurichich, Summary of The TFT LCD Material Report (www.displaysearch.com/products/samples/execsummary-materials.pdf); see also 3M product description at http://solutions9.3 m.com/wps/portal/3M/en_US/Vikuiti1/BrandProducts/main/energyefficiency.
Fabrication of laminates comprising glass and polymer films has been previously directed to safety glazing (see, e.g., U.S. Pat. Nos. 3,471,356 and 4,277,299) and to windows that reject a portion of solar light (so-called heat mirrors, see, e.g., U.S. Pat. Nos. 6,797,396 and 7,215,473). The use of polarizing films for enhancement of reflectivity in a conventional viewing mirror was discussed, e.g., in U.S. Patent Application No. 2007/0041096 and U.S. Pat. No. 7,551,354. However, fabrication of laminates containing plastic films for employment in rearview automotive mirror assemblies has not been addressed and presents problems that significantly differ from those faced in the fabrication of the abovementioned conventional products. The differences stem from the performance requirements imposed upon image-forming properties of rearview automotive mirror assemblies by commonly accepted industry standards.
For example, a polymer film laminated between a glass substrate and a glass superstrate for use in safety glazing is generally not required to possess any special optical or mechanical properties other than meeting transmission standards in visible light (i.e., at wavelengths between approximately 380 nm and 750 nm). A typical safety-glazing laminate is used in transmission, and the index matching provided by such polymer film for the glass substrate and superstrate is known to facilitate visual concealment of imperfections present at glass surfaces. In contradistinction, in a case of a plastic-film-based laminate with intended use in a rearview mirror assembly, where the laminate includes glass lites and a functional anisotropic polymer-based film and operates both in transmission and reflection, the use of an additional index-matching layer may not necessarily conceal imperfections. On one hand, such index-matching layer added to the polymer film will affect optical properties of the overall mirror system (e.g., reflectance, transmittance, and image-preserving properties such as ability to form undistorted images satisfying stringent standards of automotive industry). On the other hand, while possibly concealing the structural defects of glass surfaces, the index-matching layer may not necessarily conceal the structural defects of the polymer film itself or defects of the lamination. Moreover, plastic film-based laminates used in safety glazing do not utilize structurally anisotropic and often multilayered films such as those employed in embodiments of the present invention but, instead, conventionally utilizes homogeneous films the material properties of which are uniform. Therefore, technical approaches suitable to safety glass manufacture are not applicable to solve the problems of automotive mirror design.
Methods of conventional lamination of glasses and polymer films and the resulting laminates used in conventional applications mentioned above are well known. For example, typical flaws of a safety-glazing laminate may involve occasional inclusions of contaminating material such as particulates with dimensions on the order of a few microns that are sporadically scattered across, and embedded in, the safety-glazing laminate and may be perceived by a naked eye as annoying visual defects of the laminate. See U.S. Pat. No. 5,631,089. These flaws are examples of isolated defects characterized by high spatial frequency that do not reduce the integrity and quality of the laminate for its intended use in safety glazing. As far as safety glazing applications are concerned, prior art does not consider low-spatial-frequency optical distortions, resulting from the lamination process, to be defects of the laminates. See, e.g., Laminated Glass Product Standards, at www.viracon.com/laminatedStandards.html. Similarly, plastic films contained within heat-mirror laminates may not perfectly conform to the curvatures of the underlying window glass and may form wrinkles, pleats and even cracks in the functional layer. Although structural defects of laminates used in heat-mirrors often lead to optical defects as discussed, e.g., in U.S. Pat. Nos. 7,215,473 and 6,797,396, each of which is incorporated herein in its entirety by reference or at www.cardinalcorp.com/data/tsb/lg/LG02_05-08.pdf, these laminate defects are also known to not reduce the quality of the heat-mirror laminates for their intended use.
In contradistinction, structural defects in laminates used in an automotive rearview mirror may significantly reduce the quality of such mirror for its intended use. In fact, reflective polarizers such as APBFs, used either as stand-alone components or in laminated combinations, have not been commercialized to-date in image-forming automotive reflectors such as rearview mirrors, where the application requires image-forming quality satisfying automotive standards. Moreover, prior art specifically acknowledges the drawbacks of APBF-containing conventional mirrors known to-date by teaching that such reflectors produce inhomogeneities of reflection (both in color and direction) that result in disturbed reflected images prohibiting the use of APBFs and APBF-containing combinations of elements (such as, e.g., laminates) in automotive applications. See, e.g., U.S. Pat. No. 7,551,354. The present application addresses these well-recognized problems and offers embodiments of APBF-based laminates and automotive rearview mirrors containing such laminates that satisfy existing automotive standards.
In various applications, a primary purpose of a mirror is to form a clear and undistorted image. When a mirror assembly of interest is used as a rearview automotive mirror, and the image of the environment surrounding the driver is distorted, the unwanted image aberrations may distract the driver from correctly evaluating the traffic situation. We have empirically found that (in contrast to known applications such as safety glazing applications, or heat mirrors, for example), a conventionally performed lamination, with or without a cover plate, of an APBF to a substrate in a rearview mirror assembly compromises the quality of the resulting mirror for its intended use. Such reduction in image quality arises from lamination defects that are characterized by low spatial frequency in a Fourier domain. These defects may be described, in some embodiments, as detachments of the APBF from the substrate, rather considerable in size (generally on the order or a millimeter or more in at least one dimension) and substantially distributed across the resulting laminate's field of view (FOV). Often these defects visually present themselves to an ordinary viewer as “stretch marks” in the laminated film. As a result of such sizeable, low spatial frequency blemishes within a rearview mirror, an image of the surrounding seen by the driver is at least distorted and may be significantly aberrated in the portions of the rearview mirror affected by the described shortcomings in the APBF lamination.
Arrows 118 and 120 indicate light incident on a proximal, as observed by the viewer 115, side 124 of the mirror structure 112 and that reflected from the mirror structure, respectively. The mirror structure 112 (or, similarly, any other optical quality image-forming reflector) that includes an APBF-laminate 100, appears to have an uneven surface characterized by non-uniform and irregular low-spatial frequency waviness and extended distortions 116. An image formed in reflection from such a mirror appears, in turn, to be optically distorted, and, in the automotive context, the mirror structure 112 would be deficient in providing the driver 115 with an image of the scene behind the vehicle. An example of a reflector creating optical distortions that are prohibitive for automotive purposes is shown in
Exemplary Embodiments of a Method of the Invention.
It was discovered that the ambient humidity at which the APBF is stored prior to the fabrication process and the humidity level maintained during the fabrication process may affect optical properties, structural stability, and durability of the embodiments of the resulting laminates. In particular, the elevated levels of humidity during the pre-processing storage generally led to increased haziness (and, therefore, to reduced transmittance and increased scatter of light) in the fabricated laminates after the durability testing. Therefore, optionally, an embodiment of the fabrication process of the invention includes a step of pre-lamination processing of the APBF (shown in a dashed line as step (A) in
Alternatively or in addition, to keep a pre-lamination moisture content of the film within the preferred limits resulting in reduced haze of the final laminate, the APBF may be appropriately treated prior to the lamination process. Such treatment may include drying the APBF film under vacuum and elevated temperatures (approximately between 25° C. and 40° C.) for at least 4 hours. It shall be appreciated that measurements of moisture content in a given APBF can be carried out using different techniques. For example, a sample of DBEF-Q of a known area (e.g., dimensioned to match the full size of the rearview mirror substrate) may be precisely weighed and then subjected to particular storing conditions such as 40° C. at 95% RH, 40° C. in vacuum, or control ambient conditions (room temperature, open lab bench). The sample then may be precisely weighed at known time intervals (e.g., 2, 4, 8 hours) to determine the extent of weight gain or loss. The change in weight-% of moisture in the film is then determined from two weight measurements. The lamination processing and post-processing testing that follows allow for correlating various optical properties, including transmitted haze levels, of the laminate-containing embodiment of the invention with the determined initial levels of moisture content of the APBF. According to one embodiment of the invention it is preferred that the water content of the APBF prior to lamination be less than about 0.6 weight-%, more preferably less than about 0.4 weight-%, even more preferably less than 0.2 weight-%, and most preferably less than about 0.1 weight-%.
During the fabrication process, an optionally pre-treated at step (A) APBF 302, which may be about 100 μm thick, is disposed, at step (B) (“Assemble a Composite”) of
In a specific embodiment, the substrate may be made of optical quality glass or other materials suitable for use in an image-preserving reflector assembly and may be flat or have a selected curved shape. The configuration of the superstrate 308 may be substantially the same as that of the substrate 304, and surfaces of the substrate and superstrate may be conforming to each other. It should be realized, however, that overall dimensions of the substrate and superstrate are generally not required to be the same. In the context of rearview mirror assemblies, a component of the mirror system may perform as a substrate or a superstrate for a laminate. For example, the mirror element 2220 of
The polymer-based film 302 may be extruded or molded, or fabricated using other known methods, it may comprise a single layer (such as a layer of a low-density polyethylene, see, e.g., U.S. Pat. No. 5,631,089) or be a multi-layer film stack (such as a stack of alternating layers having high- and low refractive indices) some of the layers of which may be optically anisotropic (e.g., birefringent). For example, the film 302 may contain commercially available plastics such as acrylics, polycarbonates, silicone, polyester, polysulfone, polycyclic olefin, PVC, or the like having nominal indices of refraction from about 1.3 to about 1.8. The stack of layers with alternating refractive indices may be used to enhance the reflectance of light having a given polarization while simultaneously optimizing the transmittance of light having another polarization state. Such anisotropic layers may include, in one embodiment, a prismatically microstructured surface similar to that disclosed in U.S. Pat. No. 5,422,756 that facilitates the separation of the incident light into two components having orthogonal polarizations. In addition or alternatively, the film 302 may comprise a plurality of alternating polymeric layers of at least two types having, respectively, high and low refractive indices at one polarization and different high and low refractive indices at an orthogonal polarization. One example of such film, comprising alternating layers of crystalline naphthalene dicarboxylic acid polyester, was described in WO 95/17303. In yet another alternative embodiment, the multilayer polymer film 302 may comprise a layer that has a spatially oriented structure realized, for example, by stretching an otherwise isotropic polymer film in a chosen direction.
It should be noted that, to assure adequate flattening of the film 302 between the plates 304 and 308 at the step (B) of
During the “Laminate/Bond” step (C) of
In a related embodiment, a superstrate portion 308 of the laminate may be removed, as shown at an optional step (E), “Release Superstrate”, for example after the lamination has been complete but prior to the quality inspection step of the process of the invention. As shown in
To enhance adhesion of the DBEF or other APBF to a desired substrate or superstrate and to improve durability of the resulting laminate, the substrate and/or the superstrate is preferably cleaned (not shown) before the lamination process to remove contaminants which could interfere with adhesion and induce optical defects. Cleaning can be accomplished chemically using detergents, solvents, or etchants to remove gross contamination. In addition or alternatively, mechanical cleaning of a substrate may be employed using polishing compounds such as aluminum oxide or cerium oxide can be used to further prepare the substrate surface. In addition, at least one of the substrates and the polarizing film can be optionally pretreated (not shown) to enhance adhesion. Surface treatment such as with flame, ozone, corona plasma, or atmospheric plasma can be used to further clean and/or functionalize the surfaces to be bonded. Adhesion promoters or coupling agents such as organofunctional silanes, organotitanates, organozirconates, zircoaluminates, alkyl phosphates, metal organics or adhesion-promoting polymers can be deposited in a thin-film form using a variety of techniques. These promoters and coupling agents are used to bridge the interface between the inorganic and organic substrates and improve overall adhesion and resistance to humid environments. Examples of suitable adhesion promoters include Z-6011 silane (from Dow Corning) and Silquest A-1120 silane (from G.E. Silicones).
It shall be also understood that in an embodiment where the superstrate is removed (or released) and thus does not remain part of the laminate, the superstrate generally does not have to be made of a transparent material. In such embodiment, various superstrate materials can be suitably used such as, e.g., ceramics, metals, carbide, boron-nitride, fluorocarbon, phenolic, acetal or nylon. Moreover, in such embodiment, at the initial steps of fabrication of a laminate, the use of a superstrate 308 may not be required at all.
(1) Heat-Press Operation:
An APBF-including composite (such as, e.g., the composite 312 of
(2) Oven/Roller System:
The composite such as composite 312 of
(3) Sonic Heat Press and Inductive Heat Press provide alternative fabrication approaches. For example, heating at least one of the cover plates 304 and 308 and the film 302 during the lamination process may be accomplished ultrasonically. A sacrificial film (e.g., a film disposed between the APBF and an anvil in the embodiment of
(4) RF-Lamination Press:
Radio frequency (RF) lamination technology, such as FastFuse™ RF Glass Lamination Technology available from Ceralink Inc. (Troy, N.Y.), combines high-speed RF-heating with pressure to produce laminates and may be advantageously used to produce glass/plastic film laminates with potential time and energy savings. In practice, an APBF-including composite such as the composite 312 of
At a post-lamination processing step (G), shown in
Using a “wave-dual scan” measurement technique and applying SW and LW metrics, it has been empirically found that a reflector may be suitable for most non-automotive applications if it is characterized by SW and LW values less than about 10, preferably less than about 7, more preferably less and 5, and most preferably less than 3. In contradistinction, image-preserving reflectors with intended use in rearview automotive mirror assemblies (including those containing laminated interfaces) should preferably be characterized by SW and LW values that are less than 3, more preferably less than 2, and most preferably less than 1. The alternative use of individual Wa, Wb and We metrics indicates, however, that, in order to have a mirror system with acceptable reflective properties, at least one of these W-metrics should be less than 7, more preferably less than 5, and most preferably less than 3. It is preferred, however, that more than one of these W-metrics be less than 7, more preferably less than 5, and most preferably less than 3. It is understood that various other optical techniques such as interferometric profilometry, or measuring of light scattering, or any other known in the art approach suitable for surface characterization may be alternatively used to describe the quality of the laminate fabricated according to an embodiment of the method of the invention.
