Stacked assembly for providing targeted transmitted color and targeted reflected color

Abstract

The present invention relates to a laminated assembly comprising: a variable transmittance layer having first and second faces facing opposite sides; at least a first reflectance color-balance layer located on the first side of the variable transmittance layer; and a transmittance color-balance layer located on the first or second face of the variable transmittance layer. The variable transmittance layer may be variable between a dark state and a bright state, which may have a dark state transmittance spectrum when in a dark state and a different bright state transmittance spectrum when in a bright state.

Description

Technology Field

[0001] The present invention generally relates to a laminated assembly that is a variable transmittance filter. The assembly is also designed to exhibit an optimal reflective color. The assembly may include one or more coatings. Background Technology

[0002] Variable transmittance windows allow electromagnetic radiation transmitted through the window to be selectively filtered. For example, when integrated into a vehicle, such as a sunroof or passenger window, the variable transmittance window can influence parameters such as the light intensity inside the vehicle by controlling one or both of the intensity and wavelength of electromagnetic radiation entering and leaving the vehicle.

[0003] Some prior art in the art includes Guardian Glass W02018075005A1 or US20190248700A1, which describe a gray coated article having an absorbent layer and a low-e coating having low visible transmittance. Additionally, Guardian Glass's US20170267579A1 and US10247855 describe a gray heat-treatable coated product having a low solar factor value. SWITCH Materials Inc.'s US9588358 describes an optical filter comprising a variable transmittance layer that addresses achieving a target transmittance color.

[0004] Variable transmittance optical filters can utilize various techniques to alter visible light transmittance. Generally, these filters can switch between a higher light transmittance state (faded or bright state) and a lower light transmittance state (dark state) depending on the application, removal, or reduction of stimuli such as UV light, temperature, and / or voltage. Examples of techniques used in variable transmittance windows include photochromic, electrochromic, thermochromic, chemochromic, piezochromic, liquid crystal, or suspended particles. Some photochromic materials can darken in response to light, such as ultraviolet light, and return to a faded state when UV light is removed or reduced. Some electrochromic materials can darken upon the application of voltage and return to a faded state when the voltage is removed; alternatively, some electrochromic materials can darken in response to the application of a voltage of first polarity and fade when a voltage of opposite polarity is applied. Some thermochromic materials can darken in proportion to an increase in temperature; for example, the warmer the material becomes, the darker it may appear. Thermochromic materials may return to a faded state when the temperature decreases. Some chemochromic materials can darken or lighten in response to chemical changes in the environment, such as hydrogen gas, pH, or ion concentration. Some piezoelectric materials can darken or lighten depending on changes in pressure or mechanical stress. Liquid crystal materials and floating particle devices include crystals or particles that change their orientation in response to the application of voltage. In the absence of voltage, the crystals or particles are randomly oriented, scattering incident light to appear opaque or transmit very little light. When voltage is applied, the crystals or particles are aligned by an electric field, allowing light to be transmitted. If a variable transmittance optical filter includes an electrochromic aspect, the variable transmittance optical filter includes an electrical connector for connecting the optical filter to a control circuit, said control circuit provides power to the optical filter to cause an electrochemical color change.

[0005] Depending on the characteristics and application of the variable transmittance optical filter, additional attenuation of transmitted light or solar energy may be desirable. When the variable transmittance optical filter is used in windows of vehicles, aircraft, or buildings, reducing or blocking the transmission of infrared rays may be useful for controlling heat gain, and reducing or blocking the transmission of ultraviolet rays may be useful for protecting occupants of the vehicle or building. If impact protection is desired, it may be useful to include laminated glass ("safety glass") in the window.

[0006] Laminated glass having a neutral or gray transmittance color that simultaneously exhibits a neutral or gray reflective color is known, and US20170267579A1 and WO2018075005A1 describe coated articles designed to realize gray glass surface reflective coloring in combination with a low solar factor and / or a low solar heat gain factor. However, these applications do not mention a method for adjusting color in a window having variable light transmittance in the visible range.

[0007] Laminated glass having a tint or coloring is known, and US 4244997 and US 2009 / 0303581 describe laminated glass having a shade band, and US 7655314 describes laminated glass having an intermediate layer comprising an IR blocking component and a coloring agent that complements the yellow-green appearance of the IR blocking component, but does not mention a method for color adjustment in a window having variable light transmission in the visible range. Tinted glass with gray, bronze, or green tones may also be used to attenuate light transmitted through a window. Some tints can attenuate light almost evenly across the visible light spectrum, which can be effective in reducing overall glazing, but if the components of the laminated glass itself are colored, they may not provide color "correction" to a neutral tone and additional color correction may be required.

[0008] When laminated glass contains variable transmittance components, light transmittance may be excessive or color distortion may occur in either the faded or darkened states, or both. Similarly, for reflected light, it is difficult to tandem-balance the transmitted color (e.g., the color of the laminated assembly as observed by the eye regarding reflected light) with the desired neutral color while achieving a neutral color (e.g., the color of the laminated assembly as observed by the eye regarding light passing through the assembly). Previously, color balance in glazing products, such as automotive sunroofs and architectural windows, was achieved by altering the chemical composition of the glass itself to provide the desired color or by including a colored intermediate layer (e.g., PVB) between two glass sheets. Changing the color of variable transmittance filters is much more difficult because the materials used to generate variable transmittance cannot be easily changed to a different color while maintaining all variable transmittance characteristics. For example, since some variable transmittance filters are blue, they may be suitable for some applications but not others. Currently, even if that color does not appear to be the most desirable to the product's customers and potential customers, the overall color of the product is determined by the color of the variable transmittance filter. Including one or more additional visible light filters can further attenuate transmitted light, but it may also distort colors or worsen already distorted colors.

[0009] US9588358 describes an optical filter comprising a variable transmittance layer having a first spectrum in a dark state and a second spectrum in a faded state, and a color-balance layer having a third spectrum. When the dark state spectrum is combined with the spectrum of the color-balance layer, the resulting transmitted spectrum approximates the dark state target color. Similarly, the bright state spectrum is combined with the color-balance layer such that the resulting transmitted spectrum approximates the target bright state color. US9588358 does not provide any teaching or guidance on how to optimize the reflected color of the optical filter. An additional light attenuation layer may be included in the stack, and the optical filter may comprise a portion of laminated glass.

[0010] In one embodiment, the present invention relates to a laminated assembly comprising: a variable transmittance layer having first and second faces facing opposite directions; at least a first reflectance color-balance layer located on a first side of the variable transmittance layer; and a transmittance color-balance layer located on a first or second face of the variable transmittance layer. The laminated assembly of the present invention may further comprise a second reflectance color-balance layer on a side of the variable transmittance layer opposite to the first reflectance color-balance layer.

[0011] In another aspect, the present invention relates to a multilayer composition comprising a variable transmittance optical filter layer and one or more color-balanced layers selected to be combined with the color of the variable transmittance optical filter to achieve a desired transmittance color and a desired reflectance color. A laminated glass window having variable light transmittance, which provides a target (e.g., neutral) transmittance color in a faded state, a dark state, or both a faded state and a dark state, and provides a target (e.g., neutral) reflectance color in series in a faded state, a dark state, or both a faded state and a dark state, represents a useful addition throughout the art and may be used in automotive windows (windshields, sunroofs, moonroofs, windows, backlights, sidelights, etc.), other transportation applications such as trains and buses, architectural applications, eyeglasses and ophthalmic devices or applications, etc.

[0012] Other aspects are additionally disclosed and claimed herein. Brief explanation of the drawing

[0013] These and other features will become more apparent from the following description with reference to the attached drawings. Numbers are for illustrative purposes only and may not represent relative proportions or scales unless otherwise specified. FIG. 1 shows a cross-sectional view of a stacked assembly according to one embodiment. FIG. 2 illustrates a cross-sectional view of a stacked assembly according to another embodiment. FIG. 3 illustrates an exploded schematic diagram of a laminated assembly showing reduced levels of light transmission and reflection with an added color-balance layer. Figure 4 illustrates a color-balanced layer in the form of a layered composite coating. Figure 5 illustrates a color-balanced layer in the form of a layered composite coating. FIG. 6 illustrates a monotone L*a*b* color wheel having a target transmittance color range with a variable transmittance layer in a dark state. Figure 7 illustrates a monotone L*a*b* color wheel having a target transmittance color range with a variable transmittance layer in a bright state. FIG. 8 illustrates a monotone L*a*b* color wheel having a target reflection color range with a variable transmittance layer in a dark state. FIG. 9 illustrates a monotone L*a*b* color wheel with a target reflection color range having a variable transmittance layer in a bright state. Specific details for implementing the invention

[0014] Accordingly, in one embodiment, the present invention comprises a variable transmittance layer having first and second faces facing opposite directions; a reflectance color-balance layer located on one side of the variable transmittance layer; and a transmittance color-balance layer located on the first face or the second face of the variable transmittance layer. The laminated assembly may further comprise a second reflectance color-balance layer on the side of the variable transmittance layer opposite the first reflectance color-balance layer. At least one of the first reflectance color-balance layer and the transmittance color-balance layer may comprise, for example, a colored polymer or a plurality of colored films.

[0015] As defined in this specification, the description of transmittance and reflectance is intended to include transmittance and reflectance in either one direction or both directions. Those skilled in the art will readily understand that it is not necessary for the stacked assembly to satisfy all parts of the description of the invention in both directions for the practice of the invention.

[0016] In one embodiment, the laminated assembly of the present invention may further comprise a first polymer layer, such as PVB, on a first side of the laminated assembly, and a second polymer layer, such as PVB, on a second side of the laminated assembly. In another embodiment, at least one of the first and second polymer layers comprises a PVB coating on PET. In a further embodiment, the laminated assembly may further comprise an IR-blocking layer.

[0017] In another embodiment, the laminated assembly of the present invention may include a variable transmittance layer, a reflectance color-balance layer, and a polymer-based layer in which the transmittance color-balance layer is laminated internally, wherein the reflectance color-balance layer may be immediately adjacent to the polymer-based layer.

[0018] The laminated assembly may, in some cases, additionally include a glass plate or other rigid substrate laminated to the side facing opposite the polymer-based layer or to the side facing opposite the polymer-based layer.

[0019] In various embodiments, the variable transmittance layer may be variable between a dark state and a bright state; the variable transmittance layer may have a dark state transmittance spectrum when in a dark state and a different bright state transmittance spectrum when in a bright state; the dark state transmittance spectrum and the transmittance spectrum for the color-balance layer are selected such that when the variable transmittance layer is in a dark state, the transmitted color of the laminated assembly approximates the target transmitted color and the reflected color of the laminated assembly approximates the target reflected color in response to visible light incident on the reflectance color-balance layer; and the variable transmittance layer is preferably not opaque.