As yet another alternative, the quality of the APBF-based laminates and mirror structures containing such laminates can be characterized with the use of ONDULO technology developed by Visiol Technologies (France) based on the principle of phase shifting deflectometry and commonly used in automotive industry for evaluation of visual defects occurring when two panels are bonded together. The goal of this non-contacting technique is to quantify the structural defects in inspected reflecting interface (whether curved or flat) based on distortions of the reflection of a fiducial object in that interface. Based on the evaluation of such distortions, the data are generated representing spatial derivatives of the slope of the surface of the reflector, and a conclusion of the type and distribution of structural defects in that reflector is obtained. The metric used for evaluation of the optical distortions with this technology is defined as “Curvature Units” (CU). The advantage of using the deflectometry approach is its high spatial resolution, the ability to recognize both isolated, point defects and extended defects, and a good correlation with visual tests. We have empirically found that image-preserving laminates with intended use in rearview automotive mirror assemblies should be characterized by CU values with moduli not exceeding approximately 0.04, preferably no exceeding 0.03, more preferably not exceeding 0.02, and most preferably not exceeding 0.01. An alternative technique for quantifying medium and small scale defects in an embodiment of a laminate of the invention may be based on a (local) measurement of a difference in optical powers of a flat reflecting surface and that of a flat reference surface, caused by the presence of structural defects in the reflecting surface. See, e.g., a description by ISRA Vision AG at www.isravision.com. In this technique, a set of fiducial lines is projected onto the tested reflecting surface, moved in front of the computerized line-scan detector that captures and analyzes the reflected image in comparison with a reference image. A conclusion about the surface defects is expressed in units of millidiopters of optical power of the surface under test. According to the embodiments of the present invention, image-preserving laminates with intended use in rearview automotive mirror assemblies and measured using ISRA approach are characterized by local optical power values of less than 1,000 millidiopters, more preferably less than 750 millidiopters, even more preferably less than 500 millidiopters, and most preferably less than 250 millidiopters.
The following discussion provides some examples of lamination processes and the resulting laminate structures, obtained according to the embodiments of the invention for the intended use in automotive rearview mirror assemblies. Generally, the temperature T selected to laminate an initial composite is within a range from about 50° C. to about 160° C., preferably between about 80° C. to about 150° C., and most preferably between about 90° C. to about 110° C. The levels of substantially omnidirectional pressure P chosen for lamination are between about 25 psi to about 2,500 psi, preferably from about 50 psi to about 500 psi, and most preferably from about 100 psi to about 400 psi. The weight content of water in an APBF to be laminated is maintained as discussed above. The lamination time can generally vary between about 1 and 600 minutes, preferably between 5 and 180 minutes and most preferably between 15 and 60 minutes. However, different processing parameters may be used, provided that the quality of the optically active, polarization-affecting layer of the APBF is not compromised. Optimal time, temperature, humidity, and pressure generally depend on the choice of materials used in fabricating the APBF and particular media used in an autoclave. In some embodiments, the use of liquid in an autoclave improves the uniformity of temperature across the composite and improves heat transfer.
In one embodiment, for example, a glass-plastic composite of about 55 mm by 75 mm in size was formed by sandwiching an APBF reflective polarizing film (from Nitto Denko corporation), having a thickness of about 2 mils and a pressure-sensitive adhesive on one of its sides between a 1.6 mm thick substrate and a 1.1 mm thick superstrate, with the film's adhesive side facing the superstrate. The laminating process included assembling a composite at preferred levels of water content in the film and vacuum bagging the composite, followed by autoclaving at the temperature of about 90° C. and a gauge pressure of about 200 psi for 1 hour. Both the visual image testing, as described above, and the wave-scan BYK-Gardner testing confirmed that the quality of the laminate was satisfactory for its intended purpose in the automotive rearview mirror assembly. In particular, the wave-scan measurement of the laminated glass-polymer interface through the substrate produced normalized averaged surface figures of about SW 0.4 and LW 0.8 for the first and the second dimensional ranges of features measured by the BYK-Gardner device. When an APBF has surfaces with different texture, it may be advantageous to form a laminate in such a fashion as to have this smoother side later on placed towards the observer in the overall rearview mirror system.
In further reference to
A major effect of adding a depolarizing component to a reflective polarizer in a conventional application was considered in a prior art backlighting system, where a reflective polarizer was shown to enhance the perceived brightness of the LCD. To achieve such enhancement, the reflective polarizing film was placed between a light emitter and an LCD in such a fashion as to align polarization of light transmitted from the light emitter through the reflective polarizer with a direction required for optimal operation of the LCD. It will be realized that the addition of a depolarizing component to such a conventional backlighting system between the reflective polarizer and the LCD (i.e., on the other side of the RP as seen from the light emitter) reduces a degree of polarization otherwise resulting when only the reflective polarizing film is present. This situation is illustrated in
In a specific embodiment of the invention, at least one of the substrate and superstrate of the laminate may be made of plastic. The resulting laminate may be used, e.g., as a stand-alone component within the mirror system to provide an image-preserving rearview mirror satisfying the automotive standards. In this embodiment, plastic materials may be chosen to have corresponding glass transition temperatures exceeding the optimal temperature used in the lamination process. Examples of such materials are polycyclic olefin, polycarbonate, acrylic, polyimide, polyether-sulfone or epoxy. It shall be understood, however, that any other material suitable for use, in an image preserving reflector, as a substrate or a superstrate for a polymer-based film laminate can be used. In an embodiment where a superstrate of the laminate is not released, a component of the mirror system performing the role of the superstrate and positioned between the display and the reflective polarizer should preferably be formatted to not substantially depolarize light.
Once the lamination interface has been formed, it may be optionally protected (not shown in
Exemplary Embodiments Utilizing a Prismatic Element or an EC-Element.
Embodiments of laminar structures provided by the process of the invention (e.g., the embodiments 314 and 316 of
A) Specific Embodiments of a Switchable Mirror System Employing a Liquid-Crystal Cell and a Prismatic Mirror Element.
Furthermore, embodiments of the present invention may incorporate a “switchable” mirror system that utilizes an auxiliary LC-cell or device. Such switchable mirror system may operate at different levels of reflectance, transmittance, or both. Although such a switchable mirror may be configured to operate in either a high-reflectance or a low-reflectance state when the power to the LC-cell is off, it may be preferred to configure the switchable mirror system of the present invention to operate in the former mode. If this configuration is achieved, the mirror system will provide for and maintain the optimal rear-vision conditions when the system fails, that is when either the mirror system itself or a display behind the mirror system fails or loses power. As shown in an embodiment 420
B) Embodiments Employing a Prismatic Mirror Element.
In a specific embodiment, schematically shown in
Reflecting structures and assemblies such as rearview mirrors incorporating polymer-based films laminated according to the embodiment of the invention generally do not exhibit optical blemishes, are devoid of extended distortions, and do not produce image distortions that distract the viewer, as discussed above, thus preserving the quality of optical imaging within the requirements of automotive industry standards. Although embodiments of the invention are discussed in this application with respect to placing an APBF-containing laminate of the invention in particular locations within a rearview mirror assembly, it will be noted that, generally, positioning a laminate of the invention in other suitable locations is also contemplated. In one embodiment of the rearview mirror, e.g., an additional APBF-containing laminate may be disposed behind the display, as seen by the observer.
In a specific embodiment, an air gap or cavity can be formed between surfaces of the mirror system and later preferably sealed with a perimeter seal to avoid entrapment and/or condensation of vapors and dust. For example, a mirror assembly may include constructions such as [G/RP/air/G] or [G/RP/G/air/G/ITO/EC/ITO/G]. In these exemplary constructions, the components or media are listed starting with the one farthest from the viewer, the “air” denotes a cavity or a gap that may be defined by the perimeter seal and/or spacer disposed between the adjacent components separated from one another, “RP” refers to a layer of reflective polarizer such as APBF, for example, and “G” denotes a lite of glass or other suitable substrate material.
C) Embodiments Employing an EC-Element.
A simplified scheme, not to scale, of an embodiment 600 of the mirror assembly is shown in
As discussed above, the display subassembly shown in
From the position of the observer 115, the surfaces 636, 637, 632, 634, 624, and 640 of the structural elements of the assembly such as glass plates are viewed as the first, the second, the third, the fourth, the fifth, and the sixth surfaces, respectively, and may be alternatively labeled with roman numerals as I, II, III, IV, V, and VI, as shown in
The use of the APBF-containing laminate in conjunction with a light source in a rearview mirror assembly, for the purposes of increasing the effective brightness of the light source on the background of the ambient light, may be particularly advantageous when the employed light source generates polarized light that is preferentially transmitted by the APBF. Light sources emitting either partially or completely polarized light—such as displays equipped with an LED, or a laser diode, or an LCD—provide particularly suitable examples. When the display assembly 639 comprises an LCD, the front polarizer of the LCD may be replaced with the laminate of the invention. In an alternative embodiment, a substrate of the LCD, through which light exits the LCD, may be used as a superstrate for a laminate of the invention. In this case, a reflective polarizer included within the laminate of the invention may be used to transmit light having the first polarization and generated by the display located behind the laminate, and to reflect light having a second polarization that is orthogonal to the first polarization.
Referring again to
The following examples, described with reference to
In contradistinction with prior art and in accordance with the present invention, an embodiment of a laminate 828 containing a reflective polarizer 824 (e.g., an APBF manufactured by 3M, Inc.) may be advantageously incorporated within a rearview mirror assembly. As now described in reference to
Referring now to the embodiment 830 in
In comparison to the embodiment 836 of
Comparing now the embodiment 850 of
In the embodiment 860 of
In another embodiment of the invention, schematically shown in
If further reference to
D) Specific Embodiments of a Switchable Mirror System Employing a Liquid-Crystal Cell and an EC-Element.
Switchable mirror system (SMS) embodiments may employ various LC-cell-based devices such as, e.g., one or more cells containing a cholesteric LC-material, which manipulates (transmits and/or reflects) circularly polarized light and used with or without an additional quarter-wave plate. Embodiments may also employ a Twisted Nematic (TN) cell, a Super Twisted Nematic (STN) cell, a guest-host or phase-change LC device incorporating a dichroic dye, a Ferroelectric LC device such as a smectic ferro-electric cell, a nematic Distortion of Aligned Phases (DAP) LC device, an In-Plane Switching (IPS) device; an Optically Compensated Bend (OCB) device, or a Multi-Domain Vertical Alignment (MVA) device, which manipulate (transmit and/or reflect) linearly polarized light. Although the following embodiments of a switchable mirror system are described in reference to a TN LC-cell, it is appreciated that any of the above-mentioned devices can be generally used to provide for switchable operation of a mirror system. To reflect light of red/green/blue (RGB) colors in a particular circular polarization (right-handed, for example), three cholesteric LC-cells would be required. Therefore, it would require six cholesteric LC-cells to reflect RGB colors in both circular polarization. Broadband polychromatic Circularly polarized light can be reflected by a cholesteric cell containing a variable pitch medium, but because of the difficulty in forming the variable pitch difficulty, this technology has not been successfully commercialized. Cholesteric LC-based systems are, in addition, very temperature-sensitive because the cholesteric pitch length changes with temperature. This change results in a temperature-dependent shift in the wavelength of reflected light over as little as a 10 deg C. temperature range. Automotive mirrors, as well as architectural and aerospace windows must perform over a large temperature range (−40 deg C. to 80 deg C.), thereby making the use of cholesteric systems impractical for these applications. Therefore, devices that manipulate linearly polarized light (such as a TN LC-cell) are preferred.
For simplicity of illustrations,
As mentioned in reference to
An example of such embodiment is illustrated in
Another sample of the switchable mirror system was also fabricated according to the structure 3410, with polarization axes of the RPs 3311 and 3312 mutually aligned. The EC-element 840 included two glass substrates, each approximately 6 cm by 26 cm in size and 1.1 mm thick and carrying approximately 145 nm thick ITO electrode layers on the surfaces forming the EC-chamber. The EC-chamber of approximately 140 microns in width was assembled with the use of amine cure epoxy and filled with EC-fluid comprising 27 mM of the anodic material 5,10 dimethyl 5,10 dihydrophenazine and 32 mM of the cathodic material octylviologen tetrafluoroborate. The RPs 3311, 3312 were made of DBEF-Q sold by 3M Corp. of St. Paul, Minn. and flattened and laminated according to the method of
The switchable mirror system of Example 2 was assembled according to the method described in reference to
Generally, the embodiment 3400 has advantageous characteristics that come from its ability to combines a rapid response of an LC-cell-based switch with a large dynamic range of an EC-element. Specifically, due to the fast performance of the LC-cell 3303 the embodiment 3400 can be switched from a high-reflectance (in excess of 70%) state to a low-reflectance (several %) state very rapidly, (within approximately 100 milliseconds). At the same time, the EC-element can gradually (within 1 to 5 seconds) reduce the reflectance of the overall system from “high R” state or an intermediate-reflectance state (“mid R”, where the value of R is approximately between 35% and 70%) to a “low R” state (R of about a few percent) or, if required, to any other specified level of reflectance. As demonstrated below, the reflectance of an embodiment of the overall APBF-containing mirror system can be varied by controlling the absorption of light in the components of the system such as an EC-element or, generally, an electrooptic element located in front of reflecting layers.