[0020] In another embodiment, the variable transmittance layer is variable between a dark state and a bright state; the variable transmittance layer may have a dark state transmittance spectrum when in a dark state and a different bright state transmittance spectrum when in a bright state; the bright state transmittance spectrum and the transmittance spectrum for the color-balance layer are selected such that when the variable transmittance layer is in a bright state, the transmitted color of the stacked assembly approximates the target transmitted color and the reflected color of the stacked assembly approximates the target reflected color in response to visible light incident on the reflectance color-balance layer.

[0021] In certain embodiments, the reflectance color-balance layer may be located within or directly beneath the outer glass layer. In other embodiments, the target transmitted color and the target reflected color are nearly neutral.

[0022] Accordingly, the target transmittance color in a dark state may have an a* value of -13 to +13 and a b* value of -20 to +3, or an a* value of -10 to +10 and a b* value of -15 to +3, or an a* value of -4 to +4 and a b* value of -7 to +3. Additionally, the target transmittance color in a bright state may have an a* value of -6 to +10 and a b* value of -4 to +24, or an a* value of -5 to +8 and a b* value of -3 to +18, or an a* value of -4 to +4 and a b* value of -2 to +8. According to the present invention, the target reflectance color in a dark state may have an a* value of -10 to +22 and a b* value of -9 to +9, or an a* value of -4 to +19 and a b* value of -5 to +6, or an a* value of -2 to +15 and a b* value of -2 to +6. Additionally, the target reflection color in a bright state may have an a* value of -10 to +23 and a b* value of -2 to +22, or an a* value of -6 to +18 and a b* value of -2 to +16, or an a* value of -2 to +16 and a b* value of -2 to +12.

[0023] In the embodiments, compared to the color without the color-balance layer, the actual transmitted color may have a delta C of 20 or less, or 15 or less, or at least 5, or at least 10, and compared to the color without the actual color-balance layer, the actual reflected color also has a delta C of 20 or less, or 15 or less, or at least 5, or at least 10.

[0024] In embodiments, the variable transmittance layer may be a photochromic, electrochromic, thermochromic, liquid crystal material, chemochromic, piezochromic, floating particle device, or any combination thereof. In embodiments, the variable transmittance layer comprises a photochromic / electrochromic switching material.

[0025] In embodiments, the variable transmittance layer may be able to transition from a faded state to a dark state when exposed to electromagnetic radiation, and from a dark state to a faded state depending on the application of voltage.

[0026] In embodiments, the laminated assembly has an LT of less than about 1%, or less than about 2%, or less than about 5%, or less than about 10% in a dark state. A It may have an LT of more than about 5%, more than about 10%, more than about 15%, or more than about 20% in a faded state. In embodiments, the laminated assembly has an LT of more than about 5%, more than about 10%, more than about 15%, or more than about 20% in a faded state. A It may have. In embodiments, the transmission haze through the laminated assembly is 5% or less, 3% or less, 2% or less, or 1% or less.

[0027] In some embodiments, at least one of the reflectance color-balance layer and the transmittance color-balance layer comprises a layered optical product comprising a polymer substrate and a composite coating, wherein the composite coating comprises a first layer comprising a polyionic binder and a second layer comprising insoluble particles of electromagnetic energy-absorbing properties, and each of the first layer and the second layer comprises a binder component, and together they form a complementary binder pair. In such embodiments, the composite coating has a total thickness of 5 nm to 300 nm. The first layer may be immediately adjacent to the polymer substrate on its first face, and the second layer may be immediately adjacent to the first layer on the opposite face. The particles of electromagnetic energy-absorbing properties may comprise a fine particulate pigment, and their surface comprises the binder component of the second layer. In a specific embodiment, the laminated assembly may further comprise a second composite coating, said second composite coating comprising a first layer comprising a polyionic binder and a second layer comprising electromagnetic energy-absorbing particles, wherein the first layer of the second composite coating and the second layer of the second composite coating comprise complementary binder pairs. In a specific embodiment, the second layer of the first composite coating and the second layer of the second composite coating are combined to provide an additional effect on electromagnetic energy absorption properties and an effect of an electromagnetic energy-absorbing optical product. In a specific embodiment, the polymer substrate may be a polyethylene terephthalate film and may further comprise a UV-absorbing material. In embodiments, the polymer substrate may be an undyed transparent polyethylene terephthalate film. In embodiments, the electromagnetic energy-absorbing particles of the second layer of the first composite coating and the electromagnetic energy-absorbing particles of the second layer of the second composite coating each comprise a pigment.In embodiments, the electromagnetic energy-absorbing particles of the second layer of the first composite coating and the electromagnetic energy-absorbing particles of the second layer of the second composite coating provide an additional effect on the visually perceived color of the optical product. These layers may be formed from an aqueous solution.

[0028] In one embodiment, a layer-by-layer optical product of a laminated assembly may be formed by a method comprising the steps of: applying a first coating composition comprising a polyionic binder to a polymer substrate to form a first layer; and applying a second coating composition comprising one or more pigments to the first layer to form a second layer, wherein each of the first layer and the second layer comprises a binder component and together form a complementary binder pair. As mentioned, the electromagnetic energy-absorbing particle may be a pigment, and the surface of the pigment may comprise the binder component of the second layer. Additionally, at least one of the first coating composition and the second coating composition may be an aqueous dispersion or solution. The application steps a) and b) described immediately prior are typically performed at ambient temperature and pressure.

[0029] In another embodiment, the present invention relates to a laminated assembly comprising: a variable transmittance layer having opposing first and second faces; a transmittance color-balance layer located on the first face of the variable transmittance layer; a first reflectance color-balance layer located on the first face of the variable transmittance layer and located outboard of the transmittance color-balance layer; and a second reflectance color-balance layer located on the second face of the variable transmittance layer. The present invention may further comprise a polymer-based layer in which the variable transmittance layer, the reflectance color-balance layer, and the transmittance color-balance layer are laminated, wherein the reflectance color-balance layer may be immediately adjacent to the polymer-based layer. The present invention may further comprise other rigid substrates, such as plate glass or polycarbonate, laminated to faces opposite to the polymer-based layer.

[0030] In embodiments, the variable transmittance layer may be variable between a dark state and a bright state; the variable transmittance layer may have a dark state transmittance spectrum when in a dark state and a different bright state transmittance spectrum when in a bright state; and the dark state transmittance spectrum and the transmittance spectrum for the color-balance layer are selected such that when the variable transmittance layer is in a dark state, the transmittance color of the laminated assembly has an a* value of -13 to +13 and a b* value of -20 to +3 in response to visible light incident on the reflectance color-balance layer.

[0031] In another embodiment, the variable transmittance layer may be variable between a dark state and a bright state; the variable transmittance layer may have a dark state transmittance spectrum when in a dark state and a different bright state transmittance spectrum when in a bright state; the bright state transmittance spectrum and the transmittance spectrum for the color-balance layer are selected such that when the variable transmittance layer is in a bright state, the transmitted color of the laminated assembly in response to visible light incident on the reflectance color-balance layer has an a* value of -6 to +10 and a* value of -4 to +24, or an a* value of -5 to +8 and a* value of -3 to +18, or an a* value of -4 to +4 and a* value of -2 to +8.

[0032] In embodiments, the transmitted color may have an a* value of -10 to +10 and a b* value of -15 to +3, or the transmitted color may have an a* value of -4 to -4 and a b* value of -7 to +3.

[0033] In embodiments, the variable transmittance layer may be variable between a non-opaque dark state and a bright state; the variable transmittance layer may have a dark state transmittance spectrum when in a dark state and a different bright state transmittance spectrum when in a bright state; the bright state transmittance spectrum and the transmittance spectrum for the color-balance layer are selected such that when the variable transmittance layer is in a bright state, the transmitted color of the laminated assembly has an a* value of -6 to +10 and a b* value of -4 to +24 in response to visible light incident on the reflectance color-balance layer, or the transmitted color may have an a* value of -5 to +8 and a b* value of -3 to +18, or the transmitted color may have an a* value of -4 to +4 and a* value of -2 to +8.

[0034] In embodiments, the variable transmittance layer may be variable between a non-opaque dark state and a bright state; the variable transmittance layer may have a dark state reflectance spectrum when in a dark state and a different bright state reflectance spectrum when in a bright state; the dark state reflectance spectrum and the reflectance spectrum for the color-balance layer are selected such that when the variable transmittance layer is in a dark state, the reflective color of the laminated assembly has an a* value of -10 to +22 and a b* value of -9 to +9 in response to visible light incident on the reflective color-balance layer, or the reflective color has an a* value of -4 to +19 and a* value of -5 to +6, or the reflective color has an a* value of -2 to +15 and a* value of -2 to +6.

[0035] In an embodiment of the present invention, the variable transmittance layer is variable between a non-opaque dark state and a bright state; the variable transmittance layer has a dark state reflectance spectrum when in a dark state and a different bright state reflectance spectrum when in a bright state; the bright state reflectance spectrum and the reflectance spectrum for the color-balance layer are selected such that when the variable transmittance layer is in a bright state, the reflective color of the laminated assembly has an a* value of -10 to +23 and a b* value of -2 to +22 in response to visible light incident on the reflective color-balance layer, or the reflective color has an a* value of -6 to +18 and a b* value of -2 to +16, or the reflective color has an a* value of -2 to +16 and a* value of -2 to +12.

[0036] Accordingly, in one embodiment, the present invention comprises a variable transmittance layer having first and second faces facing opposite directions; a reflectance color-balance layer located on the first face of the variable transmittance layer; and a transmittance color-balance layer located on the first face or the second face of the variable transmittance layer. In certain embodiments, it is important to note that the variable transmittance layer may be deposited directly on glass, such as the exterior glass of a vehicle, for example. In this case, the reflectance color-balance layer and the transmittance color-balance layer may both be on the same face of the variable transmittance layer, wherein preferably the reflectance color-balance layer is located closest to the viewer, i.e., the driver.

[0037] In one embodiment, the present invention provides a multilayer composition comprising a variable transmittance layer which may be a variable transmittance optical filter having at least a first transmission spectrum and a first reflection spectrum in a dark state, and a second transmission spectrum and a second reflection spectrum in a decolorized state, and one or more color-balanced layers each having a transmission spectrum and a reflection spectrum; each spectrum includes a UV portion, a visible portion, and an IR portion; and the spectra of the layers combined provide a color of the multilayer composition that approximates a target transmitted color in a dark state and a target reflected color in a dark state and a bright state. The present invention also provides, in one embodiment, a laminated glass comprising such a multilayer composition. The present invention also provides, in one embodiment, an automotive glazing or architectural glazing comprising the multilayer composition or the laminated glass. The multilayer composition may further comprise one or more of a light attenuation layer, a UV blocking layer, and an IR blocking layer.