It is appreciated that alternative implementation of a switchable mirror system may include wire-grid reflective polarizers used instead of APBF-based reflective polarizers in either of the embodiments of
Segmentation of a Mirror System:
Overall, embodiments employing a combination of an LC-cell with a prismatic element or an EC-element, such as those of
Components located behind the segmented portion of the mirror may include a photosensor, a camera, an icon (indicia) with or without a backlight. If the photosensor that detects glare conditions at night is located behind the switchable mirror in an eyehole area, the corresponding “eyehole” area could be segmented in order to remain in the “high R” stealth mode during daytime (directed by the forward-looking photosensor) and switch to the “mid R/high T” mode during nighttime. Similarly, when information from a camera located behind the mirror assembly is not required, the segmented area in front of the camera could remain in the “high R” stealth mode and then switch to the “mid R/high T” mode of operation when image information from the camera becomes necessary. Such switching could happen at a rate consistent with the response frequency of the LC-cell based device. Accordingly, operation of the camera, the sensor, the lighted icon or the indicator could be modulated at the rate of switching of a corresponding segmented area of the switchable mirror so that pictures or measurements are taken, or the icon or indicator light source is turned on and off, only during the periods of “high transmittance” of such segmented area of the SMS. (At a switching rate of about 30 Hz or higher, for example, the human eye would not detect the “flicker” of the switching event.) Depending on the requirements of the system, the relative on/off time, period, and duty cycle of switching of a particular segment of the SMS can be adjusted to balance the needs of the sensor (or the camera) and the desire to maintain a stealth appearance for the mirror. If the camera or sensor is sensitive to aberrations caused by polarized light, a de-polarizer could be placed in front of the camera or sensor. Likewise, a visual icon or indicia can be hidden behind a segmented portion of the mirror in the “high R” mode and made visible (preferably with a backlight switching on) at the same time as the corresponding mirror segment switches from “high R” to “mid R/high T” mode. All of these examples refer to switching of the TN LC-cell section of the SMS that is positioned between two polarizers.
It should be noted that, generally, any element of the switchable mirror system can be segmented. A EC-element portion of the mirror if present can be segmented and selectively switched. So can a GH LC-cell portion described below. Similarly, the TN LC-cell portion of the mirror can be segmented and selectively switched.
In a specific embodiment, the LC-cell could be segmented so as to facilitate transmission of numeric or alpha-numeric images from the display through a mirror system to the viewer. Alternatively, the LC-cell could be segmented in a dot-matrix fashion. Images could then be displayed to the viewer by alternating the high and low reflection states of the segments of the mirror system or, if the area is back-lit, by alternating the high and low transmission states of the segments.
Combinations of Liquid-Crystal Cells with Polarizers:
Embodiments of various LC-cells in combinations with polarizers (either reflective or absorptive), and an EC-element or a prism element are schematically illustrated in
Another stage of operation, when the LC-cell 4624 is on, is characterized by: a) the overall reflectance, R, of less than 50%, preferably less than 30%, more preferably less than 20%, and most preferably less than 10%; and b) the polarized transmittance, PT, of more than 50%, preferably more than 60%, and most preferably more than 70%. It is understood that switching among the multiple stages of operation of the embodiments I, II of
D1) Specific Embodiments of a Switchable Mirror System Employing a Combination of Liquid-Crystal-Cell Based Devices
A rearview assembly incorporating a mirror system and a source of light such as a display behind the mirror system should allow for operation in a “display” mode, when the image formed with the use of light-output from the display is projected through the mirror system for viewing by the user, as well as in a “mirror” mode, when it is the image of the surrounding formed in reflection of the ambient light by the mirror system that the viewer pays attention to. It is appreciated that, for the purposes of the invention, the optimized embodiment of the mirror system in such an assembly should have maximized transmittance and minimized reflectance in the “display” mode in order to assure that the brightness of the displayed image is optimal, especially when ambient light is plentiful. In the “mirror” mode, however, the same embodiment of the mirror system should be configured to have transmittance as low as possible and reflectance as high as possible to assure that amount of light reaching the viewer from behind the mirror system is minimized so that the quality of the image of the surrounding does not suffer. In other words, the dynamic range of reflectance/transmittance characteristics in an embodiment of a switchable mirror system (SMS) of the rearview assembly should be maximized. From the discussion provided in reference to
We have discovered that configuring a mirror system (and, in particular, the switchable mirror system that includes an LC-cell-based device) in such a fashion as to provide for independent attenuation of light components having different polarization states further increases the attainable dynamic range of reflectance/transmittance characteristics of the rearview assembly for the purposes of the invention. In particular, a switchable polarizer that operates in two modes (transparent for light with any polarization in the first mode and absorbing light with a particular polarization in a second mode) may be incorporated into a mirror system. Examples of such switchable polarizer are provided by a Guest-Host Liquid Crystal (GH LC) element containing a dye and an EC-element containing an orientated EC-medium such as stretched polyaniline, as described by P. Anderson in Appl. Phys. Lett., 83(7), 1307-1309 (2003). This publication is incorporated herein by reference in its entirety. The first example (GH LC-cell with a dye such as an anthraquinone dye or an azo dye) is predominantly used below in describing embodiments of a switchable mirror system of the invention. It shall be appreciated, however, that the EC-element containing an orientated EC-medium can be used instead of the GH LC-cell, which use is within the scope of the present invention.
Incorporating such switchable polarizer as part of a switchable mirror in front of the SMS that contains an RP allows for selectively absorbing a portion of ambient incident light that is reflected by the RP towards the front of the mirror system without significantly attenuating a portion of light having a different polarization.
An exemplary embodiment 5200 configured according to this principle is schematically illustrated in
Principle of Operation:
The LC-medium-alignment layers 5326 and the reflective polarizers 3311, 3312 are configured within the embodiment 5300 in such a way as to assure that the LC-molecules 5312 (and, accordingly, the dye molecules 5314) are aligned predominantly parallel to both reflection axes of the RPs 3311, 3312 (y-axis in
Similarly, in further reference to
Table 2B summarizes the discrete states of reflection/transmission of unpolarized light by the switchable mirror system of the embodiment 5300 depending on the operational status of each of the switchable absorptive polarizer 5310 and the TN LC-cell 3303, as well as reflectance/transmittance values estimated for conventional guest-host LC media and materials used in fabrication of the TN LC-cell. The “low R” values represent an embodiment where surface I is not AR-coated. AR-coating of surface I will reduce the values of reflectance even further. In comparison, Table 2B1 summarizes the discrete states of reflectance/transmittance of unpolarized light by a similar SMS where, instead of the GH LC-cell 5310, an EC-element containing orientated EC-medium is used.
As shown, therefore, an embodiment of the switchable mirror system of the invention can be operated in a tri-state reflectance mode (“high R”, “mid R”, and “low R”) to reduce glare or optimize the brightness of the display (specifically, in “mid R” and “low R” modes of operation). In addition to that, the embodiment assures an operation in a dual transmission mode (“low T” to be used when the display 1850 is “off” and “high T” mode to be used when the display 1850 is “on”). A comparison with Table 2A shows that the embodiment 5300 offers an advantage over the embodiment 3400 in that only the former can be operated in a “low R/high T” mode and thus has a higher dynamic range of reflectance/transmittance modes of operation.
Gradual Variation of Optical Performance:
It shall be further appreciated, however, that the operation of embodiments of the invention is not limited to discrete reflectance/transmittance levels listed in Table 2C but may be further controlled in a continuous, variable, “grey scale” fashion between these levels. Specifically, the “grey scale” operation can be achieved by adjusting the voltage V5310 applied to the switchable polarizer 5310 in a continuous fashion. For example, as the applied voltage is gradually increased from the zero level, the host-medium LC molecules 5312 and the guest-medium dye molecules 5314 rotate from a default orientation parallel to the chamber wall surfaces 5320, 5322 to that perpendicular to the chamber wall surfaces. Due to this rotation the amount of ambient light 5412 absorbed by the dye 5314 (
If a rearview assembly incorporating the embodiment 5300 is to operate in a glare-reduction mode with the TN LC-cell 3303 performing in a high transmission mode (V3303≠0), care must be taken to minimize the amount of light reflected off of assembly components located behind the mirror system. All surfaces behind the mirror system should be coated with an AR coating or be blackened to maintain stealthy appearance. To improve the stealthy appearance further, a second switchable polarizer 5510 can be employed. For example, as shown in
It is appreciated that in applications requiring only a portion of the display of the rearview assembly to be visible at any given time (e.g., to activate a particular indicator), the use of the second GH LC-cell device 5510 disposed at the back of the switchable mirror facilitates blocking an undesired light transmission through selected areas of the mirror thereby resulting in a more aesthetically pleasing product.
It is recognized that variation on embodiments of a SMS described herein could be used not only in a rearview automotive assembly but also in windows in architectural, transportation or aerospace applications.
Reduction of Double Imaging:
“Double imaging” is a familiar phenomenon arising from reflection of light from several surfaces in a multi-surface structure and often referred to as parallax. Multiple images formed in reflection from multiple surfaces obscure the main image of interest and are mutually offset, in the image plane, by distances that are dependent on the geometry of the positioning of the multiple reflective surfaces and the optical properties of the media involved. In the well-known example of a multiple reflection of the incident beam I of light from a plane-parallel optical plate, schematically illustrated in
For example, when the RPs of the embodiments of the invention are separated by about 1.8 mm and viewed at an angle of about 25 degrees then the resulting transverse offset between the two images formed in reflection from the RPs is about Δa=1 mm and this separation represents a limit that may be acceptable for automotive applications. Accordingly, embodiments of the invention are judiciously configured so as to assure that the transverse offset between the two images formed in reflection of ambient light in the RPs of the invention is less than 0.75 mm, more preferably less than 0.50 mm, and most preferably less than 0.25 mm.
One approach to minimization of the double imaging is a reduction of separation distance between the reflecting surfaces at issue. In a practical embodiment of the SMS that contains a LC-cell-based device and two RPs such approach implies that the separation between the RPs should be reduced. It is appreciated that, in general, the RPs used in embodiments of the SMS of the invention may be either APBF-based or wire-grid based.
It is appreciated that a combination of the wire-grid and APBF-based RPs may also be employed in an embodiment of the invention, as shown in
In another embodiment of the SMS of the invention employing two RPs, one of the RPs may be disposed within the TN LC-cell of the embodiment while another is disposed outside of the cell. This structure is illustrated in an embodiment of
The wire-grid layer only has high conductivity in the direction of the wire Therefore, in any embodiment where the wire-grid polarizer is used as an electrode, it may be necessary to supplement the conductivity with a TCO layer under or over the wire-grid layer. Such a TCO layer is shown in
As shown in examples of
Overall, the APBF-based RPs used in embodiments of a SMS may include DBEF-Q, APF-25, APF-35, APF-50 or other equivalent plastic-based reflective polarizer materials. When the employed RP is APBF-based, it is preferably laminated to a corresponding substrate, using the method of the invention discussed in reference to
Another approach to minimization of the spurious imaging is modification of the substrates of an embodiment.
It is appreciated that, generally, the substrates of the SMS of the invention could be made of glass or plastic materials. In addition, in certain embodiments it is advantageous for the substrate to preserve the polarization states of reflected and transmitted light. In certain embodiments it is desirable for either the first or the second substrate (where the first substrate is one closest to the viewer) or both the first and second substrates to depolarize light. It is preferable to have at least one or more substrates be less than 1.2 mm thick, more preferable less than 0.75 mm thick and most preferably less than 0.5 mm thick. If, as an example, the RPs of the embodiment of
Using thinner substrates and/or reducing the number of substrates and/or using transparent plastic substrates rather than glass substrates is contemplated by the embodiments of the invention and will reduce the weight of the overall mirror system which is desirable in the transportation and aeronautic applications. Reducing the thickness of the overall mirror system also allows for thinner, sleeker, and more aesthetically pleasing mirror package designs.
As a baseline example, an SMS embodiment having two DBEF layers as RPs is configured according to the following sequence (when viewed from the front of the mirror system): Glass/TCO/LC1/TCO/Glass/RP1/Glass/TCO/LC2/TCO/LC/Glass/RP2/Glass. Here, TCO represents a transparent conduction oxide or the like, LC1 represents a guest-host LC medium or an orientated EC-medium, and RP represents an APBF. The LC-cells are preferably produced first and then bonded/laminated to the RP material. In fabrication, the two LC-cells are placed on either side of a first reflective polarizer RP1, the second reflective polarizer RP2 is disposed between the second LC-cell and another lite of glass. The entire five-lite structure further undergoes a bonding/lamination process described in reference to
It is recognized that, in a specific embodiment, the number of substrates used to configure the SMS of the invention may be reduced. For example,
Depending on the quality of the glass, it may be necessary to have each lite of glass be 1.6 mm thick or even thicker. (Thinner, less expensive glass may have inadequate optical distortion properties, but its use is also contemplated) The total mass of this construction then is approximated as weight of a piece of glass having transverse dimensions of a substrate and thickness of about 8 mm. Given the density of glass of about 2.44 grams/cm3, the preferred net weight of the embodiment per unit area is about 2.0 grams/cm2. (The TCO and RP layers are relatively thin and can be ignored to the first order of magnitude). In some applications the weight per unit area of 2.0 grams/cm2 may not be acceptable. For instance, in automotive rearview mirrors where the mirror is suspended from the windshield, minimization of arising vibrations of the mirror may dictate a reduction of its weight. Therefore, weight per unit area of the embodiments of the SMS of the invention, regardless of the number of substrates used, is preferably less than 2.0 g/cm2, more preferably less than 1.2 g/cm2, more preferably less than 1.0 g/cm2 and most preferably less than 0.75 g/cm2. For instance, if 1.6 mm thick glass substrates are used in a structure defined above, the weight per unit area of the SMS embodiment would be about 1.17 g/cm2. If higher quality glass were used, the thickness of the lites could be reduced to 0.7 mm and the weight per unit area would be approximately 0.51 g/cm2.