[0038] Definitions and Terms

[0039] When it is said that light or energy is "blocked," regardless of whether it is visible, UV, or IR, the term is intended to include not only absorbed and reflected light but also any light within the wavelength range scattered by optical products.

[0040] A spectrum refers to the characteristic light transmission or reflection of a multilayer composition or its components according to various modes and embodiments. The transmitted light will typically have UV, visible, and IR components or portions. Spectra from various layers can be mathematically combined, and the visible region of the generated spectrum can be described by reference to color (e.g., L*a*b* values, RGB, etc.).

[0041] A variable transmittance layer or variable transmittance optical filter is a layer capable of adjusting or changing the transmittance of electromagnetic radiation of any wavelength, such as UV, visible light, or infrared, as a function of, for example, a material or physical stimulus. Physical stimuli include mechanical, pressure, electromagnetic radiation, heat, chemical, or electrical stimuli.

[0042] As mentioned, these layers or filters may use various techniques to change transmittance. Generally, such filters can switch between a higher light transmittance state (faded or bright state) and a lower light transmittance state (dark state) upon the application, removal, or reduction of stimuli such as UV light, temperature, and / or voltage. Examples of techniques used in variable transmittance windows include photochromic, electrochromic, polarimetric, thermochromic, chemochromic, liquid crystal, or suspended particles. Some photochromic materials can darken in response to light, such as ultraviolet light, and return to a faded state when UV light is removed or reduced. Some electrochromic materials can darken in response to the application of voltage and return to a faded state when the voltage is removed; alternatively, some electrochromic materials can darken in response to the application of a voltage of first polarity and fade when a voltage of opposite polarity is applied. Some thermochromic materials can darken proportionally in response to a rise in temperature; for example, the warmer the material becomes, the darker it may appear. Thermochromic materials can return to a discolored state when the temperature decreases. Liquid crystal materials and floating particle devices include crystals or particles that change their orientation in response to the application of voltage. In the absence of voltage, liquid crystal molecules or particles are randomly oriented and absorb or scatter incident light, appearing dark, bright, or opaque, or transmitting almost no light. When voltage is applied, liquid crystal molecules or particles align according to the electric field, allowing light to be absorbed or transmitted to different degrees. If a variable transmittance optical filter includes an electrochromic mode, the variable transmittance optical filter may include an electrical connector for connecting the optical filter to a control circuit, and the control circuit provides power to the optical filter to perform the electrochromic color change.

[0043] Accordingly, a variable transmittance optical filter or layer is an optical filter with different transmittance or transmission, wherein the transmittance may be in one state (e.g., dark state) under a specific set of conditions and in a second state (e.g., bright state) under a different set of conditions. An intermediate state is also possible. Some examples of variable transmittance filters include electrochromic optical filters, photochromic optical filters, photochromic / electrochromic optical filters, floating particle devices, liquid crystal devices, thermochromic optical filters, etc., as described in the prior art. According to some embodiments of the present invention, a variable transmittance optical filter is based on a photochromic / electrochromic material that darkens when exposed to electromagnetic radiation ("light") and fades when a voltage is applied to the material. Some photochromic / electrochromic materials may fade when light of a selected wavelength is incident on a switching material.

[0044] The variable transmittance optical layer will provide a stacked assembly having a desired or targeted transmittance color that is typically nearly neutral. For example, in a dark state, the target transmittance color of the stacked assembly may have an a* value of -13 to +13 and a b* value of -20 to +3, or an a* value of -10 to +10 and a b* value of -15 to +3, or an a* value of -4 to +4 and a b* value of -7 to +3. Additionally, in a bright state, the target transmittance color may have an a* value of -6 to +10 and a b* value of -4 to +24, or an a* value of -5 to +8 and a b* value of -3 to +18, or an a* value of -4 to +4 and a b* value of -2 to +8.

[0045] When describing other layers described herein, such as the variable transmittance layer or color-balance layer of the present invention, as having first and second sides facing opposite directions, the numbering of these sides may be entirely arbitrary unless the context clearly requires otherwise.

[0046] One or more color-balance layers of the present invention will each have a transmission and a reflection spectrum. These color-balance layers are intended to balance the color of the laminated assembly, for example, that occurs in the variable transmittance layer. These color-balance layers may be polymer films, for example, such as PVB, or may be deposited on or incorporated therein onto plate glass or a polymer film when present in the assembly or stack of the present invention. Thus, the reflectance color-balance layer preferably affects the reflected color of the laminated assembly, whereas the transmittance color-balance layer preferably affects the transmitted color of the laminated assembly of the present invention and the color of an object illuminated by light passing through the variable transmittance layer. It is understood that the reflectance color-balance layer will be most effective in preferably affecting the reflected color of the laminated assembly of the present invention when it is positioned closest to the observer.

[0047] According to the present invention, the laminated assembly of the present invention may further exhibit a target reflection color in a dark state having an a* value of -10 to +22 and a b* value of -9 to +9, or an a* value of -4 to +19 and a b* value of -5 to +6, or an a* value of -2 to +15 and a b* value of -2 to +6. Additionally, the target reflection color in a bright state may have an a* value of -10 to +23 and a b* value of -2 to +22, or an a* value of -6 to +18 and a b* value of -2 to +16, or an a* value of -2 to +16 and a b* value of -2 to +12.

[0048] In another embodiment, the actual transmitted color compared to the target transmitted color may have a delta C of 20 or less, and the actual reflected color compared to the target transmitted color may also have a delta C of 20 or less.

[0049] In another aspect of the present invention, the laminated assembly has an LT of less than about 1%, or less than about 2%, or less than about 5%, or less than about 10% in a dark state. A It may have. In addition, the laminated assembly has an LT exceeding approximately 5%, approximately 10%, approximately 15%, or approximately 20% in a faded state. A It may have. In another embodiment, the transmission haze through the laminated assembly may be 5% or less, 3% or less, 2% or less, or 1% or less.

[0050] With respect to the variable transmittance layer described above, it will be understood that such variable transmittance layer typically has at least first and second surfaces, and that a color-balance layer will advantageously be located on one or the other of these surfaces. Thus, the reflectance color-balance layer and the transmittance color-balance layer may be located on opposite sides or on the same side of the variable transmittance layer. If the color-balance layer is on the same side of the variable transmittance layer, either of them may be immediately adjacent to the variable transmittance layer. However, those skilled in the art will understand that the reflectance color-balance layer is most effective when it is closest to the observer, which may mean that it is located on or functionally adjacent to the transmittance color-balance layer.

[0051] The term "reflectance color-balanced layer" as used herein means a layer or element that causes the reflected visible light of a laminated assembly to be closer to a target reflective color or spectrum, for example, a target reflective color in a dark state having a* value of -10 to +22 and a* value of -9 to +9, or a* value of -4 to +19 and a* value of -5 to +6, or a* value of -2 to +15 and a* value of -2 to +6; and a target reflective color in a bright state having a* value of -10 to +23 and a* value of -2 to +22, or a* value of -6 to +18 and a* value of -2 to +16, or a* value of -2 to +16 and a* value of -2 to +12.

[0052] The term "transmittance color-balanced layer" as used herein means a layer or element in which transmitted visible light satisfies a target transmitted color or spectrum, for example, a target transmitted color in a dark state having a* value of -13 to +13 and a* value of -20 to +3, or a* value of -10 to +10 and a* value of -15 to +3, or a* value of -4 to +4 and a* value of -7 to +3; and a target transmitted color in a bright state having a* value of -6 to +10 and a* value of -4 to +24, or a* value of -5 to +8 and a* value of -3 to +18, or a* value of -4 to +4 and a* value of -2 to +8.

[0053] Those skilled in the art will understand that when considering a method for color balancing of transmittance, both the view through the glazing from inside the vehicle to the outside and the color effects of the light transmitted through the glazing must be taken into account.

[0054] The term 'stack' or 'stacked assembly' may generally be used to describe two or more layers (glass, intermediate layer, color-balanced layer, light-attenuating layer, layer-by-layer coating, adhesive layer, etc.), more specifically, the stacked assembly of the present invention through which light is transmitted or reflected. The stack may be described with respect to color, spectrum, transmitted light, or reflected light, or with respect to the difference between the color of the transmitted light or reflected light of the stack and a target (LT A , L*a*b*, Delta C, Delta E, etc.).

[0055] As used herein, the term "mil" means a unit of length for 1 / 1000 inch (.001). 1 mil is about 25 microns, and this dimension may be used to describe the thickness of an optical filter or a component of an optical filter according to some embodiments of the present invention. Those skilled in the art may convert the dimension of 'mil' to microns or vice versa.

[0056] When referring to measurable values ​​such as quantity, temporal duration, etc., the term "about" as used herein means including a variation of ±20% or ±10% from a specific value, more preferably ±5%, much more preferably ±1%, and even more preferably ±0.1%, because such variation is suitable for performing the disclosed method.

[0057] The color of the laminated glass comprising a switching material, layer, multilayer composition, or multilayer composition is color values ​​L*a* and b* known in the art (according to light source D65, 10-degree observer) and / or visible light transmittance LT known in the art A It may be described as (luminescent transmission, light source A, 2nd-degree observer). LT Aand L*a*b* values ​​can be measured according to the SAEJ1796 standard. The L*a*b color space provides a means to describe observed colors. L* defines luminosity (where 0 is black and 100 is white), a* defines the level of green or red (where + a* values ​​are red and - a* values ​​are green), and b* defines the level of blue or yellow (where + b* values ​​are yellow and - b* values ​​are blue). Referring to neutral gray, transmitted or reflected colors can be described by calculating the C (or C*ab) value independently of L* (where C = (a 2 + b 2 ) 1 / 2 lim).

[0058] To describe the scalar relationship between the target color and the achieved color (from combining one or more layers and a variable transmittance optical filter), ΔC (delta C) is calculated as follows.

[0059] Delta C = Stack's C* ab - Target's C* ab

[0060] To describe the vector relationship between the target color and the achieved color, ΔE (Delta E) is calculated as follows.

[0061] Delta E* ab = [(Delta L*) 2 +(Delta a*) 2 + (Delta b*) 2 ] 1 / 2

[0062] As an example to illustrate the range of C values ​​that can be considered neutral, transmission spectra were obtained from 10 commercial sources of 'gray' glass (LT A (normalized for), this showed a maximum C value (Cmax) of 4.4 and an average C value (Cavg) of 1.6, but LT across the entire visible spectrumA The reduction is substantially similar. Other L*a*b* values ​​across the gray tone range are described below. Therefore, neutral colors are 'achromatic' (similar or nearly similar LT across the visible range). A It can be described as having). Two or more spectra can be described as 'complementary' when the visible portions of the spectra, when combined, provide an achromatic spectrum ("neutral color"). When judged "by the eye," the neutral color is substantially not yellow / blue or red / green. The lower the Delta C or Delta E value, the smaller the color difference between the target color and the stack color. Generally, a stack that approximates the target color will have a Delta C of about 0 to about 20, or any amount between them, or a Delta E of about 0, or any amount between them. For clarity, the range of about 0 to about 20 or any amount between them includes about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19, or any amount between them.

[0063] Directional terms such as “top,” “bottom,” “up,” “down,” “vertically,” “laterally,” “inner,” and “outer” are used herein solely for the purpose of providing relative reference and are not intended to suggest any limitation on how any article is positioned or mounted in an assembly or environment during use. Additionally, the term “couple” and variations thereof such as “coupled,” “couple,” and “coupling” as used herein are intended to include indirect and direct connections, unless otherwise indicated. For example, where a first article is coupled to a second article, the coupling may be made through a direct connection or through an indirect connection via another article.

[0064] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as generally understood by those skilled in the art to which the present invention pertains. In the event that the definitions disclosed in this section conflict with or do not agree with the definitions disclosed in the literature by reference herein, the definitions disclosed herein shall prevail over the definitions by reference.

[0065] Examples

[0066] Generally, a window comprising a variable transmittance component (e.g., a variable transmittance optical filter, a layer or element, or variable transmittance laminated glass, etc.) can separate an interior space from an exterior space. Depending on the components of the window, various layers and various arrangements of layers may be considered. It may be desirable to change the observed (reflected) color or the color of the transmitted light of the window to match or approximate a target color different from the color of the variable transmittance layer. For example, it may be desirable to match or approximate the target color to harmonize the appearance of the window with the exterior color of a building envelope or vehicle, or to harmonize the appearance of the window with other components of the window, such as a frame. FIGS. 1 through 6 provide various configurations and arrangements of layers in a multilayer composition that can be used in such a window. In some embodiments, the relative positions of the layers may be described with reference to the space partially defined by the variable transmittance layer and the incident light or the window.

[0067] In an embodiment of the present invention, FIG. 1 illustrates a multilayer stack according to the present invention comprising a laminated glass stack (100). The laminated stack comprises two layers of glass (101 and 102), two layers of polyvinyl butyral (PVB) (103 and 104), and a variable transmittance layer (105). In this embodiment, the PVB layer (103), which also acts as a color-balance layer, is located inboard of the variable transmittance layer (105). In this embodiment, the PVB layer (103) would be closer to the interior space if it is part of a window installed in a building or vehicle. Similarly, in this embodiment, the PVB layer (104), which also acts as a color-balance layer, is located outside of the variable transmittance layer (105). Incident light from a light source (106) may be natural light or simulated sunlight, or artificial light from any suitable source. The incident light may include the entire visible light spectrum and may exclude most light outside the visible light spectrum, or the incident light may include UV and / or infrared / near-infrared components.

[0068] The variable transmittance layer (105) comprises a variable transmittance optical filter and itself comprises a switching material (switchable material). According to one embodiment, the variable transmittance layer (105) comprises a photochromic / electrochromic switching material. Examples of variable transmittance optical filters are described in US844107 and WO2013 / 106921, the relevant parts of which are incorporated herein by reference in their entirety without contradicting the present invention. Additional examples of switching materials are described in US8441707 and US10054835, the relevant parts of which are incorporated herein by reference in their entirety without contradicting the present invention. The variable transmittance layer (105) may be any color in a faded or dark state. In some examples, the faded state will be substantially colorless or faintly colored (e.g., some switching materials containing photochromic / electrochromic compounds are pale yellow in the faded state), and will be substantially colored in the dark state (e.g., some switching materials containing photochromic / electrochromic compounds are blue or cyan, or pink / red or magenta in the dark state). Other switching materials or technologies, such as electrochromic, photochromic, floating particle devices, or liquid crystal-based technologies, may also be used instead of the photochromic / electrochromic variable transmittance layer.

[0069] According to the embodiment, the variable transmittance layer may be in the form of a sealed multilayer plastic film and then laminated between two layers (101 and 102) of glass using PVB layers (103 and 104). The variable transmittance may have a dark state, a bright state, and a state in between. The transmitted or reflected color of the variable transmittance layer itself may not be desirable for a specific application or customer. If a neutral color of the multilayer composition or laminated glass is required, one or both of the PVB layers (103 and 104) may be colored to change the transmitted light and / or reflected light.

[0070] In this embodiment, the PVB layer (103) is plum-colored PVB, and the PVB layer (104) is light gray PVB. As described in examples of some prior art, the plum-colored PVB layer (103) can be used to color-balance an example of a photochromic / electrochromic variable transmittance filter (105) by changing the spectrum of light transmitted through the laminated assembly to match a more neutral target color in a dark state and / or a bright state. In examples of prior art, the plum-colored PVB layer is located outside the variable transmittance filter. This achieves a target that provides a transmitted color closer to the target color, but does not take into account the reflective color of the laminated glass stack.

[0071] Experimentally, it has been confirmed that the reflective color when viewed from the outside is dominated by the color of the first layer inside the glass, or in some cases, by the color of the glass itself or the layer on the glass. As such, the reflective color is dominated by the plum PVB in the example of the prior art because it is located outside the variable transmittance layer. Customers may want a more neutral reflective color. Referring again to FIG. 1, an example of a laminated glass stack (100) is shown that provides a more neutral reflective color when viewed from the outside, while providing color balance to the target transmittance color.

[0072] In the embodiment illustrated in FIG. 1, a plum-colored PVB layer (103) is located on the inner side of the variable transmittance layer (105), and a second light gray PVB layer (104) is located on the outer side of the variable transmittance layer (105) and immediately on the inner side of the outer glass layer (101). Regardless of the location of the plum-colored PVB layer (103) (whether on the outer side or the inner side of the variable transmittance layer (105)), the transmitted color is the same, but in this embodiment, by placing the plum-colored PVB layer (103) on the inner side of the variable transmittance layer (105) and including the light gray PVB layer (104) on the outer side of the layer (105), the reflected color when viewed from the outside is greatly improved (i.e., made more neutral). The light gray PVB layer used in this embodiment may be a 15 mil thick PVB layer (103) with a visible light transmittance of about 71%. The light gray PVB layer (104) will reduce the total amount of light transmittance through the stack, but depending on the customer, it may be desirable for the stack to be darker overall. Otherwise, the stack may be made brighter, for example, by reducing the amount of switching material of the variable transmittance layer (105) and / or by increasing the light transmittance of the plum PVB layer (103) (i.e., making it brighter) or by other means.

[0073] FIG. 2 illustrates a laminated glass stack (200) having a plum PVB layer (103) on the outer side of the variable transmittance layer (105) and a light gray PVB layer (104) on the inner side of the variable transmittance layer (105). The plum PVB (103) performs the same function of color-balancing the transmittance color of the variable transmittance layer (105) in dark and / or bright states. To achieve a desired reflective color, two gray PVB layers are used. A light gray PVB layer (104) is located on the inner side of the variable transmittance layer (105) to make the reflective color of the glass laminated stack (200) appear more neutral from the inside. A dark gray PVB layer (201) is located on the outer side of the plum PVB layer (103) to make the reflective color of the glass laminated stack (200) appear more neutral from the outside. Since the dark gray PVB layer (201) is the first layer inside the glass layer (101), it has the greatest effect on the reflectivity of the stack when viewed from the outside. In this embodiment, a neutral reflective color is desired, and an additional dark gray PVB layer (201) helps to achieve this target. The dark gray PVB layer (201) may be, for example, a 15 mil thick PVB layer having a visible light transmittance of about 43%.

[0074] FIG. 3 shows how light reflected by various layers of a laminated glass stack (200) according to this embodiment is affected. In FIG. 3, the width of the arrows indicates the intensity of the light. The largest portion of the reflected light comes from the layer immediately below the outer glass layer (101). In this case, the dark gray PVB layer (201) reflects neutral colors, and because it is the layer closest to the glass, the neutral colors reflected by this layer tend to dominate the overall color of the reflected light. As the light penetrates deeper into the stack, less light is reflected from subsequent layers as it is already attenuated by the dark gray PVB layer (201). Additionally, the reflected light is attenuated further because it must travel through the dark gray layer (201) again to reach the outside. For example, the light reflected from the plum PVB layer (103) is greatly reduced and has much less effect on the reflected color, and the light reflected from the variable transmittance layer (105) is greatly reduced. Light reflected from the PVB layer (104) on the inner side of the variable transmittance layer (105) can be almost ignored. Note that in this embodiment, since the light gray PVB layer (104) will dominate the reflection of light from inside the multilayer stack (201), light reflected from inside the vehicle or building will also be more neutral.

[0075] Although a specific PVB interlayer has just been described, various interlayer materials may be used. Preferably, the interlayer will be colored to achieve the desired transmittance and reflectance.

[0076] Where the intermediate layer comprises PVB, the PVB resin may be produced by a known acetalization process by reacting polyvinyl alcohol ("PVOH") with butyraldehyde in the presence of an acid catalyst, followed by separation, stabilization, and drying of the resin. Such acetalization processes are disclosed, for example, in U.S. Patents No. 2,282,057 and 2,282,026 and in the literature [Vinyl Acetal Polymers, in Encyclopedia of Polymer Science & Technology, 3rd edition, Volume 8, pages 381-399, by BE Wade (2003)], the full contents of which are incorporated herein by reference. The resin is commercially available in various forms, such as Butvar® Resin from Solutia Inc., a wholly owned subsidiary of Eastman Chemical Company. As used herein, the residual hydroxyl content of PVB (calculated as % vinyl alcohol or %PVOH by weight) represents the amount of hydroxyl groups remaining in the polymer chain after the treatment is completed. For example, PVB can be prepared by hydrolyzing poly(vinyl acetate) into poly(vinyl alcohol (PVOH)) and then reacting the PVOH with butyraldehyde. In the hydrolysis process of poly(vinyl acetate), typically, not all acetate side groups are converted into hydroxyl groups. Furthermore, the reaction with butyraldehyde will typically not result in the conversion of all hydroxyl groups into acetal groups. Consequently, all finished PVB resins will typically contain residual acetate groups (as vinyl acetate groups) and residual hydroxyl groups (as vinyl hydroxyl groups) as side groups on the polymer chain. The residual hydroxyl content and residual acetate content used herein are measured on a weight percentage (weight%) basis according to ASTM D1396.