Minimization of Transmission in a “Low Transmission” Mode:
One possible shortcoming of a segmented switchable mirror system employing RPs may stem from the fact that light from a display backlight or a backlight illuminator of such system may leak through the segments of the mirror that are not active at the moment. An example of such situation is provided by a rearview assembly employing a segmented mirror system and a TFT-LCD, which is continuously illuminated but only a portion of which has to be viewable at any given moment through a corresponding segment of the mirror (e.g., to provide visible readings of a compass heading, time, or temperature to the viewer). One possible solution to the light-leakage problem and assuring that transmission of the segmented mirror system in “high R/low T” mode is minimized is the use of RPs having high polarizing efficiency. For efficient use in rearview mirror assemblies the light leakage through the mirror system operating in the low-transmission state should be below 7%, preferably below 4%, and most preferably below 2% of the amount of incident light. The efficiency of a given polarizer can be determined by measuring the light transmission through a combination of the given RP and an efficient absorptive polarizer. Table 2C shows the polarizing efficiencies for several types of polarizers based on measurements, while paired with an absorptive polarizer, in two configurations: a) transmission axes of the two polarizers are collinear; and b) transmission axes of the two polarizers are perpendicular.
In a segmented mirror system employing a TN LC-cell device and a pair of RPs (see, e.g., embodiments of
Yet another solution to minimize the transmission of the mirror system in a “high R/low T” mode of operation would be to add an absorptive polarizer behind the front RP (relative to the viewer) such that the absorption axis of the former is collinear with the reflection axis of the latter.
The same techniques used to enhance the viewing angle and contrast ratio of LCD's can be used to improve the performance of the LC switchable mirror element. The combination of liquid crystal fluid and element cell gap can be optimized for the best optical performance in the 1st, 2nd, or 3rd minima with a first minima device being preferred. Compensating films can be used to improve off angle performance such as uniaxial and biaxial oriented retardation films, coated liquid crystal films or modified TAC films. These films are available from Fujifilms (Wide View), Nippon Oil, Zeon Chemical, LG Chemical, JSR and Konica-Minolta.
Multiple Electrode Surface Multiple Electrode Segments Contact Methods:
In switchable mirror systems described in this specification there is a substrate having electrodes with many segments and a substrate that can have electrodes on one or both surfaces. Making reliable electrical contact between these electrodes and a printed circuit board or drive electronics is challenging. The substrates can be offset in an alternate pattern in either transverse direction with respect to a direction of propagation of light (i.e., along either x- or y-axis or along both axes) to expose the electrode surfaces and enable contact. If a substrate has an electrode on both surfaces, or if two substrates that have electrodes oriented back-to-back share the same offset, electrical contact can be made to both electrodes with, for instance, a C-shaped clip. Alternatively, both electrodes could be patterned in an alternating offset contact configuration so as to allow for the C-shaped clip to be set in contact with the top electrode, the bottom electrode, or both electrodes. In this way the top and bottom electrodes could be addressed independently. If the top and bottom electrodes were segmented and the multiple segments were offset relative to one another, the segments could also be addressed independently. Contact can be made to electrodes with offset substrates that form a contact ledge with a multiple contact spring connector inserted onto the contact ledge, multiple C shaped clips with a leg commonly called dual or single in line clips in the LCD industry, a C shaped buss clip with a soldered wire or spring connector, a heat or pressure bonded connection to a flexible circuit ribbon or a conductive elastomer type connector. If there is no offset between the substrates a conductive material such as a coating or metal filled ink or adhesive could be applied such that it contacts the electrode and rolls over onto perimeter edge of the substrate to allow that electrode connections could be made to the edge of the substrate. Electrical connection to the conductive portion on the edge of the substrate could be made with a spring clip compressed by or molded into a bezel assembly, a L shaped clip, a Z shaped clip or a J shaped clip. One portion of the clip could be attached to the back surface of the mirror assembly if desired. If the spacing between the substrates allows, part of a J shaped clip cold be inserted between the substrates to make contact to the electrode. Another method of contacting the electrode surface is to use wire bonding to connect the electrode surface to a control module or electrical distribution system.
It is recognized that the configuration of the TN LC-cell (such as cell 3303), which rotates the polarization of light by 90 degrees upon traversal of the powered “off” cell and which is used in conjunction with the two aligned RPs (such as RPs 3311, 3312), is intentionally chosen. The purpose of such configuration is to assure that in the case of failure (power off) the switchable mirror system of any of the embodiments discussed in reference to
Moreover, it is desirable to have a failed (powered off) switchable mirror system have reflectance that meets or exceeds minimum reflectance standards required by regulation (reflectance greater than 35% in the US and greater than 40% in Europe). When any embodiment of an SMS described above in reference to
Embodiments of rearview assembly that combine means for recirculation of light emitted by a backlight (emitter) to illuminate the LCD and an embodiment of the SMS of the invention are also within the scope of the present invention. Such embodiments include generally include more than two RPs, one of which is employed outside of the SMS. As shown in
E) Exemplary Embodiments with Tailored Optical Characteristics.
The effect produced by a reflectance-enhancing coating on the overall (unpolarized light) reflectance and polarized transmittance characteristics of a mirror assembly may be quantified by defining a figure of merit such as, e.g., the ratio of the polarized transmittance and the overall reflectance (PT/R). This figure of merit is listed in Table 3, together with the corresponding reflectance and transmittance data discussed above with reference to embodiments of
For example, applying quarter-wave dielectric coatings to at least one of surfaces I and II in a mirror assembly embodiment that comprises an EC-element and a reflective polarizer (such as embodiments of
The reflectance of a surface overcoated with a single dielectric overlayer can also be enhanced by adding a pair of layers to the single dielectric overlayer. The refractive index of one such layer, designated as low (or L), should be smaller than the refractive index of the single dielectric overlayer, while the index of the second layer, designated high (or H), should be larger than the refractive index of the L layer. The H layer may be made of the same material as the single dielectric overlayer, or it may be made of a different material. The degree to which the overall reflectance of an optical surface is enhanced depends on the index contrast of the thin-film materials used for such enhancement. The equivalent optical thickness of each of the H and L layers in the enhancing pair of layers should be about a quarter-wave so as to maximize the resulting reflectance of the thin-film stack. Preferably, in such a pair of layers, the refractive index of the reflectance-enhancing layer with the “high index” value is greater than about 1.7, and more preferably greater than 2.0. In some embodiments, such index may be on the order of or even exceed 2.4. Preferably, the difference between indices of the H and L layers should be greater than about 0.4 and more preferably greater than about 0.7. In some embodiments, the index of L-layer may be more than 1.0 below that of H-layer. Additional high/low pairs can be added to further enhance the reflectance. For instance, the overall material stack may comprise (starting with materials farthest from viewer) G/RP/H/G.
Alternative embodiments of the structures having enhanced reflectance, for use in automotive mirror assemblies may be, e.g., G/RP/H/L/H/G, or G/RP/H/L/H/G/ITO/EC/ITO/G and similar structures, where, instead of a layer of the ITO on surface Ill, a semi-transparent layer of metal (preferably Ag or Ag-based alloy such as silver-gold alloy, which is known to be chemically stable when in contact with most fluid-based EC media) may be used for enhancement of reflectance. Additional layers may be employed to attain color neutrality in reflection, as discussed in various commonly-assigned patent applications. In the abovementioned structures, G denotes a glass layer (substrate); RP corresponds to a reflective polarizer component; H and L conventionally denote dielectric layers with high and low refractive indices, respectively; and EC symbolizes a layer of electrochromic medium. The H and L layers or any combination of such layers may be deposited directly onto the glass substrate or, alternatively, may be disposed directly onto the reflective polarizer component, depending on the requirements of a given application. The refractive index of any bulk layer interface in the reflective polarizer system can also play a role in modifying, attenuating or enhancing the reflectance. In general, to enhance reflectance a larger difference in refractive index between two neighboring materials is preferred. Conversely, minimizing the difference in the refractive index between neighboring materials typically will reduce the reflectance. Any additional interface materials present on the reflective polarizer can influence the reflectance due to the refractive index mismatch phenomena.
If an additional depolarizer (in the form of a depolarizing layer, for example), or pressure sensitive adhesive or other material is placed between the reflective polarizer and a coated or uncoated glass surface then the refractive index of this material will be a determining factor in the final reflectance. For example, in one embodiment, when a high-index reflectance-enhancing layer is present on surface IV of the system, the system reflectance may be maximized if the neighboring material has a relatively low refractive index—the lower the better. It is understood that optimization of the entire system is required to achieve a desired set of properties. The optimal refractive indices of materials used will generally depend on the indices of surrounding materials and may vary depending on the application.
In other possible embodiments, as discussed below, the use of a graded index material between the reflective polarizer and the adjacent glass surface may result in the optimal reflectance effects if the there are divergent requirements for the reflective polarizer and the coated or uncoated neighboring surface or interface. Non-limiting examples of suitable high refractive index layers are: antimony trioxide, cadmium sulfide, cerium oxide, tin oxide, zinc oxide, titanium dioxide or various titanium oxides, lanthanum oxide, lead chloride, praseodymium oxide, scandium oxide, silicon, tantalum pentoxide, thallium chloride, thorium oxide, yttrium oxide, zinc sulfide, zirconium oxide, zinc tin oxide, silicon nitride, indium oxide, molybdenum oxide, tungsten oxide, vanadium oxide, barium titanate, hafnium oxide, niobium oxide, and strontium titanate. Non-limiting examples of suitable low refractive index layers are: aluminum fluoride, aluminum oxide, silicon oxide, silicon dioxide, calcium fluoride, cerium fluoride, lanthanum fluoride, lead fluoride, lithium fluoride, magnesium fluoride, magnesium oxide, neodymium fluoride, sodium fluoride, thorium fluoride or a porous film with high density of voids. The reflectance value of the mirror system and spectral properties of light reflected by the system can be further tuned by using at least one optical layer having material properties that vary with layer thickness. A common example of such materially non-uniform layer is known as a graded composition coating (GCC). In comparison with the graded thickness layers (characterized by spatially uniform material properties and spatially non-uniform thickness), a GCC may have a spatially non-uniform material composition resulting, e.g., in a refractive index that varies as a function of thickness. In one embodiment, the mirror assembly may include a GCC formed with a variable mixture of SiO2 (refractive index of about 1.45) and TiO2 (refractive index of about 2.4). For example, next to a substrate onto which the GCC is deposited, the GCC may predominantly contain SiO2 (and, therefore, have a refractive index approaching 1.45). Throughout the thickness of the GCC, the material composition of the GCC is varied to increase the content of TiO2. As a result, the refractive index of the outer portion of the GCC may be approaching 2.4.
Alternatively or in addition, the overall reflectance of the rearview mirror assembly containing a multi-layered RP may be increased by altering the layers of the RP component. This may be accomplished, e.g., by adjusting thicknesses of different layers in a multilayered plastic-film based reflective polarizer. Alternately, the indices of these layers may be altered. The net reflectance and transmittance may thus be adjusted or tuned to the needs of a given application. In an typical inside rearview automotive mirror the reflectance is preferably greater than about 45%, more preferably greater than 55%, even more preferably greater than 60% and most preferably greater than about 65%.
The spectrum of light reflected (and that of light transmitted) by an embodiment of the mirror system of the invention can be tuned or modified by adjusting the thickness of the reflectance-enhancing layers. The peak reflectance will vary with optical design wavelength and this will result in a change in color gamut of the reflected (and transmitted) light. In discussing color distributions (i.e., spectra of light), it is useful to refer to the Commission Internationale de I'Eclairage's (CIE) 1976 CIELAB Chromaticity Diagram (commonly referred to the L*a*b* chart or quantification scheme). The technology of color is relatively complex, but a fairly comprehensive discussion is given by F. W. Billmeyer and M. Saltzman in Principles of Color Technology, 2nd Edition, J. Wiley and Sons Inc. (1981). The present disclosure, as it relates to color technology and uses appropriate terminology, generally follows that discussion. According to the L*a*b* quantification scheme, L* represents brightness, a* is a color coordinate that denotes the color gamut ranging from red (positive a*) to green (negative a*), and b* is a color coordinate that denotes the color gamut ranging from yellow and blue (positive and negative values of b*, respectively). As used in this application, Y (sometimes also referred to as Cap Y), represents the overall reflectance. For example, absorption spectra of an electrochromic medium, as measured at any particular voltage applied to the medium, may be converted to a three-number designation corresponding to a set of L*a*b* values. To calculate a set of color coordinates, such as L*a*b* values, from the spectral transmission or reflectance, two additional parameters are required. One is the spectral power distribution of the source or illuminant. The present disclosure uses CIE Standard Illuminant A to simulate light from automobile headlamps and uses CIE Standard Illuminant D65 to simulate daylight. The second parameter is the spectral response of the observer. Many of the examples below refer to a value Y from the 1931 CIE Standard since it corresponds more closely to the spectral reflectance than L*. The value of“color magnitude”, or C*, is defined as C*=√{square root over ((a*)2+(b*)2)} and provides a measure for quantifying color neutrality. The metric of “color difference”, or ΔC* is defined as ΔC*=√{square root over ((a*−a*′)2+(b*−b*′)2)}, where (a*, b*) and (a*′,b*′) describe color of light obtained in two different measurements. Additional CIELAB metric is defined as ΔE*=(Δa*+Δb*2+ΔL*2)1/2. The color values described herein are based, unless stated otherwise, on the CIE Standard D65 illuminant and the 10-degree observer.
Table 4 illustrates the calculated changes in spectral distribution of light reflected by the embodiment of
Plastic films having little absorption in the visible portion of the spectrum and, in particular, polymer-based RP films employed in embodiments of the present invention may be susceptible to degradation upon exposure to UV and/or short-wavelength visible light. Similarly, in embodiments of the invention that include LC-cell based devices, LC-medium may be similarly vulnerable. Protection of the APBFs and LC-cells from such degradation may be required and may be achieved in a number of ways. Possible ways of UV-protection are discussed below with respect to APBFs, but are understood to equally apply to UV-protection of the LC-cell-based devices contained within the embodiments of the invention.