[0077] The PVB resin of the present invention typically has a molecular weight greater than 50,000 daltons, or less than 500,000 daltons, or about 50,000 to about 500,000 daltons, or about 70,000 to about 500,000 daltons, or about 100,000 to about 425,000 daltons when measured by size exclusion chromatography using low-angle laser light scattering. In this specification, the term “molecular weight” means weight-average molecular weight.

[0078] Various adhesion modifiers (“ACAs”) may be used in the intermediate layer of the present invention to control the adhesion of the intermediate layer sheet to glass. In various embodiments of the intermediate layer of the present invention, the intermediate layer may comprise about 0.003 to about 0.15 parts of ACA per 100 parts of resin; about 0.01 to about 0.10 parts of ACA per 100 parts of resin; and about 0.01 to about 0.04 parts of ACA per 100 parts of resin. Such ACAs include, but are not limited to, the ACA disclosed in U.S. Patent No. 5,728,472 (the whole of which is incorporated herein by reference), residual sodium acetate, potassium acetate, magnesium bis(2-ethyl butyrate), and / or magnesium bis(2-ethylhexanoate).

[0079] Other additives may be incorporated into the intermediate layer to improve performance in the final product and impart specific additional properties to the intermediate layer. These additives include, but are not limited to, dyes, pigments, stabilizers (e.g., UV stabilizers), antioxidants, anti-blocking agents, flame retardants, IR absorbers or blockers (e.g., indium tin oxide, antimony tin oxide, lanthanum hexaboride (LaBe), and cesium tungsten oxide), processing aids, flow enhancers, lubricants, impact modifiers, nucleating agents, heat stabilizers, UV absorbers, dispersants, surfactants, chelating agents, coupling agents, adhesives, primers, reinforcing additives, and fillers among other additives known to those skilled in the art.

[0080] Although the aforementioned embodiments refer to the polymer resin as PVB, it will be understood by those skilled in the art that the polymer may be any polymer suitable for use in multilayer panels. Typical polymers include, but are not limited to, polyvinyl acetal (PVA) (e.g., poly(vinyl butyral) (PVB) or its isomer poly(vinyl isobutyral) (PVisoB), polyurethane (PU), poly(ethylene-co-vinyl acetate) (EVA), polyvinyl chloride (PVC), poly(vinyl chloride-co-methacrylate), polyethylene, polyolefin, ethylene acrylate ester copolymer, poly(ethylene-co-butyl acrylate), silicone elastomer, epoxy resin, and acid copolymers derived from any of the possible thermoplastic resins, such as ethylene / carboxylic acid copolymers and their ionomers, and combinations of the foregoing. PVB and its isomer polymer PVisoB, polyvinyl chloride, and polyurethane are generally polymers particularly useful for intermediate layers; PVB (and its isomer polymer) is particularly preferred.

[0081] In a further embodiment, the diffusion interlayer may be a multilayered interlayer. For example, the multilayered interlayer may be composed of PVB / / PVisoB / / PVB. Other examples include PVB / / PVC / / PVB or PVB / / PU / / PVB. Further examples include PVC / / PVB / / PVC or PU / / PVB / / PU. Alternatively, the skin and core layers may both be PVB using the same or different starting PVB resins.

[0082] At least one of the PVB layers will typically additionally include at least one coloring agent. Those skilled in the art will understand that multiple PVB layers having different colors may be combined, or that individual colored layers of plastic such as PET may be added or used instead of PVB.

[0083] Alternatively, PVB layers are described in U.S. Patents No. 6,455,141 and No. 9,248,628, the entirety of which is incorporated herein by reference to the extent that it does not conflict with the present invention. In this embodiment, the adhesive-coated plastic material may be used, for example, in a laminate assembly.

[0084] According to this embodiment, the coated plastic interlayer can be bonded to one of the glass sheets using a very thin (e.g., 0.25 to 5 mil) (0.006 mm to 0.127 mm) adhesive layer that provides the coated plastic interlayer with a highly flat texture. This flatness is maintained when the glass sheet-adhesive-plastic film composite is incorporated into a final laminated glass structure using a second adhesive layer and a second glass sheet.

[0085] This product comprises a first glass sheet having a smooth first surface; and a first adhesive layer that attaches a plastic film to the smooth surface of the first glass sheet. This first adhesive layer is thin, i.e., less than 5 mil (0.127 mm) in thickness. The plastic film is registered and matched to the smooth surface of the first glass sheet. The plastic film may include an energy-reflective coating. The glass laminate is completed by a second adhesive layer that bonds the plastic film to a second glass sheet. The energy-reflective layer may be on either side of the plastic film, but a better result is achieved when the thin adhesive layer faces the first glass sheet.

[0086] In another embodiment, this embodiment provides an intermediate for the final product just described. This intermediate is a plastic film comprising an energy blocking layer and an adhesive coating of 5 mil (0.127 mm) or less on one side of the film, preferably on the side comprising an energy reflective layer, wherein this provides a final product having greater stability and product life along with improved corrosion resistance for the energy reflective layer.

[0087] In a further embodiment, a method for preparing such an intermediate is provided in which an energy-reflective layer coated plastic film is coated with an adhesive solution (preferably on the energy-reflective coating). Then, the solvent is removed from the solution coating, leaving a layer of adhesive on the energy-reflective layer comprising the plastic film. The coating thickness of the adhesive solution can be predetermined to obtain a final clean (neat) adhesive layer with a thickness of less than 5 mil (0.127 mm).

[0088] This process may be part of an overall laminated window production plan, where a plastic film having an adhesive-coated reflective layer is bonded and matched to the smooth surface of a first glass sheet, a second adhesive layer is applied, and then a second glass sheet is applied so that the entire structure is laminated.

[0089] Additionally, an adhesive, which may be PVB, once applied to a plastic layer, can be grooved or textured to allow previously trapped air to escape between the layers of the laminated assembly during the lamination process. This allows the adhesive layer to be made thinner while still providing a final product that is relatively bubble-free and optically satisfactory, or substantially free of optical defects caused by waviness in the plastic layer between two PVB sheets and / or wrinkles in the plastic sheets.

[0090] In an alternative embodiment, one or more color-balanced layers may be formed using a layer-by-layer technique, for example, as disclosed and claimed in U.S. Patent No. 9,453,949 (the whole is incorporated herein by reference). In this embodiment, referring now to FIGS. 4 and 5, a color-balanced layer is formed as an optical product (10) comprising a polymer substrate (15) and a composite coating (20). The composite coating comprises a first layer (25) and a second layer (30). Preferably, the first layer (25) is immediately adjacent to the polymer substrate (20) on a first face (28), and the second layer (30) is immediately adjacent to the first layer (25) on an opposite face (32). The first layer (25) comprises a multiionic binder, while the second layer (30) comprises insoluble particles that are electromagnetic energy-absorbing. Each layer (25, 30) comprises a coupling component having a coupling component of a first layer and a coupling component of a second layer, which constitute a complementary coupling pair. As used herein, the phrase “complementary coupling pair” means that a bonding interaction, such as electrostatic bonding, hydrogen bonding, van der Waals interaction, hydrophobic interaction, and / or chemically induced covalent bonding, exists between the coupling component of the first layer and the coupling component of the second layer of the composite coating layer. A “coupler component” is a chemical functional group that establishes one or more of the bonding interactions described above in cooperation with the complementary coupling component. The components are complementary in the sense that bonding interactions are generated through their respective charges.

[0091] The first layer (25) of the composite coating may comprise a polyionic binder defined as a macromolecule containing a plurality of positively charged or negatively charged moieties along a polymer backbone. A polyionic binder having a positive charge is known as a polycationic binder, and one having a negative charge is called a polyanionic binder. Furthermore, it will be understood by those skilled in the art that some polyionic binders may function as either polycationic binders or polyanionic binders depending on factors such as pH, and are known to be amphoteric. The charged moieties of the polyionic binder constitute the "binding component" of the first layer.

[0092] Examples of suitable polycationic binders include poly(allylamine hydrochloride), linear or branched poly(ethyleneimine), poly(diallyldimethylammonium chloride), macromolecules called polyquaternium or polyquat, and various copolymers thereof. Blends of polycationic binders are also considered by the present invention. Examples of suitable polyanionic binders include carboxylic acid-containing compounds such as poly(acrylic acid) and poly(methacrylic acid), as well as sulfonate-containing compounds such as poly(styrene sulfonate) and various copolymers thereof. Blends of polyanionic binders are also considered by the present invention. Polyionic binders of both polycationic and polyanionic types are generally well known to those skilled in the art, for example, as described in U.S. Published Patent Application No. US20140079884 by Krogman et al. Examples of suitable polyanionic binders include polyacrylic acid (PAA), poly(styrene sulfonate) (PSS), poly(vinyl alcohol) or poly(vinyl acetate) (PVA, PVAc), poly(vinyl sulfonic acid), carboxymethyl cellulose (CMC), polysilicic acid, poly(3,4-ethylenedioxythiophene) (PEDOT), and other polymers and combinations thereof (e.g., PEDOT:PSS), polysaccharides, and copolymers of the aforementioned. Other examples of suitable polyanionic binders include trimethoxysilane-functionalized PAA or PAH or biological molecules, e.g., DNA, RNA, or proteins. Examples of suitable polyvalent cationic binders include poly(diallyldimethylammonium chloride) (PDAC), chitosan, poly(allylamine hydrochloride) (PAH), polysaccharides, proteins, linear poly(ethyleneimine) (LPEI), branched poly(ethyleneimine) BPEI, and copolymers of the above.

[0093] The concentration of the polyionic binder in the first layer may be selected based in part on the molecular weight of its charged repeating unit, but will typically be 0.1 mM to 100 mM, more preferably 0.5 mM to 50 mM, and most preferably 1 to 20 mM based on the molecular weight of the charged repeating unit comprising the first layer. Preferably, the polyionic binder is a polycationic binder, and more preferably, the polycationic binder is polyallylamine hydrochloride. Most preferably, the polyionic binder is soluble in water, and the composition used to form the first layer is an aqueous solution of the polyionic binder. In an embodiment where the polyionic binder is polycationic and the first layer is formed from an aqueous solution, the pH of the aqueous solution is 5 to 95%, preferably 25 to 75%, and more preferably, approximately half of the ionizable groups are protonated. Other optional components of the first layer include a biocide or a shelf-life stabilizer.

[0094] The second layer (30) of the composite coating (20) may comprise insoluble particles that are electromagnetic energy-absorbing. The phrase “electromagnetic energy-absorbing” implies that the particles are intentionally selected as components of the optical product to preferentially absorb at specific spectral wavelength(s) or wavelength range(s). The term “insoluble” implies that the particles exist as particles in the optical product structure without being substantially dissolved in the composition used to form the second layer (30). The insoluble particles that are electromagnetic energy-absorbing are preferably visible electromagnetic energy absorbers such as pigments, but may also be insoluble particles such as UV absorbers or IR absorbers that do not necessarily exhibit color, or absorbers in various parts of the electromagnetic spectrum. The electromagnetic energy-absorbing particles are preferably present in the second layer in an amount of 30% to 60% by weight based on the total weight of the second layer. To achieve the desired final electromagnetic energy absorption level, the second layer must be formed from a composition containing insoluble electromagnetic energy-absorbing particles in an amount of 0.25 to 2 weight percent based on the total weight of the composition.

[0095] In a preferred embodiment of the second layer, the pigment suitable for use as an insoluble particle capable of absorbing electromagnetic energy is preferably a fine particle pigment having an average particle diameter of 5 to 300 nanometers, more preferably 10 to 50 nanometers, which is often referred to in the art as a nanoparticle pigment. Even more preferably, the surface of the pigment comprises the linker component of the second layer. Suitable pigments are commercially available as colloidally stable aqueous dispersions from manufacturers such as Cabot, Clariant, DuPont, Dainippon, and DeGussa. Particularly suitable pigments include those available from Cabot Corporation as Cab-O-Jet.RTM. Examples include the designations 250C (cyan), 265M (magenta), 270Y (yellow), or 352K (black). To be stable in water as a colloidal dispersion, the surface of the pigment particles is typically treated to impart ionizable properties, thereby providing a pigment having the desired linker component on its surface. Commercially available pigments are sold in various forms such as suspensions, dispersions, etc., and those skilled in the art will understand that commercial forms of pigments should be evaluated and, in particular, that care should be taken to modify them as necessary to ensure compatibility and performance with optical product components, especially in embodiments where the pigment surface also functions as a binder component of the second layer.

[0096] While multiple pigments may be used in the second layer to achieve a specific hue, shade, or color in the final optical product, those skilled in the art will understand again that when multiple pigments are to be used, they must be carefully selected to ensure both compatibility and performance with each other and with the optical product components. This is particularly relevant in embodiments where the pigment surface also functions as a binder component of the second layer, for example, because particulate pigments may exhibit different surface charge densities due to different chemical modifications that can affect compatibility.

[0097] Preferably, the second layer of the composite coating further comprises a screening agent. The “screening agent” is defined as an additive that promotes uniform and reproducible deposition of the second layer through improved dispersion of electromagnetic energy-absorbing insoluble particles within the second layer by increasing ionic strength and reducing interparticle electrostatic repulsion. Screening agents are generally well known to those skilled in the art, for example, as described in U.S. Published Patent Application No. US20140079884 by Krogman et al. Sodium chloride is typically a preferred screening agent based on component cost. The presence and concentration level of the screening agent may allow for higher loading of electromagnetic energy-absorbing insoluble particles, such as that desired in optical products with lower transmittance, and also enable the achievement of a level of customizable and carefully controllable optical products with customizable and carefully controllable loading of electromagnetic energy-absorbing insoluble particles.

[0098] These layered optical products may be composed of a single pigment or of a pigment blend as disclosed and claimed in U.S. Patent No. 9,817,166, the entirety of which is incorporated herein by reference. These may be used in place of or in addition to the colored PVB layers already described.

[0099] In a more specific embodiment, layered optical products exhibiting neutral reflection such as those disclosed and claimed in U.S. Patents No. 10,613,261 and No. 10,627,555 may be used, the entire contents of which are incorporated herein by reference.

[0100] In one embodiment, according to U.S. Patent No. 10,613,261, such a neutral reflective layer-by-layer optical product may comprise a composite coating having a multi-layer of first and second layers, each provided with a coupling component, which together form a complementary coupling pair, and said multi-layer comprises: one or more layers a) composed of a first pigment or pigment blend having a color reflectance value of less than about 2.5; one or more layers b) composed of a pigment or pigment blend having a color reflectance value of less than about 2.5; and one or more layers c) composed of a second pigment or pigment blend having a color reflectance value of less than about 2.5, wherein the optical product selectively blocks visible light in a wavelength range of interest while having a color reflectance value of less than about 2.5.

[0101] In this embodiment, the wavelength range of interest may be, for example, a 75 nm wavelength range, or a 50 nm wavelength range, or as described elsewhere. Similarly, in various aspects, the wavelength range of interest may be 400 nm to 450 nm, or 600 nm to 650 nm, or 500 nm to 600 nm, or 525 nm to 575 nm, or as described elsewhere in this invention.

[0102] In this embodiment, the optical product may further comprise one or more double layers d) deposited on one or more double layers c) which are composed of a pigment or pigment blend that selectively blocks visible light when formed into a double layer, wherein the pigment or pigment blend that selectively blocks visible light in a wavelength range of interest, which may be the same as or different from the pigment or pigment blend of double layer b) when formed into a double layer; and one or more double layers e) which are composed of a neutral pigment or pigment blend that exhibits a color reflectance value of less than about 2.5 when formed into a double layer and may be the same as or different from the pigment or pigment blend of double layer a) or double layer c).

[0103] In a further embodiment of this aspect, the optical product may have a color reflectance value of about 2.0 or less, or about 1.5 or as described elsewhere in this invention. As mentioned, the substrate of these optical products may comprise a polyethylene terephthalate film, and separately, the composite coating may have a total thickness of 5 nm to 1000 nm.

[0104] In another embodiment, according to U.S. Patent No. 10,627,555, such neutral reflective layer-by-layer optical product may comprise a composite coating which is deposited on a substrate and at least one double layer having a first layer and a second layer, each having a coupling component and together forming a complementary coupling pair. One or more double layers comprise a pigment blend comprising a) two or more pigments that, when mixed together to form a double layer, exhibit a color reflectance value of about 2.5 or less; and b) one or more pigments that, when mixed together to form a double layer, selectively block visible light in a wavelength range of interest.

[0105] In addition, in this embodiment, the wavelength range of interest may be a 75 nm wavelength range or a 50 nm wavelength range, or a wavelength range of 400 nm to 450 nm, or 600 nm to 650 nm, or 500 nm to 600 nm, or 525 nm to 575 nm, or as described elsewhere in the present invention.

[0106] In this embodiment, at least one double layer of the optical product of the present invention may comprise at least three double layers, or as described elsewhere in this specification. In another embodiment, the color reflectance value of the optical product of the present invention may be less than about 2.0, or less than about 1.5, or as described elsewhere in this specification.

[0107] In addition, in this embodiment, the optical product may include a polyethylene terephthalate film as a substrate. In another aspect, the composite coating of the optical product of the present invention may have a total thickness of 5 nm to 1000 nm, or as described elsewhere in this specification.

[0108] When it is said that an optical product or film of such neutral reflective layer-by-layer coating, or an individual double layer or a plurality of double layers, selectively blocks visible light within a wavelength range of interest, or within a limited wavelength range or a predetermined wavelength range, this means that the amount of light blocked within that wavelength range is greater than the amount of light blocked in other wavelength ranges of the same width within the visible light spectrum (i.e., about 400 nm to 700 nm) or within the range described elsewhere in this invention. When it is said that light is selectively blocked, the definition of "blocked" is intended to include any light within the wavelength range scattered by the optical product, as well as absorbed and reflected light; that is, any light that does not pass through the film or optical product so as to be measurable is considered "blocked," regardless of whether the blocked light is absorbed, reflected, or scattered. Of course, the wavelength of interest may be predetermined, and, for example, a pigment that absorbs light within a predetermined or predetermined wavelength range may be selected. Conversely, in the sense that pigments can be attempted for novelty or aesthetic effect and selected based solely on their influence on appearance and transmitted color, the wavelength range of interest can be selected randomly as long as the desired relatively neutral reflection defined by the color reflection value is also achieved.

[0109] The light measurements used in these embodiments, which are described in greater detail in U.S. Patents No. 10,613,261 and No. 10,627,555 by reference in their entirety without contradiction to the present disclosure, are determined using the 1976 CIE L*a*b* color space. The CIE L*a*b* is a relative color system based on Richard Hunter's early (1942) system, denoted as L, a, and b. In the CIE L*a*b* color space, three coordinates represent the following: the brightness of the color (L* = 0 produces black, and L* = 100 produces diffuse white); the position between red and green (a*, negative values ​​represent green, and positive values ​​represent red); and the position between yellow and blue (b*, negative values ​​represent blue, and positive values ​​represent yellow).

[0110] Therefore, these layer-by-layer optical products can be used to replace one or both of the aforementioned colored PVB layers.

[0111] The performance of laminated glass or multilayer compositions as described in this specification is in accordance with standard technologies in the field, e.g., VLT, LT A It can be tested by conducting research using measurements of color and haze. WO2010 / 142019 describes methods, equipment, and techniques that can be used to evaluate the performance of optical filters.

[0112] Tables 1 and 2 below show color balance data for an embodiment using a multilayer glass-laminated stack similar to that shown in FIGS. 2 and 3, except that in the following embodiment, the plum-colored PVB layer (103) is a plum-colored PET layer. Table 1 shows the reflected L*, a*, b*, and delta C values ​​when the variable transmittance layer (105) is in a dark state. Table 2 shows the reflected L*, a*, b*, and delta C values ​​when the variable transmittance layer (105) is in a bright state. Table 3 shows the transmitted L*, a*, b* and delta C values ​​when the variable transmittance layer (105) is in a dark state. Table 4 shows the transmitted L*, a*, b* and delta C values ​​when the variable transmittance layer (105) is in a bright state. Values ​​for various combinations of neutral gray PVB layers (layers 104 and 201) are displayed. The percentage figures displayed in the top row measure the amount of black pigment in layer (201) (first figure) and layer (104) (second figure), where the 100% value corresponds approximately to the desired total loading of black pigment divided between layers (104 and 201). In all tested devices, the plum PET layer (103) remains the same. Plum PET is included in the stack to ensure that the transmitted color approximates the transmitted color target. Data L*, a*, b* values ​​and Delta C figures for the reflected color are shown for the stack when viewed at the top (outer, outermost position) and bottom (inner, innermost position) of the stack.