For example, using protecting components that facilitate reflection and/or absorption of UV-light either within or in front of the APBF will generally diminish the degree of degradation of the APBF. However, improvements in UV-stability of the APBF should be carefully weighed against possible changes in other system characteristics. For example, changing the composition of glass substrates or a laminate stack in order to improve UV-stability of the APBF-containing mirror system may reduce the overall durability of the system as measured by one of the tests discussed above. Optical distortions, haze, optical angular sensitivity, depolarization effects, color characteristics (especially, yellowish hue) of the system are but only several examples of parameters that need to be considered while improving UV-light durability of the system. The use of UV-agents in the system could also affect the color of an RGB display of the system, as perceived by the viewer, if such UV-attenuators alter the transmission of the system in the visible range. (In this respect, the use of an RGB display that emits light within very narrow bandwidths around the chosen red, blue, and green wavelengths of operation may be preferred because in such a case the UV-agents protecting the APBF are less likely to interfere with light emanating from the display.) Incorporation of UV-agents may also affect the ability of a given component to withstand the fabrication process and its resulting mechanical characteristics (e.g., pliability and inclusions of particles). For example, UV-protection means used on the first surface of the mirror system may affect susceptibility to scratches, solvent resistance, as well as hazing or fogging of that surface. Finally, cost-efficiency of employed UV-protection and commercial availability of UV-agents and methods of UV-protection present an additional factor. Some issues of attenuation of UV-light within a range of wavelengths of particular sensitivity to some types of reflective polarizing films (e.g., wavelengths below 380 nm) and related test methods are discussed in U.S. Pat. Nos. 7,557,989 and 7,124,651 and a U.S. Patent Application No. 2009/0262422, assigned to 3M, Inc. U.S. Patent Application No. 2004/0241469 discusses, for example, protection of polyethylene napthalate articles from UV exposure and other external influences. Disclosure of each of the abovementioned patent documents is incorporated herein by reference in its entirety. In the art of automotive mirrors, discussions of light exposure and related tests and pass/fail criteria can be found in SAE J1960 and SAE J1885, which are weathering methods defined by Society of Automotive Engineers. In particular, acceptable exposure of an inside rearview mirror per SAE J1885 to radiation emitted by a xenon arc light source can be as high as 600 kJ/m2 or even 800 kJ/m2, with a resulting color change of ΔE*<3 measured in reflectance. Other cosmetic requirements may also apply such as uniformity of fading of color, or yellowing, or haziness that might occur during testing. Additional methods on material testing solutions is provided by Atlas material Testing Technology LLC and may be found at http://www.atlas-mts.com/en/client_education/client_education_event_overview/weatherometer_workshops/index.shtml.
Several technologies that may be useful for light attenuation to protect the reflective polarizer in various embodiments of the invention. Embodiments of the present invention may employ, for example, vacuum sputtered or sol-gel interferential coatings on one of the surfaces in front of the APBF as viewed by the observer. Some embodiments of these techniques are described in U.S. Patent Application No. 2002/0122962 and U.S. Pat. Nos. 5,332,618 and 7,153,578. Examples of applicable sol-gel coatings are taught, for example, in U.S. Pat. Nos. 5,371,138 and 7,288,283. Disclosure of each of the abovementioned patent documents is incorporated herein by reference in its entirety. By way of example only, such coatings may be used on surfaces I, II, III, and IV of the embodiment 838 of
In addition or alternatively, material composition of any substrate in embodiments of the invention may be modified as described, e.g., in U.S. Pat. Nos. 5,350,972 and 7,435,696, the disclosure of each of which is incorporated herein by reference in its entirety. It is understood that only those lites with modified material composition that are located in front of the APBF as viewed by the outside observer will produce the desired result of protecting the APBF from UV-component of the ambient light. In a specific embodiment, a particular substrate may include more than one component or plate one of which is made of material containing a UV-agent. For example, in reference to the embodiment 404 of
In embodiments where the APBF is located behind an electro-optic cell such as an EC-element or a cholesteric element, it is possible to dispose the UV-attenuating agents within the electro-optics cell. In reference to
Adhesive films such as PSAs and UV-curable adhesive and PVB that are used in a mirror system at locations in front of an APBF may also contain UV-absorbing agents. Although not necessary, the layers of these adhesives and PVB may be as thick as a few mils. Auxiliary polymeric films, such as those utilized to minimize UV-light transmission through residential or commercial windows may be laminated or co-laminated into an embodiment of the invention. For example, a subdivision of a prism mirror element into a wedge and a flat piece with a PVB adhesive layer is disclosed in U.S. Pat. Nos. 4,902,108 and 5,481,395. In a specific embodiment, such UV-blocking films may be employed as cladding layer(s) during the manufacture of a multilayered ABPF itself. Such a film product may have the benefit of both selective light attenuation and depolarization. It is understood that several different methods of light attenuation may be combined in order to produce desired results.
Adjustment of the overall reflectance in embodiments of the present invention may be carried out by employing laminates containing more than one APBF elements. For example, embodiments of laminates of the invention characterized in Table 6 were structured as [Glass/RP/RP/Glass].
Some applications may require a neutral spectral distribution of reflectance of the mirror assembly (such distribution may, for example, lack high purity hues). In one embodiment of the current invention the color magnitude C* may be smaller than about 15. In a related embodiment, the color magnitude may be smaller than about 10, and, in a specific embodiment, it may be most preferably less than about 5.
In some embodiments, the area of the display may be smaller than the area of the mirror element. Such embodiments are illustrated, for example, in
In addition, as discussed below, in a specific embodiment of the invention, at least some edges of the opacified areas around the perimeter of the display region may be formatted to gradually vary the transmittance of the mirror across its surface from fully transparent to fully opaque (and to accordingly gradually vary the reflectance of the mirror across its surface). Literature provides some solutions for aesthetic gradual transitions from a display area to adjacent areas have been discussed in the literature. For example, in the area of the rearview automotive mirrors the need for good match in color and reflectance has been recognized and thin-film coating-based solutions have been proposed in, e.g., commonly assigned U.S. patent application Ser. Nos. 11/713,849, 12/138,206, and 12/370,909, the disclosure of each of which is incorporated herein by reference in its entirety. A graded-thickness coating has been used in front of an APBF in, e.g., U.S. Patent Publication 2006/0164725 as a means of gradual variation of reflectance across the surface of a conventional viewing mirror employing a display. The same publication discussed additional means of hiding the edges of the display area in conventional viewing mirrors by adding a supplementary coated substrate, having a relatively high reflectance and low transmittance, in front of the APBF. Although the solution provided in U.S. 2006/0164725 facilitates concealing the edges of the display area, it suffers from the effect of parallax, whereby the spurious images are formed in reflection from the viewing mirror. Additional disadvantages of this solution stem from reduction in brightness and contrast of the display, now perceived by the viewer through the viewing mirror and the supplementary substrate. Overall, solutions proposed in prior art were recognized to be inapplicable to the field of automotive mirrors. The trade-off between a clearly discernable edge of the aperture or a parallax condition is generally recognized and no viable solution which avoids parallax and has a stealthy edge at the display area of the mirror has been realized so far. Other prior art means to adjust the reflectance (such as changing the density of reflective particles contained within a coating placed in front of the RP included in the mirror system) may result in varying haze levels (scattering from agglomerated particles within the coating) and make the edges of the aperture noticeable. In an embodiment of the present invention, the reflectance may be varied from specular to non-specular or the intensity of light reflected from the mirror may be varied or graded along the edge of the opacified area. In an embodiment of the APBF-containing rearview mirror of the present invention, depending on the size and location of the display, it may be preferred to grade either some or all of the edges of the opacified areas around the display region. The required gradations of transmittance or reflectance may be implemented by, for example, either spatially modifying the transmittance of the opacifying material itself or by patterning such material in a spatially non-uniform fashion. Such gradations may be implemented in various ways such as those described in a commonly assigned U.S. patent application Ser. No. 12/370,909. In a specific embodiment such pattern may comprise, for example, a pattern of dots created with varying spatial density.
Structurally, embodiments of the mirror system of the invention containing graded-thickness opacifying layers (also referred to as opacifying layers having a gradually changing thickness) may differ. For example, in an exemplary EC-type embodiment 884 of the invention, schematically shown in
Grading the edges of an opacifying layer as described above effectuates acceptable aesthetics of the mirror system due to the gradual transition between the transflective and opaque zones of the system. Hard-edged (abrupt) transitions between the zones of a multi-zone mirror system can also be used, provided that an adequate match of reflectance and reflected color is maintained between the zones as perceived by the viewer. Several additional examples of implementation of hard-edged transitions in embodiments of the invention are discussed further in reference to
In further reference to the structure of
In reference to
It should be noted that, in specific embodiments, the reflectance-enhancement coating may be configured so as to include a quarter-wave stack of thin-film layers such as titania (TiO2) and silica (SiO2), for example. Table 6A below provides some examples of implementation of the reflectance-enhancement coating 846 in embodiments of
Generally, a means for opacification and a means for reflectance enhancement may be combined or used alternatively in the areas of the mirror assembly outside the display area (such as areas 644 of
Various surfaces of the mirror assembly can be treated to simultaneously achieve the opacification and reflectance-enhancing effects, depending on the requirements of a given application. For instance, in an embodiment comprising an EC element in front of the reflective polarizer as viewed by the observer (see, e.g., the embodiment 836 of
Both the overall (unpolarized light) reflectance of the mirror assembly and the reflectance of light having a particular polarization depend on a material structure of the assembly. A description of a material structure of a mirror assembly can be provided, e.g., by listing material components of such a structure in the order starting from a component that is distal to the viewer towards a component that is proximal to the viewer. A structure of the embodiment 830 of
Referring again to
Table 7 shows experimentally determined reflectance and color-qualification parameters associated with various embodiments of the invention. In the following, Samples 1 through 7 are located in air (i.e., air is the incident medium). Sample 1, representing a simple mirror formed by an approximately 500 Å thick single layer of chromium on a glass substrate, has a reflectance of 57%. Sample 2 represents a laminate including a reflective polarizer (DBEF-Q film) laminated to surface IV of an EC-element (with ITO coatings on surfaces II and III) according to the method of the invention, and corresponds to the embodiment 836 of
Sample 6, discussed in reference to Table 7 and having a chromium/ruthenium bi-layer, demonstrates spectrally neutral reflectance (with a* and b* values near zero). Other metals or compounds contemplated in this embodiment may be used to provide opacification, reflectance enhancement and/or color tuning. Different metals and compounds may have different reflected colors and can therefore be used to tune the color of the coating stack in the region outside the display area as taught, for example, in U.S. patent application Ser. No. 11/833,701 (now published as U.S. 2008/0310005) and Ser. No. 12/370,909 (now published as U.S. 2009/0207513), each of which is incorporated herein in its entirety by reference.
By analogy with graded opacifying layers discussed in reference to
Color Difference=ΔC*=√{square root over ((a*−a*′)2+(b*−b*′)2)}
where (a*, b*) and (a*′,b*′) are the values describing color of light reflected by the mirror system at two different positions across the mirror.
In another example of a sample made in accordance with embodiment 884 of
The graded zone may generally consist of a single graded metal, alloy or compound, or it may consist of multiple layers selected and designed to attain desired reflectance and transmittance in the opaque region, the desired reflected color in the opaque region, and the transition behavior between the display and opaque regions. The transition region may be characterized by the rate of change of reflectance or color, or the layers may be designed to minimize the color difference between the two zones with no undesired color behavior in the transition zone.
Exemplary Embodiments for Use in Conjunction with an External Polarizing Element.
In some embodiments, light generated by the display of the embodiments is polarized, for example, when a LCD is used with a mirror assembly. In reference to the embodiments of
Typically, polarizing sunglasses employ a linear polarizer to reduce the intensity of an apparent glare originating from reflection of ambient light from various surfaces. The reflection of light is described by well-known Fresnel equations that take into account a polarization state of light. For example, polarizing sunglasses that utilize a polarizing filter with a transmission axis oriented vertically (i.e., along they-axis as seen in
In one embodiment, the light output of the display may be depolarized by a depolarizer such as a stretched polyester film, for example, or any other suitable depolarizer. The use of a depolarizer is described generally above and in detail in a commonly assigned U.S. Patent Publication 2008/0068520. As shown in
The samples described in a “Reflectance” portion of Table 9 (the “reflectance samples”) show about a 40% to 50% improvement in the extinction. Visual examination of these samples with Polaroid sunglasses showed a substantially decreased sensitivity to head tilt and, therefore, less changes due to head tilt in the reflected and transmitted light. The term head tilt refers to rotation of the polarization system of the polarizing sunglasses. The mirror system containing such samples has lower initial extinction values than the system containing samples described in “Transmittance” portion of Table 9 (the “transmittance samples”). This is due to the presence of a metal layer behind the reflective polarizer reflecting a substantial percentage of the “low” polarization state. The presence of chrome layer in “reflectance samples” adds approximately 40% more light of the low polarization state relative to the high state. This gives the initial reference system without the depolarizer an extinction value of about 26%, essentially comparable with or better than that of the system that includes a “transmission sample” and a depolarizer. The extinction value can be further reduced by substituting the chrome with a metal having higher reflectance. This, as noted above, will increase the reflectance of the system and simultaneously reduce the extinction value by adding more light in the “low” polarization state. This beneficial characteristic enables another possible embodiment—the benefits of a depolarizer can be obtained without a depolarizer in the area where the chrome, metal or other reflectance enhancement means is present and the adjustment of the LCD/reflective polarizer's polarization angle can be judicially performed to more closely match the transmitted state of the Polaroid sunglasses (as discussed above). The reflected image in the area of the display would be reduced in a commensurate amount when viewed with Polaroid sunglasses but the image in the remainder of the mirror would remain relatively high. A viewer not using Polaroid sunglasses would not be affected by this particular configuration.