[0113] In this embodiment, the target reflected and transmitted colors are both completely neutral, where the a* and b* values ​​are 0. If these target reflected and transmitted colors are perfectly matched, the delta C becomes 0. However, as previously discussed, a delta C of 0 to 20 represents a good approximation to the target color and will be acceptable in most applications. As can be seen in Table 1, even in a dark (most colored) variable transmittance filter (105), it is possible to achieve a delta C value of less than 20 in the reflected color from the outside through the addition of a gray PVB layer (201) and also from the inside through the addition of a gray PVB layer (104). Without these gray layers, the delta C value for the light reflected from both the outside and the inside would be much higher.

[0114] In Table 1, it is noted that, generally, the darker the gray (the higher the percentage of black pigment), the more effective it is in dominating the reflected color and reducing the delta C value. For example, using a gray PVB layer containing 55% of the total black pigment (PVB layer (201) in FIG. 2 and 3), the delta C of the reflected light from the top is 4.6, which is higher than the delta C value of 1.4 achieved by the same stack using a darker (90% of black pigment) gray PVB layer in Example 4, as described in Example 1. It is noted that a clear trend exists across Examples 1 through 4, namely that the higher the proportion of black pigment in the gray PVB layer, the lower the delta C value (the more neutral). In all these examples, the color filter may be a commercially available filter or a custom filter designed to transmit and reflect a specific spectrum to match the desired application or to work more optimally with a specific variable transmittance filter.

[0115] Reflected color coordinates and Delta C values ​​using a variable transmittance filter in a dark state Black pigment loading of gray layer (104 / 201) (inner side / outer side), expressed as a percentage, where 100% is the approximate desired total loading to be divided between the two gray layers. Example 1 55% / 45% Example 2 67% / 33% Example 3 90% / 15% Example 4 90% / 10% Top L*,a*,b* 28.9, 4.5, 0.8 28.2, 2.7, 0.5 26.8, 0.2, 1.0 26.7, -0.2, 1.4 Top Delta C 4.6 2.7 1.0 1.4 Bottom L*,a*,b* 29.7, 5.0, 1.8 30.1, 7.2, 4.5 35.0, 11.6, 6.5 37.3, 13.7, 8.8 Bottom Delta C 5.3 8.5 13.3 16.3

[0116] In Table 1, the delta C values ​​of the light reflected from the bottom of the stack (inside; most of the inside positions) are also all less than 20, so the light reflected from the bottom also approaches the neutral color target very well. The delta C values ​​also show a similar increasing trend with the lighter gray layer used as the PVB layer (104) right next to the glass facing inside (102). In Example 1, with a 45% black pigment loading, a delta C of 5.3 is achieved, whereas in Example 4, a 10% black pigment loading produces a delta C of 16.3.

[0117] Since variable transmittance filters have both dark and bright states with different light transmittance and color characteristics, it may be important in some applications to ensure that the reflected color closely approximates the target color when the variable transmittance filter is in both dark and bright states. Table 2 below shows the reflected L*a*b* and delta C values ​​for the same four examples using variable transmittance filters in the bright state. The delta C values ​​are generally higher for the variable transmittance filters in the bright state, which indicates that the reflected color in the bright state is slightly more difficult to color-balance than the reflected color in the dark state. However, almost all delta C values ​​are still below 20, showing a good approximation to the target. The only delta C value slightly higher than 20 appears in the bottom reflection value of Example 4, which has an inner gray PVB layer with a 10% black pigment loading, suggesting that a slightly darker gray PVB would help make the reflected light more neutral in this case.

[0118] Reflected color coordinates and Delta C values ​​using a variable transmittance filter in a faded state Black pigment loading of gray layer (104 / 201) (inner side / outer side), expressed as a percentage, where 100% is the approximate desired total loading to be divided between the two gray layers. Example 1 55% / 45% Example 2 67% / 33% Example 3 90% / 15% Example 4 90% / 10% Top L*,a*,b* 30.0, 7.0, 1.6 29.2, 5.3, 0.8 27.3, 2.0, 1.1 27.3, 1.8, 1.6 Top Delta C 7.2 5.4 2.2 2.4 Bottom L*,a*,b* 31.9, 7.4, 3.0 33.5, 10.3, 6.4 40.5, 14.0, 10.1 43.8, 15.3, 13.7 Bottom Delta C 7.9 12.1 17.2 20.5

[0119] Table 2 shows the calculated delta C value when the target transmitted light and target reflected light are completely neutral gray, which means that the a* and b* values ​​are 0 and are indicated as the origin on the a*b* color wheel. However, the transmitted and reflected target colors can be set within a range close to the origin on the a*b* color wheel, and a neutral appearance can still be achieved even with non-zero a* and b* values. In other applications, other regions of the color wheel close to the neutral origin may be preferred (e.g., a slight blue tint may be perceived as more acceptable than a slight orange tint), and different targets may exist when the variable transmittance filter layer (105) is in a dark state versus a bright state.

[0120] Transmitted color coordinates, Delta C, and LT using a variable transmittance filter in dark conditions A value Black pigment loading of gray layer (104 / 201) (inner side / outer side), expressed as a percentage, where 100% is the approximate desired total loading to be divided between the two gray layers. Example 1 55% / 45% Example 2 67% / 33% Example 3 90% / 15% Example 4 90% / 10% L*,a*,b* 2.0, -2.2, -6.0 2.2, -3.0, -6.2 2.8, -3.7, -5.7 2.5, -3.0, -6.3 Delta C 6.4 6.9 6.8 7.0 LT A 0.1 % 0.1 % 0.2 % 0.2 %

[0121] Tables 3 and 4 indicate that the plum-colored PET layer (103) is effective in neutralizing the transmitted color for the same series of test devices (Examples 1 to 4), demonstrating that the target transmitted color can be achieved in the faded and dark states while providing the target reflected color in series at both the top (outer, outermost position) and bottom (inner, innermost position) of the stack. When the variable transmittance filter (105) is in the dark state (Table 3), the delta C value is 7 or less, which indicates that the actual color is close to the target color. Similarly, when the variable transmittance filter (105) is in the bright state (Table 4), the delta C value is less than 20, which indicates that the actual color is also close to the target color. In Examples 1, 2 and 4, the same loading of black pigment is present in the combined gray PVB layer (201 and 104) (100%), and the same is true for the plum PET layer, which is the transmitted color coordinates and LT when the variable transmittance filter (105) is in a dark or bright state. A Note that the values ​​are very similar.

[0122] Transmitted color coordinates, Delta C, and LT using a variable transmittance filter in bright conditions A value Black pigment loading of gray layer (104 / 201) (inner side / outer side), expressed as a percentage, where 100% is the approximate desired total loading to be divided between the two gray layers. Example 1 55% / 45% Example 2 67% / 33% Example 3 90% / 15% Example 4 90% / 10% L*,a*,b* 23.3, 3.7, 18.2 23.0, 3.6, 17.9 21.5, 4.5, 17.1 22.7, 4.6, 17.9 Delta C 18.6 18.2 17.7 18.4 LT A 4.3 % 4.2 % 3.8% 4.2 %

[0123] Exemplary target color range for light transmission through a multilayer stack

[0124] FIG. 6 illustrates an a*b* color wheel (400) having an exemplary target transmittance color range when the variable transmittance filter is in a dark state. In this embodiment, circle (401) represents an a* value of -13 to +13 and a b* value of -20 to +3, which is a preferred color range for the transmittance color target. Circle (402) represents an a* value of -10 to +10 and a b* value of -15 to +3, which is a more preferred color range for the transmittance color target. Circle (403) represents the most preferred range and represents an a* value of -4 to +4 and a b* value of -7 to +3.

[0125] Similarly, FIG. 7 illustrates an a*b* color wheel (500) having an exemplary target transmittance color range when the variable transmittance filter is in a bright state. In this embodiment, circle (501) represents an a* value of -6 to +10 and a b* value of -4 to +24, which is a preferred color range for the transmittance color target. Circle (502) represents an a* value of -5 to +8 and a b* value of -3 to +18, which is a more preferred color range for the transmittance color target. Circle (503) represents the most preferred range and represents an a* value of -4 to +4 and a b* value of -2 to +8.

[0126] Exemplary target color range for light reflectance from a multilayer stack

[0127] FIG. 8 illustrates an a*b* color wheel (400) having an exemplary target reflection color range when the variable transmittance filter is in a dark state. In this embodiment, circle (601) represents an a* value of -10 to +22 and a b* value of -9 to +9, which is a preferred color range for the reflection color target. Circle (602) represents an a* value of -4 to +19 and a b* value of -5 to +6, which is a more preferred color range for the transmission color target. Circle (603) represents the most preferred range and represents an a* value of -2 to +15 and a b* value of -2 to +6.

[0128] Similarly, FIG. 9 illustrates an a*b* color wheel (400) having an exemplary target reflection color range when the variable transmittance filter is in a bright state. In this embodiment, circle (701) represents an a* value of -10 to +23 and a b* value of -2 to +22, which is a preferred color range for the transmitted color target. Circle (702) represents an a* value of -6 to +18 and a b* value of -2 to +16, which is a more preferred color range for the transmitted color target. Circle (703) represents the most preferred range and represents an a* value of -2 to +16 and a b* value of -2 to +12.

[0129] In one example, a multilayer stack requiring a neutral color for both transmission and reflection has a delta C of 20 or less when the target color is within a desirable range for both transmission and reflection for a dark state, a bright state, or both states. In another example, the multilayer stack has a delta C of 20 or less when the target color is within a more desirable range for both transmission and reflection for a dark state, a bright state, or both states. In another example, the multilayer stack has a delta C of 20 or less when the target color is within a most desirable range for both transmission and reflection for a dark state, a bright state, or both states.

[0130] The above examples describe target color ranges for achieving more neutral transmitted and reflected light in a multilayer stack including variable transmittance filters. However, according to other examples, the target color for transmission and / or reflection does not necessarily have to be a neutral color. For example, a vehicle designer may want to match the reflective color to the car's light-colored paint, or an architect may want to design a building to reflect a specific target color of light.

[0131] In this example, the multilayer stack may include a color other than plum for the transmitted light color-balance layer or gray for the reflected light color-balance layer. The goal of this example remains the same, which is to simultaneously achieve a transmitted color having a delta C of 20 or less from the target transmitted color regardless of what the target transmitted color is for a specific application, and a transmitted color having a delta C of 20 or less from the target reflected color regardless of what the target reflected color is. Although it may not be possible to achieve a delta C of 20 or less for all combinations of the transmitted color target and the reflected color target, the same general principle applies: using a color layer that reflects the desired color as close as possible to the outer glass plate on the outer side of the variable transmittance filter, and using a color layer below this layer to balance the transmitted color.