In a related embodiment, the brightness of the display, perceived by the driver wearing polarizing sunglasses, may be increased by rotating the vector of polarization of the display-generated light, upon light's passing through the mirror assembly towards the driver, to make it co-linear with the transmission axis of the sunglasses. As shown in
In an alternative embodiment (not shown), it may be preferred to dispose the LCD as a whole (or, alternatively, only the polarizing components of the LCD) at a predetermined angle in an xy-plane within the rearview mirror so as to produce light emission 820 that is initially polarized along the transmission axis of the sunglasses worn by the driver. In such alternative embodiments, light 820 emitted by the LCD 639 may be p-polarized (i.e., polarized along the x-axis). If, in addition, the reflecting polarizer (which may be a part of transflective mirror assembly 1304 according to any of embodiments of the present invention) is oriented so as to maximize the transmission of the LCD light 820 through the transflective assembly, the brightness of the LCD perceived by the driver 115 through the sunglasses 1306 may be also optimized. For example, in reference to
In the following, additional embodiments of the invention are discussed and compared in reference to
In contradistinction, and as a comparative example of a commercial product produced with a reflective polarizer having unacceptable reflective optical properties, a laminate-containing reflector (formed by a display of “Miravision” mirror-television set, manufactured and sold by Philips Corporation, model number 17MW9010/37, S/N 1BZ1A0433816730, manufacture date August 2004) was also evaluated for distortions. The inside frame dimensions of the sample are indicated in a diagram of
Durability Testing.
(1) High Temperature, High Humidity, and Thermal Shock Testing.
In certain applications the laminate containing a reflective polarizer is exposed to relatively harsh environments. Automotive applications are an example of an environment that requires a component to pass stringent durability tests (environmental durability tests) for the product to be qualified for use. The durability tests vary by automotive company but there are a number of common tests a product is expected to pass. The tests are designed to ensure that a product will function adequately for the life of a vehicle. One of the tests is a so-called “high temperature/high humidity” test, where the part or component is placed in a test chamber, e.g., at approximately 85° C. and 85% humidity. (The precise temperature, humidity and duration of the test can vary depending on the requirements of an automotive company.) Another test is a “high temperature storage” test where the component is kept at about 105° C. for various lengths of time. (Four days or 96 hours is a common duration of such test.) In other tests the component is kept at lower temperature (85° C.) for up to 1,500 hours. Yet another test is a so called “thermal shock” test, where the component repeatedly undergoes heating and cooling in cycles, e.g., between −40° C. and +85° C., with 1 hour dwell, often with high humidity conditions. The hold time, ramp time, temperature extremes and number of cycles may vary depending on the requirements imposed by an automotive company. Other tests have been developed which combine the extreme conditions of the tests listed above to examine interaction effects. A failure in one or more of these tests may be sufficient to prevent a given embodiment of a fabricated component or product from being commercialized. As a result of environmental testing of various laminate embodiments of the invention it was discovered that, generally: (i) embodiments fabricated at lower levels of pressure, such as 50 psi, have decreased durability; (ii) with increase in lamination time, the durability of embodiments tends to increase; (iii) an embodiment of the laminate of the invention having both a substrate and a superstrate (such as embodiment 314 of
Specifically, comparison of environmental durability of laminates having a superstrate and those with a superstrate release was determined by fabricating and testing the samples made by laminating an APBF film between the EC-element and the third lite of glass, according to the structure of the embodiment 850 of
A similar set of experiments was directed to more completely understand the effect of a post-lamination superstrate release on the durability of a laminate of the invention. In this case, an APBF film was laminated, according to the embodiment 850 of
The following series of samples were laminated via vacuum bagging and autoclaving (the latter occurring in pressurized gas or liquid) at 200 psi and approximately 90° C. The different embodiments are contrasted using thermal storage at 105° C. and 48 hours. These particular test conditions are not meant to be limiting and subtle differences between the tests and laminates may be found with other tests or durations:
A laminate structured as [G/PSA/DBEF-Q/G], with PSA thickness of about 1 mil, resulted in good image-forming quality and retained good quality following 48 hours of 105° C. storage.
A laminate structured as [G/DBEF-Q/G], where one of the glass plates had been pretreated with a release agent (Aquapel™ available from PPG Industries, Inc.) and then removed after the lamination procedure according to an embodiment of the invention, had good initial mirror quality and retained good optical properties, i.e., image preserving reflector, following 48 hours of 105° C. storage.
The long-term stability of laminate-containing embodiments was monitored by measuring the haze within the display region of the mirror structure. According to the standards of ASTM (American Society for Testing and Materials), haze is defined as percentage of light that, during transmission through a sample, deviates by more than 2.5 degrees from the direction of the incoming beam of light. Haze measurements of laminates structured according to the embodiment 850 of
We found that fabrication, according to embodiments of the invention, of APBF-based laminates having high image-forming automotive optical quality is consistent with but not necessarily limited to laminating an APBF directly to a rigid optical substrate so as to provide a substantially direct physical contact between at least one side of the film and a surface of a rigid optical substrate. Stated differently, we unexpectedly discovered that a laminate containing substantially no or a minimal amount of initially soft curable material such as pressure-sensitive adhesive (PSA) or other curable adhesive along at least one lamination interface is very likely to satisfy the imaging quality requirements. We also found that simultaneous presence of some adhesive at both lamination interfaces (in the case of a laminate structured according to
We have also unexpectedly discovered that, for retaining a good mirror quality after 48 hours of 105° C. storage, it may be beneficial to employ embodiments of the APBF-containing laminates of the invention where at least one side of the APBF is not be directly adhered to a rigid substrate. That is, a laminate may be formed without a superstrate according to a general embodiment of
(2) Testing of Samples Employing UV-Protection Means.
The following provides examples of experimentally measured changes in reflected spectra of APBF-containing embodiments of the invention that correspond to different UV attenuation means and methods. These test results are for exposure to the weatherometer conditions utilizing light source, filters, Automatic irradiance, Black panel temperature, and Dry bulb temperature of the light cycle of SAE J1885 (relative humidity was not controlled). One hour of exposure under these conditions corresponds to a radiant exposure of roughly 2 kJ/m2 as it is calculated in various test requirements. For these examples the color values were measured using the CIE Standard D65 illuminant and a 2-degree observer.
Sample A of Table 16A included a DBEF-Q laminated between a surface of the 1.6 mm thick glass and a coated with opaque layer of Chromium surface of another lite of glass. The color change value ΔE*=6.67 after two weeks of testing which was found to be excessive for automotive purposes. Transmission spectra for 1.6 mm glass of the type used to make Sample A are shown in Table 16B and
Sample B of Table 16A included a DBEF-Q laminated between a surface of the glass prism and a coated with opaque layer of Chromium surface of another lite of glass. The corresponding color change value was ΔE*=11.37 after two weeks of testing which was found to be excessive for automotive purposes. Transmission values for prism glass of the type used to make Sample B were not measured.
Sample C of Table 16A included a DBEF-Q laminate between a surface of glass containing a UV-blocking coating ClimaGuard-SPF® (from Guardian Industries) and a coated with opaque layer of Chromium surface of another lite of glass. The color change value was, as shown in Table 16A, ΔE*=1.99 after two weeks of testing, which is acceptable for automotive purposes. Transmission values for used ClimaGuard® glass are shown in Table 16B and
Sample D of Table 16A included a DBEF-Q laminated between a treated surface of the Tru Vue Museum® glass (Tru Vue Inc.) and a coated with opaque layer of Chromium surface of another lite of glass. The color change value was ΔE*=2.50 after two weeks of testing, which is acceptable for automotive purposes. Transmission values for Tru Vue Museum® glass used are shown in Table 16B and
Sample E of Table 16A included a DBEF-Q laminate between a 1.6 mm-thick raw glass and a coated with opaque layer of Chromium surface of another lite of glass. In addition, a glass plate with an interferential coating, DSI Ultra Block™ (Deposition Sciences Inc), was placed in front of the 1.6 mm raw glass as a filter. Sample E was exposed in the weatherometer with the filter plate in place, but color measurements were taken with the filter plate removed. The measured color change value ΔE*=0.72 after 13 days of testing which is acceptable for automotive purposes. Transmission values for DSI Ultra Block™ filter plate are shown in Table 16B and
Sample F of Table 16A included a DBEF-Q laminated between the UV blocking glass from China Building Materials Academy Quartz and Special Glasses Institute and a coated with opaque layer of Chromium surface of another lite of glass. The color change value was ΔE*=0.61 after 13 days of testing which is acceptable for automotive applications. Transmission values for glass of the type used to make Sample F are shown in Table 16B and
Sample G of Table 16A included a DBEF-Q laminated between a piece of Solarphire® (PPG Inc.) and an overcoated with a bi-layer (ruthenium on top of chromium) surface of another lite of glass so as to have DBEF-Q and Ru-layers to be adjacent. The color change value was ΔE*=10.52 after 13 days of testing which is too excessive for automotive applications. Transmission values for Solarphire® glass of the type used shown in Table 16C and
Sample H of Table 16A included a DBEF-Q laminated between Solarphire PV® (PPG Inc) and an overcoated with a bi-layer (ruthenium on top of chromium) surface of another lite of glass so as to have DBEF-Q and Ru-layers to be adjacent. The color change value was ΔE*=21.53 after 13 days of testing which is excessive for automotive applications. Transmission values for Solarphire PV® glass of the type used are shown in Table 16C and
Sample I of Table 16A included a DBEF-Q laminated between Solarphire AR® (PPG Inc) and an overcoated with a bi-layer (ruthenium on top of chromium) surface of another lite of glass so as to have DBEF-Q and Ru-layers to be adjacent. The UV blocking coating of Solar4phire PV was placed towards the DBEF-Q. The color change value was ΔE*=2.78 after 13 days of testing, which is acceptable for automotive applications. Transmission values for Solarphire AR® glass are shown in Table 16C and
Sample J of Table 16A included a 1.6 mm-thick raw glass laminated to 3M PSA 8172P (3M) laminated to DBEF-Q laminated to a coated with opaque layer of Chromium lite of glass. The color change value was ΔE*=1.27 after 13 days of testing which is acceptable for automotive applications. Transmission values for a laminate of 3M PSA 8172P and two pieces of 1.6 mm glass of the type used are shown in Table 16C and
Sample K of Table 16A is of the construction of 1.6 mm raw glass laminated to DBEF-Q which is laminated to coated glass where the layer in contact with the DBEF-Q is opaque chrome with the addition of Gila Fade Control Clear (CP Films Inc) which was adhered to the front surface of the 1.6 mm glass top plate after the removal of the release liner. The color change value was ΔE*=2.16 after 13 days of testing which is acceptable for automotive applications. Transmission values for Gila Fade Control Clear with PSA and release liner used are shown in Table 16C and
Generally, in order to meet acceptable UV durability requirements in the J1885 test, it is desirable to attenuate UV light at wavelengths shorter than about 360 nm, preferably shorter than about 370 nm, more preferably shorter than about 380 nm and most preferably shorter than about 390 nm. It is preferred to attenuate more than 50% of the targeted wavelengths, more preferably more than 70% and even more preferably more than about 85%. One non-limiting criteria of sample acceptance is a color change value ΔE* that is less than 3 after 300 hours of the light on condition of J1885 which is approximately 600 kJ/m2 of exposure per the specification.
Characterization of Optical Distortion Characteristics of Exemplary Embodiments.
Table 17 shows the samples of data representing characterization of the extended distortions and the resulting optical properties of various embodiments of the invention. These results demonstrate that method of the invention allows for fabrication of embodiments that, as evidenced by SW, LW, Wa, Wb, We and Millidiopter readings, meet the optical requirements of the most demanding applications.
Characterizations were conducted with the use of wave-scan technique and by measuring the changes in optical power of the surface-under-test as discussed above. As shown, samples 1 through 3 represent inherent distortions observed in original reflective polarizer materials, and samples 4, 5, and 26 represent base-line distortions for a glass substrate, an EC-element having ITO-coatings on surfaces II and III, and an uncoated prism element, respectively. As other samples demonstrate, these inherent distortions may be compensated or reduced when the fabrication of a mirror system is carried out according to the process of the invention. In a case when the fabrication process is not adequately controlled, these inherent distortions may be magnified and translated into the final product. Samples 6 and 24 represent the properties of an embodiment 2100 structured according to [G/PSA/DBEF], see
Generally, embodiments of the invention may be configured to define a convex element, an aspheric element, a planar element, a non-planar element, an element having a wide FOV, or a combination of these various configurations in different areas to define a mirror element with generally complex shape. In case of an electrochromic rearview mirror assembly, the first surface of the first substrate may comprise a hydrophilic or hydrophobic coating to improve the operation. The embodiments of the reflective elements may comprise an anti-scratch layer on the exposed surfaces of at least one of the first and second substrates. Examples of various reflective elements are described in U.S. Pat. Nos. 5,682,267, 5,689,370, 5,825,527, 5,940,201, 5,998,617, 6,020,987, 6,037,471, 6,057,956, 6,062,920, 6,064,509, 6,111,684, 6,166,848, 6,193,378, 6,195,194, 6,239,898, 6,246,507, 6,268,950, 6,356,376, 6,441,943, and 6,512,624. The disclosure of each of these patents is incorporated herein in its entirety by reference.
Electrochromic mirror assemblies utilizing embodiments of the present invention contain an electrochromic medium that is preferably capable of selectively attenuating light traveling therethrough and preferably has at least one solution-phase electrochromic material and preferably at least one additional electroactive material that may be solution-phase, surface-confined, or one that plates out onto a surface. However, the presently preferred media are solution-phase redox electrochromics, such as those disclosed in commonly assigned U.S. Pat. Nos. 4,902,108, 5,128,799, 5,278,693, 5,280,380, 5,282,077, 5,294,376, 5,336,448, 5,808,778 and 6,020,987. The entire disclosure of each of these patents is incorporated herein in by reference. If a solution-phase electrochromic medium is utilized, it may be inserted into the chamber through a sealable fill port through well-known techniques, such as vacuum backfilling and the like. In addition, the disclosure of each of U.S. Pat. Nos. 6,594,066, 6,407,847, 6,362,914, 6,353,493, 6,310,714 is incorporated herein by reference in its entirety.
Electrochromic medium preferably includes electrochromic anodic and cathodic materials that can be grouped into the following categories:
(i) Single Layer:
The electrochromic medium is a single layer of material that may include small inhomogeneous 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. U.S. Pat. No. 6,193,912 entitled “NEAR INFRARED-ABSORBING ELECTROCHROMIC COMPOUNDS AND DEVICES COMPRISING SAME”; U.S. Pat. No. 6,188,505 entitled “COLOR STABILIZED ELECTROCHROMIC DEVICES”; U.S. Pat. No. 6,262,832 entitled “ANODIC ELECTROCHROMIC MATERIAL HAVING A SOLUBLIZING MOIETY”; U.S. Pat. No. 6,137,620 entitled “ELECTROCHROMIC MEDIA WITH CONCENTRATION ENHANCED STABILITY PROCESS FOR PREPARATION THEREOF AND USE IN ELECTROCHROMIC DEVICE”; U.S. Pat. No. 6,195,192 entitled “ELECTROCHROMIC MATERIALS WITH ENHANCED ULTRAVIOLET STABILITY”; U.S. Pat. No. 6,392,783 entitled “SUBSTITUTED METALLOCENES FOR USE AS AN ANODIC ELECTROCHROMIC MATERIAL AND ELECTROCHROMIC MEDIA AND DEVICES COMPRISING SAME”; and U.S. Pat. No. 6,249,369 entitled “COUPLED ELECTROCHROMIC COMPOUNDS WITH PHOTOSTABLE DICATION OXIDATION STATES” disclose anodic and cathodic materials that may be used in a single layer electrochromic medium, the entire disclosures of which are incorporated herein by reference. 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. Pat. No. 5,928,572, entitled “IMPROVED ELECTROCHROMIC LAYER AND DEVICES COMPRISING SAME” or International Patent Application No. PCT/US98/05570 entitled “ELECTROCHROMIC POLYMERIC SOLID FILMS, MANUFACTURING ELECTROCHROMIC DEVICES USING SUCH SOLID FILMS, AND PROCESSES FOR MAKING SUCH SOLID FILMS AND DEVICES,” and U.S. patent application Ser. No. 11/272,552 titled “Electrochromic Compounds and Associated Media and Devices and filed Nov. 10, 2005. The disclosure of each of these patent documents is incorporated herein in its entirety by reference.
The entire disclosure of each of the U.S. patent application Ser. No. 12/284,701, filed Sep. 24, 2008, entitled ULTRAVIOLET LIGHT STABILIZING COMPOUNDS AND ASSOCIATED MEDIA AND DEVICES, U.S. Pat. No. 7,428,091 entitled ELECTROCHROMIC COMPOUNDS AND ASSOCIATED MEDIA AND DEVICES, and U.S. Pat. No. 7,256,924 entitled MULTI-CELL ELECTROCHROMIC DEVICES, disclosing additional teachings related to the EC-element, is incorporated herein by reference in its entirety.
At least three electroactive materials, at least two of which are electrochromic, can be combined to give a pre-selected color as described in U.S. Pat. No. 6,020,987 entitled “ELECTROCHROMIC MEDIUM CAPABLE OF PRODUCING A PRE-SELECTED COLOR,” the entire disclosure of which is incorporated herein by reference. This ability to select the color of the electrochromic medium is particularly advantageous when designing information displays with associated elements.
The anodic and cathodic materials can be combined or linked by a bridging unit as described in International Application No. PCT/WO97/EP498 entitled “ELECTROCHROMIC SYSTEM,” the entire disclosure of which is incorporated herein by reference. It is also possible to link anodic materials or cathodic materials by similar methods. The concepts described in these applications can further be combined to yield a variety of electrochromic materials that are linked.
Additionally, a single layer medium includes the medium where the anodic and cathodic materials can be incorporated into the polymer matrix as described in International Application No. PCT/WO98/EP3862 entitled “ELECTROCHROMIC POLYMER SYSTEM,” U.S. Pat. No. 6,002,511, or International Patent Application No. PCT/US98/05570 entitled “ELECTROCHROMIC POLYMERIC SOLID FILMS, MANUFACTURING ELECTROCHROMIC DEVICES USING SUCH SOLID FILMS, AND PROCESSES FOR MAKING SUCH SOLID FILMS AND DEVICES,” the entire disclosures of which are incorporated herein by reference.
Also included is 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.
(ii) 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. Examples of this type of electrochromic medium are the metal oxide films, such as tungsten oxide, iridium oxide, nickel oxide, and vanadium oxide. A medium, which contains one or more organic electrochromic layers, such as polythiophene, polyaniline, or polypyrrole attached to the electrode, would also be considered a multilayer medium.
In addition, the electrochromic medium may also contain other materials, such as light absorbers, light stabilizers, thermal stabilizers, antioxidants, thickeners, or viscosity modifiers.
It may be desirable to incorporate a gel into the electrochromic device as disclosed in commonly assigned U.S. Pat. No. 5,940,201 entitled “AN ELECTROCHROMIC MIRROR WITH TWO THIN GLASS ELEMENTS AND A GELLED ELECTROCHROMIC MEDIUM”. The entire disclosure of this U.S. patent is incorporated herein by reference.
In at least one embodiment of a rearview mirror assembly utilizing a mirror element according to the present invention, the rearview mirror assembly is provided with an electro-optic element having a substantially transparent seal. Examples of EC-structures, substantially transparent seals and methods of forming substantially transparent seals are provided in U.S. Pat. No. 5,790,298, the entire disclosure of which is included herein by reference. U.S. Pat. Nos. 6,665,107, 6,714,334, 6,963,439, 6,195,193, 6,157,480, 7,190,505, 7,414,770, and U.S. patent application Ser. No. 12/215,712 disclose additional subject matter related to seals and seal materials. The disclosure of each of theses documents is incorporated herein by reference in its entirety.
In at least one embodiment, a mirror structure according to the invention or a rearview mirror assembly utilizing such mirror structure may include a spectral filter material and/or a bezel for protecting the associated seal from damaging light rays and to provide an aesthetically pleasing appearance. Examples of various bezels are disclosed, e.g., in U.S. Pat. Nos. 5,448,397, 6,102,546, 6,195,194, 5,923,457, 6,238,898, 6,170,956 and 6,471,362, the disclosure of each of which is incorporated herein in its entirety by reference.
As discussed above, in at least one embodiment, an embodiment of the APBF-containing laminate of the invention can be used in conjunction with a display such as an RCD, or another light source such as one generated polarized light, for example a laser source. Discussion of various displays that can be used with embodiments of the invention is provided, e.g., in U.S. Provisional Application No. 60/780,655 filed on Mar. 9, 2006; U.S. Provisional Application No. 60/804,351 filed on Jun. 9, 2006; U.S. Patent Application Publication Nos. 2008/0068520, U.S. Pat. No. 7,221,363; and U.S. patent application Ser. Nos. 11/179,798 and 12/193,426. The entire disclosure of each of these applications is incorporated herein by reference. Generally, a light source can be disposed as a stand-alone component separated from the mirror structure or it can be in physical contact with the mirror structure. An embodiment of the laminate of the invention can also be beneficially used in applications utilizing rear-projection displays utilizing laser sources, e.g. a rear-projection display by Mitsubishi Corporation described at www.lasertvnews.com/features.asp.
In at least one of embodiments, a mirror structure including an APBF-based laminate of the invention may be configured in a rearview mirror assembly that may include a glare light sensor or an ambient light sensor, which are described in commonly assigned U.S. Pat. Nos. 6,359,274 and 6,402,328. The disclosure of each of these patents is incorporated herein by reference in its entirety. The electrical output signal from either or both of these sensors may be used as inputs to a controller on a circuit board of the assembly that controls the intensity of display backlighting. The details of various control circuits for use herewith are described in commonly assigned U.S. Pat. Nos. 5,956,012; 6,084,700; 6,222,177; 6,224,716; 6,247,819; 6,249,369; 6,392,783; and 6,402,328, the disclosures of which are incorporated in their entireties herein by reference. In addition or alternatively, the rearview mirror assembly may include at least one additional device such as, without limitation, an interior illumination assembly, a voice activated system, a trainable transceiver, a microphone, a compass system, a digital sound processing system, a highway toll booth interface, a telemetry system, a moisture sensor, a global positioning system, a vehicle vision system, a wireless communication interface, a camera, a transflective reflector, a navigation system, a turn signal, and an adaptive cruise control system. These systems may be integrated, at least in part, in a common control with information displays and/or may share components with the information displays. In addition, the status of these systems and/or the devices controlled thereby may be displayed on the associated information displays.
The embodiments of the invention described above are intended to be merely exemplary; numerous variations and modifications will be apparent to those skilled in the art.
Examples of Modifications.
It is understood that an APBF-containing embodiment of the invention may be structured as any of multi-zone EC-reflectors disclosed in the Multi-Zone Mirror Application. Any such embodiment will contain various optical thin-film layers described therein that enhance the performance of the multi-zone mirror system of the invention. In particular, any of the multi-zone reflector embodiments described in the Multi-Zone Mirror Application—be it an embodiment utilizing an abrupt transition between the opaque and transflective zones of the mirror element, such as, e.g., one of the embodiments described in reference to
It is also understood that UV-protection of the polymer-based RP component of the embodiments discussed above may be achieved without employing additional UV-blocking agents but through the use of appropriately designed reflectance-enhancing layers. The following Examples A and B illustrate the performance of some thin-films coatings that, when employed in front of an APBF in one of embodiments of the invention, may allow for simultaneous optimization of reflectance-enhancement of a mirror system of the invention and minimization of transmission of UV-light through the stacks towards the APBF. Optical constants for materials used to simulate the performance of these coatings (with a reference wavelength of 250 nm and a zero-degree angle of incidence) are presented in
Table 23 lists design parameters of a thin-film stack on a glass substrate, while
Design parameters for this alternative stack on a glass substrate, affording an approximately 45% reflectance in the visible spectral region and reduced transmittance at wavelengths below 400 nm as shown in
Design parameters for this alternative stack on a glass substrate, affording an approximately 45% reflectance in the visible spectral region but providing improvement in UV-blocking as compared to the coating of Example B, as evidenced by
In comparison with Examples A and B, Example D illustrates a design of a thin-film coating that not only has UV-blocking and reflectance-enhancing properties but is also tailored to provide for preferentially high transmittance values in RGB-bands where a color display, located behind a mirror system of the invention, may operate. For the purpose of this example, the “blue” wavelength pass-band is defined by a 440-460 nm region, the “green” pass-band is defined as a 540-560 nm region, and a “red” pass-band is defined as a 630-660 nm region. Design parameters for this coating, deposited on a glass substrate, are listed in Table 26, and some optical characteristics of light (D 65, CIE 1964 observer) incident on this coating at zero degrees are shown in
The following additional Examples E and F pertain to the use of reflectance-enhancing coatings of the Examples B and D, respectively, in a transflective zone of a specific embodiment. This specific embodiment comprises, in the order viewed by the observer: 1) a 1.6 mm-thick first glass substrate with an ITO layer (150 nm) deposited on surface II, 2) an EC-medium (150 nm), 3) a 1.6 mm-thick second glass substrate with an ITO layer (150 nm) deposited on surface II, and 4) an APBF (DBEF-Q) laminated within the transflective zone between surface IV (of the second substrate) and surface V (of a 1.1 mm thick third lite of glass) that is overcoated with a reflectance-enhancing coating. In particular, in Example E, the reflectance-enhancing coating deposited on surface V is that from Example B. The transmission characteristics of the resulting embodiment are shown in
Example G corresponds to a transflective zone of an embodiment that includes, in the order viewed by the observer: 1) a 1.6 mm-thick first glass substrate with an ITO layer (150 nm) deposited on surface II, 2) an EC-medium (150 nm), 3) a 1.6 mm-thick second glass substrate with an ITO layer (150 nm) deposited on surface II, and 4) an APBF (DBEF-Q) laminated within the transflective zone between surface IV (of the second substrate) and an uncoated surface V of a 1.1 mm-thick third lite of glass. The optical characteristics of such a design are shown in Table 30. A comparison among the Examples E and F and Example G, all of which included a reflectance-enhancing coating containing forty three thin-film layers, illustrates the improvement in reflectance characteristics. Furthermore, Example F simultaneously attains UV blocking, reflectance enhancement and transmittance enhancement in the light bands of LCD. It is understood that by appropriately designing the coatings a UV blocking function may be removed from Examples D and F, leaving the coating to demonstrate reflectance enhancement and transmittance enhancement only.
The influence of material absorption on optical characteristics of the overall mirror system is illustrates in additional Examples H, I, and J. In particular, Example H provides a value for eye-weighed absorption of ambient light that has traversed a glass substrate and a half-wave-thick ITO coating deposited on one of the substrate's surfaces. Example I provides a value for eye-weighed absorption of ambient light that has traversed an EC-element comprising an EC-medium placed between two glass substrates each having one surface overcoated with a half-wave ITO-layer. Finally, Example J demonstrates eye-weighed values for polarized transmittance and unpolarized reflectance of the embodiment of Example G. Calculations of all values thus defined were done for different thicknesses of glass substrates and different absorbance values (calculated using appropriately scaled coefficients of extinction of the ITO material), as indicated in Table 31. The eye-weighing has been performed in the range between approximately 360 nm and 750 nm. The results in Table 31 clearly demonstrate the benefit of using an electrooptic element having a low absorption front of the APBF. The amount of light absorption that is acceptable in a particular embodiment may vary. Preferably, the electrooptic element will have an absorption less than 10%, more preferably less than 5% and most preferably less than 2.5%. RELs may not be needed if the absorption is properly controlled, or the RELs may contain fewer layers thus simplifying the overall structure of the assembly and reducing costs.
As an alternative embodiment of the invention and in reference to
In additional embodiments of the invention, an APBF-containing mirror system that utilizes an EC-element can be constructed with air gap(s) between an EC-cell and the APBF laminate. Such embodiments would be represented by replacing a prism 408 in embodiments of
In another alternative embodiment, described in reference to
Additionally, as has been previously discussed, once the lamination interface has been formed according to an embodiment of the method of the invention, this interface may be optionally protected from oxygen, water, or other contaminants by having the edge of the laminate sealed. If necessary, the APBF may be cut slightly smaller than the substrate and superstrate thus providing a notch therebetween for the sealing material to reside.
In other modifications, the reflectance-enhancing and opacifying layers of any multi-zone embodiment of an APBF-containing rearview mirror assembly of the invention may generally be disposed in any pre-determined order adjacent at least one of the surfaces of the structure to which the APBF is bonded, preferably adjacent a surface located between the APBF and the light source. An APBF may substantially cover only a transflective zone of the mirror structure. Alternatively, the APBF may substantially cover the FOV of the multi-zone mirror element. The transflective zone of the mirror structure may contain additional transflective layers. A light source may be part of the laminate structure or a stand-alone component. All such variations and modifications are intended to be within the scope of the present invention as defined in any appended claims.
The present application is a divisional application of U.S. patent application Ser. No. 12/774,721, filed May 5, 2010, now issued as U.S. Pat. No. 9,254,789 on Feb. 9, 2016, which is a continuation-in-part of U.S. patent application Ser. No. 12/629,757 filed on Dec. 2, 2009, now issued as U.S. Pat. No. 8,282,224 on Oct. 9, 2012, which is a continuation-in-part of U.S. patent application Ser. No. 12/496,620 filed on Jul. 1, 2009, now issued as U.S. Pat. No. 8,545,030 on Oct. 1, 2013, which claims priority from U.S. Provisional Applications Nos. 61/079,668 filed on Jul. 10, 2008 and 61/093,608 filed on Sep. 2, 2008. The present application claims priority from each of the above-mentioned applications. The disclosures of each of the above-mentioned applications are incorporated herein by reference in their entirety.
| Number | Name | Date | Kind |
|---|---|---|---|
| 2645158 | Bertell | Jul 1953 | A |
| 3473867 | Byrnes | Oct 1969 | A |
| 4039254 | Harsch | Aug 1977 | A |
| 4240709 | Hornell | Dec 1980 | A |
| 5056899 | Warszawski | Oct 1991 | A |
| 5076673 | Lynam | Dec 1991 | A |
| 5135298 | Feltman | Aug 1992 | A |
| 5179471 | Caskey | Jan 1993 | A |
| 5422756 | Weber | Jun 1995 | A |
| 5568316 | Schrenk et al. | Oct 1996 | A |
| 5631089 | Center et al. | May 1997 | A |
| 5668663 | Varaprasad et al. | Sep 1997 | A |
| 5686979 | Weber et al. | Nov 1997 | A |
| 5699188 | Gilbert et al. | Dec 1997 | A |
| 5724187 | Varaprasad et al. | Mar 1998 | A |
| 5762823 | Hikmet | Jun 1998 | A |
| 5798057 | Hikmet | Aug 1998 | A |
| 5808589 | Fergason | Sep 1998 | A |
| 5965247 | Jonza | Oct 1999 | A |
| 5986730 | Hansen | Nov 1999 | A |
| 6008871 | Okumura | Dec 1999 | A |
| 6028656 | Buhrer | Feb 2000 | A |
| 6045643 | Byker et al. | Apr 2000 | A |
| 6064508 | Forgette et al. | May 2000 | A |
| 6072549 | Faris | Jun 2000 | A |
| 6106121 | Buckley | Aug 2000 | A |
| 6111684 | Forgette et al. | Aug 2000 | A |
| 6111685 | Tench et al. | Aug 2000 | A |
| 6166847 | Tench et al. | Dec 2000 | A |
| 6166848 | Cammenga et al. | Dec 2000 | A |
| 6170956 | Rumsey et al. | Jan 2001 | B1 |
| 6188505 | Lomprey et al. | Feb 2001 | B1 |
| 6195194 | Roberts et al. | Feb 2001 | B1 |
| 6239898 | Byker et al. | May 2001 | B1 |
| 6310714 | Lomprey et al. | Oct 2001 | B1 |
| 6346698 | Turnbull | Feb 2002 | B1 |
| 6356376 | Tonar et al. | Mar 2002 | B1 |
| 6396637 | Roest | May 2002 | B2 |
| 6407847 | Poll et al. | Jun 2002 | B1 |
| 6433914 | Lomprey et al. | Aug 2002 | B1 |
| 6473143 | Li | Oct 2002 | B2 |
| 6512624 | Tonar et al. | Jan 2003 | B2 |
| 6657708 | Bechtel et al. | May 2003 | B1 |
| 6572233 | Northman et al. | Jun 2003 | B1 |
| 6594065 | Byker et al. | Jul 2003 | B2 |
| 6594067 | Poll et al. | Jul 2003 | B2 |
| 6597489 | Guarr et al. | Jul 2003 | B1 |
| 6646697 | Sekiguchi | Nov 2003 | B1 |
| 6661830 | Reed et al. | Dec 2003 | B1 |
| 6671080 | Poll et al. | Dec 2003 | B2 |
| 6672745 | Bauer et al. | Jan 2004 | B1 |
| 6674504 | Li | Jan 2004 | B1 |
| 6678083 | Anstee | Jan 2004 | B1 |
| 6700692 | Tonar et al. | Mar 2004 | B2 |
| 6710831 | Winker | Mar 2004 | B1 |
| 6759945 | Richard | Jul 2004 | B2 |
| 6797396 | Liu et al. | Sep 2004 | B1 |
| 6800871 | Matsuda et al. | Oct 2004 | B2 |
| 6842276 | Poll et al. | Jan 2005 | B2 |
| 6870655 | Northman et al. | Mar 2005 | B1 |
| 6885414 | Li | Apr 2005 | B1 |
| 6951681 | Hartley et al. | Oct 2005 | B2 |
| 6952312 | Weber et al. | Oct 2005 | B2 |
| 6977702 | Wu | Dec 2005 | B2 |
| 6999649 | Chen | Feb 2006 | B1 |
| 7096418 | Lin et al. | May 2006 | B1 |
| 7057681 | Hinata et al. | Jun 2006 | B2 |
| 7193764 | Lin et al. | Mar 2007 | B2 |
| 7215473 | Fleming | May 2007 | B2 |
| 7338177 | Lynam | Mar 2008 | B2 |
| 7362505 | Hikmet et al. | Apr 2008 | B2 |
| 7379243 | Horsten et al. | May 2008 | B2 |
| 7495719 | Adachi et al. | Feb 2009 | B2 |
| 7502156 | Tonar et al. | Mar 2009 | B2 |
| 7528906 | Robinson | May 2009 | B2 |
| 7551354 | Horsten et al. | Jun 2009 | B2 |
| 7567291 | Bechtel et al. | Jul 2009 | B2 |
| 7633567 | Yamada et al. | Dec 2009 | B2 |
| 7656586 | Rosario | Feb 2010 | B2 |
| 7728927 | Nieuwkerk | Jun 2010 | B2 |
| 7787077 | Kongoh et al. | Aug 2010 | B2 |
| 7903335 | Nieuwkerk | Mar 2011 | B2 |
| 7916380 | Tonar et al. | Mar 2011 | B2 |
| 20030189754 | Sugino et al. | Oct 2003 | A1 |
| 20040229049 | Kobayashi et al. | Jun 2004 | A1 |
| 20040241469 | McMan et al. | Dec 2004 | A1 |
| 20040251804 | McCullough et al. | Dec 2004 | A1 |
| 20050024591 | Lian et al. | Feb 2005 | A1 |
| 20050259326 | Weber et al. | Nov 2005 | A1 |
| 20060007550 | Tonar et al. | Jan 2006 | A1 |
| 20060274218 | Xue | Dec 2006 | A1 |
| 20070041096 | Nieuwkerk et al. | Feb 2007 | A1 |
| 20070146481 | Chen | Jun 2007 | A1 |
| 20070183037 | De Boer | Aug 2007 | A1 |
| 20080002106 | Van Der Witte | Jan 2008 | A1 |
| 20080068520 | Minikey et al. | Mar 2008 | A1 |
| 20080106705 | Cortenraad et al. | May 2008 | A1 |
| 20080247169 | Zou et al. | Oct 2008 | A1 |
| 20090015736 | Weller | Jan 2009 | A1 |
| 20090033837 | Molsen et al. | Feb 2009 | A1 |
| 20090040465 | Conner et al. | Feb 2009 | A1 |
| 20090040588 | Tonar et al. | Feb 2009 | A1 |
| 20090040778 | Takayanagi et al. | Feb 2009 | A1 |
| 20090096937 | Bauer et al. | Apr 2009 | A1 |
| 20090258221 | Diehl et al. | Oct 2009 | A1 |
| 20090262422 | Cross et al. | Oct 2009 | A1 |
| 20090296190 | Anderson et al. | Dec 2009 | A1 |
| 20100110553 | Anderson et al. | May 2010 | A1 |
| 20120002121 | Pirs | Jan 2012 | A1 |
| Number | Date | Country |
|---|---|---|
| 0299509 | Jun 1995 | EP |
| 2008870 | Dec 2008 | EP |
| 1376207 | Jun 2009 | EP |
| 199838547 | Sep 1998 | WO |
| 2003021343 | Mar 2003 | WO |
| 2003079318 | Sep 2003 | WO |
| 2004100534 | Nov 2004 | WO |
| 2005024500 | Mar 2005 | WO |
| 2005045481 | May 2005 | WO |
| 2005050267 | Jun 2005 | WO |
| 2005071645 | Aug 2005 | WO |
| 2005071646 | Aug 2005 | WO |
| 2007053710 | May 2007 | WO |
| Entry |
|---|
| Peter Andersson, “Switchable Optical Polarizer Based on Electrochromism in Stretch-Aligned Polyaniline,” Applied Physics Letters, Aug. 18, 2003, 3 pages, vol. 83, No. 7, American Institute of Physics, Britian. |
| Reda Hsakou, “Curvature: The Relevant Criterion for Class-A Surface Quality,” JEC Composites Magazine, Mar. 23, 2006, 4 pages, No. 23. |
| Cardinal LG, “Optical Distortion in Sea-Storm Laminated Glass Fabricated with an Encapsulated PET Film,” Cardinal Glass Industries Company, May 2008, 1 page, bulletin #LG02. |
| Viracon, “Laminated Glass Product Standards,” printed off-line on May 13, 2008, 3 pages, www.viracon.com/laminatedStandards.html. |
| 3M Vikuiti, “Energy Efficient Displays,” printed off-line on Jul. 9, 2008, 2 pages, http://solutions9.3m.com/wps/portal/3M/en_US/Vikuiti1/BrandProducts/main/energyefficie . . . . |
| Tian AN HK TDG Co., “Thermal Film,” printed off-line Dec. 8, 2008, 2 pages, http://www.tiananhk.com/products/EVABOPPFILM/index.html. |
| Isra Vision AG, “Machine Vision,” printed off-line Jun. 11, 2009, 1 page, http://www.isravision.com/likecms.php?site=site.html&dir=isra&nav=156. |
| Nguyen, Thong, Office Action in U.S. Appl. No. 12/496,620 dated Jul. 27, 2012, 46 pages, United State Patent and Trademark Office. |
| Authorized Officer Blaine R. Copenheaver, International Search Report and the Written Opinion of the International Searching Authority, International Application No. PCT/US/2009/049458, dated Sep. 9, 2009, 9 pages. |
| Authorized Officer Blaine R. Copenheaver, International Search Report of the International Searching Authority, International Application No. PCT/US2010/058529, Feb. 2, 2011, 4 pages. |
| Authorized Officer Blaine R. Copenheaver, International Written Opinion of the International Searching Authority, International Application No. PCT/US2010/058529, Feb. 2, 2011, 6 pages. |
| Authorized Officer Blaine R. Copenheaver, International Written Opinion of the International Searching Authority, International Application No. PCT/US09/49458, Apr. 27, 2011, 7 pages. |
| Authorized Officer Blaine R. Copenheaver, International Preliminary Report on Patentability, International Application No. PCT/US09/49458, Dec. 13, 2011, 22 pages. |
| Steve Jurichich, PhD, “Summary of the TFT LCD Materials Report,” date printed unknown, Display Search, www.displaysearch.com/products/samples/execsummary-materials.pdf. |
| BYK—Gardner USA, “Orange Peel/DOI,” description of wave-scan dual, date printed unknown, 4 pages, www.analis.be/filesIVprodFilesl1529/bykwavescandual.pdf. |
| Visuol Technologies, “Development of a Tool to Measure Bond-Line Read-Through Defects,” date printed unknown, 20 pages, http://www.visuol.com/upload/4diel_AdvertisingBrochure_Ondulo.pdf. |
| Number | Date | Country | |
|---|---|---|---|
| 20160193963 A1 | Jul 2016 | US |
| Number | Date | Country | |
|---|---|---|---|
| 61079668 | Jul 2008 | US | |
| 61093608 | Sep 2008 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12774721 | May 2010 | US |
| Child | 14980085 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12629757 | Dec 2009 | US |
| Child | 12774721 | US | |
| Parent | 12496620 | Jul 2009 | US |
| Child | 12629757 | US |