[0132] According to some examples, multilayer stacks have an LT of less than about 1%, or less than about 2%, or less than about 5%, or less than about 10% in a dark state. A It may have. According to some examples, a multilayer stack has an LT exceeding approximately 4%, or exceeding approximately 5%, or exceeding approximately 10%, or exceeding approximately 15%, or exceeding approximately 20% in a faded state. A Can have.

[0133] According to some examples, a multilayer stack has an LT of about 1% to about 10% or any amount or range in between in a dark state. A, and in a faded state, about 5% to about 30% or any amount or range of LT between these. A It may have, for example, a multilayer composition or laminated glass about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 25, or 30%, or any amount or range between these, of dark or faded LT. A It can have, provided that the dark state is LT than the faded state A The value is smaller. When the target transmission and reflection colors are neutral color 'stacks', the multilayer stack according to various embodiments may have an L* value of about 40 to about 60 or any amount between these in a faded state.

[0134] As shown in FIGS. 1, 2 and 3, the lamination of a multilayer stack using PVB can be achieved using a standard PVB lamination process by applying heat and pressure to the stack for a fixed period (e.g., in an autoclave), thereby allowing the PVB to flow and bond to both the variable transmittance layer (105) and the glass layers (101, 102). In this example, a PVB layer is shown because using PVB is one of the most common materials for laminating glass, but other types of laminating layers can be used instead of PVB to bond the stack together. For example, ethylene-vinyl acetate (EVA), thermoplastic polyurethane (TPU), SentryGlas® ionoplast polymer interlayers, and various pressure-sensitive adhesives (PSAs) are all examples of materials that can be used to bond glass to glass and film to glass, which can also be easily colored or dyed to provide colors suitable for achieving the present invention.

[0135] Color is also not necessarily included only in the PVB layer. It may be provided in the layer-by-layer optical product already described, or alternatively, and is typically deposited on a substrate such as PET. In a further embodiment, the laminated assembly of the present invention may be colored using one or more colored PET layers, for example, a dyed PET film.

[0136] It is also possible to use gray glass instead of gray PVB, or more generally, to use colored glass instead of colored polymer. For example, if the glass layer (101) of FIG. 3 is replaced with gray glass instead of clear glass, the gray PVB layer (201) is no longer needed or can be replaced with clear PVB. Gray glass can be used instead of gray PVB to achieve the target reflective color. Similarly, the gray PVB layer (104) can also be replaced with a clear PVB layer if gray glass is used in the glass layer (102).

[0137] Alternatively, the color-balance layer for the transmittance and reflectance of the stack may be composed of a material other than PVB. In some examples, the colored layer may be a polyethylene terephthalate (PET) layer attached to the variable transmittance layer using a pressure-sensitive adhesive, and then the entire stack may be bonded to glass using PVB or another material. Not only may the pressure-sensitive adhesive layer itself be colored, but in some examples of the variable transmittance layer, the PET substrate containing the transparent conductive electrode may also be colored. Other films such as polyethylene naphthalate (PEN), polycarbonate, or thin glass films are also possible. In some examples, some of these layers may be flexible or rigid. The reflective color-balance gray layer may also be a coating on the outer glass layer that can be applied by sputtering, chemical vapor deposition, spraying, slot die, painting, or other methods known in the art.

[0138] Low haze may be a desirable feature in some applications. In one example, the multilayer stack has a total permeable haze of about 5% or less, about 3% or less, about 2% or less, about 1.5% or less, or about 1% or less, or about 0 to 2%, or about 0.5% to about 3%, or any amount or range between these.

[0139] The color-balance layer may also include a UV adsorbent and / or UV stabilizer that generates a UV cutoff wavelength, or an additional layer having such material may be added to the stack. For example, an adhesive layer such as PVB may contain an additive that blocks UV (e.g., US 6627318). In one example, the UV blocking material is located on the outer side of the variable transmittance filter layer (105) to prevent lethal UV from reaching the variable transmittance layer. For example, the gray PVB layer (201) may also include a UV absorber that blocks UV at wavelengths below 380 nm or 400 nm.

[0140] One or more layers may also include an IR-blocking component. For example, a solar control film may be included in a multilayer stack or laminated glass. Examples of such films include US 2004 / 0032658 and US 4368945, the disclosures of which are incorporated herein by reference to the extent that they do not contradict the present invention. Alternatively, an IR blocking material may be incorporated into a glass layer or an adhesive layer. The IR blocking layer may reflect or absorb IR light. In one example, an IR reflective material layer is located on the outer side of the variable transmittance layer (105) to keep the stack cooler by reflecting the thermal energy of the IR out of the stack before the IR passes through and is absorbed by another layer in the stack.

[0141] The multilayer stack may also include a low emissivity (low E) coating. In one example, the low E coating is located on the inner side of the variable transmittance layer (105) on one of the surfaces of the glass layer (102). The location of these layers helps to prevent heat radiation from the multilayer stack to the vehicle or building.

[0142] Other modes of implementation

[0143] Any embodiment discussed herein may be implemented or combined with any other embodiment, method, composition, or aspect, and vice versa.

[0144] The present invention has been described in relation to one or more embodiments. However, it will be obvious to those skilled in the art that many variations and modifications can be made without departing from the scope of the invention as defined in the claims. Accordingly, although various embodiments of the invention are disclosed herein, many modifications and modifications can be made within the scope of the invention in accordance with the ordinary general knowledge of those skilled in the art. Such modifications include substituting known equivalents for any embodiment of the invention to achieve the same results in substantially the same manner. Numerical ranges include numerical values ​​defining the range. The terms "approximately" and "about" mean + / - 10% of the value when used with a value. In this specification, the word "comprising" is used as an open term substantially equivalent to the expression "comprising but not limited thereto," and the word "comprising" has a corresponding meaning. Singular expressions used in this specification include plural references unless the context clearly indicates otherwise. References cited herein shall not be construed as an acknowledgment that such references are prior art to the present invention, or as an acknowledgment of the contents or dates of the references. All publications are cited herein by reference as specifically and individually described and fully disclosed herein, as each individual publication is cited herein by reference. The present invention includes all embodiments and variations substantially described above with reference to the embodiments and drawings.

Claims

Claim 1 i. a variable transmittance layer having first and second sides facing oppositely; ii. at least a first reflectance color-balancing layer located on the first side of the variable transmittance layer; and iii. a transmittance color-balancing layer located on the first or second side of the variable transmittance layer, and further comprising a second reflectance color-balancing layer on the side of the variable transmittance layer opposite the first reflectance color-balancing layer, a layered assembly. Claim 2 delete Claim 3 A laminated assembly according to claim 1, wherein at least one of the first reflectance color-balance layer and the transmittance color-balance layer comprises a plurality of colored films. Claim 4 A laminated assembly according to claim 1, further comprising a first polymer layer on a first surface of the laminated assembly and a second polymer layer on a second surface of the laminated assembly. Claim 5 In claim 4, a laminated assembly wherein at least one of the first and second polymer layers comprises a PVB coating on PET. Claim 6 A stacked assembly according to claim 1, wherein the stacked assembly further comprises an IR-blocking layer. Claim 7 A laminated assembly according to claim 1, wherein at least the first reflectance color-balance layer comprises a colored PVB, and the laminated assembly further comprises a rigid substrate laminated to the first reflectance color-balance layer. Claim 8 A laminated assembly according to claim 1, wherein both the first reflectance color-balance layer and the second reflectance color-balance layer comprise colored PVB, and the laminated assembly further comprises a rigid substrate laminated to the first reflectance color-balance layer and the second reflectance color-balance layer, respectively. Claim 9 A laminated assembly according to claim 1, wherein the laminated assembly further comprises a polymer-based layer, wherein the variable transmittance layer, the first and second reflectance color-balance layers and the transmittance color-balance layer are laminated within the same, and the first and second reflectance color-balance layers are immediately adjacent to the polymer-based layer. Claim 10 A laminated assembly according to claim 4, further comprising a rigid substrate laminated to the first polymer layer and the second polymer layer, respectively. Claim 11 A laminated assembly according to claim 9, further comprising a rigid substrate laminated on each side facing opposite to the polymer-based layer. Claim 12 A stacked assembly according to any one of claims 1 and 3 through 11, wherein i. the variable transmittance layer is variable between a dark state and a bright state; ii. the variable transmittance layer has a dark state transmittance spectrum when in a dark state and a different bright state transmittance spectrum when in a bright state; and iii. the dark state transmittance spectrum and the transmittance spectra for the first and second reflectance color-balance layers and the transmittance color-balance layers are selected such that when the variable transmittance layer is in a dark state, the transmittance color of the stacked assembly approximates a target transmittance color and the reflectance color of the stacked assembly approximates a target reflectance color in response to visible light incident on the first and second reflectance color-balance layers. Claim 13 A stacked assembly according to any one of claims 1 and 3 through 11, wherein i. the variable transmittance layer is variable between a dark state and a bright state; ii. the variable transmittance layer has a dark state transmittance spectrum when in a dark state and a different bright state transmittance spectrum when in a bright state; and iii. the bright state transmittance spectrum and the transmittance spectra for the first and second reflectance color-balance layers and the transmittance color-balance layer are selected such that when the variable transmittance layer is in a bright state, the transmittance color of the stacked assembly approximates a target transmittance color and the reflectance color of the stacked assembly approximates a target reflectance color in response to visible light incident on the first and second reflectance color-balance layers. Claim 14 A stacked assembly according to claim 12, wherein the target transmittance color in the dark state has an a* value of -13 to +13 and a* value of -20 to +3, or an a* value of -10 to +10 and a* value of -15 to +3, or an a* value of -4 to +4 and a* value of -7 to +3. Claim 15 A stacked assembly according to claim 13, wherein the target transmittance color in the bright state has an a* value of -6 to +10 and a* value of -4 to +24, or an a* value of -5 to +8 and a* value of -3 to +18, or an a* value of -4 to +4 and a* value of -2 to +8. Claim 16 A stacked assembly according to claim 12, wherein the target reflection color in the dark state has an a* value of -10 to +22 and a b* value of -9 to +9, or an a* value of -4 to +19 and a b* value of -5 to +6, or an a* value of -2 to +15 and a b* value of -2 to +6. Claim 17 A stacked assembly according to claim 13, wherein the target reflection color in the bright state has an a* value of -10 to +23 and a b* value of -2 to +22, or an a* value of -6 to +18 and a b* value of -2 to +16, or an a* value of -2 to +16 and a b* value of -2 to +12. Claim 18 A laminated assembly according to claim 12, wherein the difference between the actual transmitted color compared to the transmittance of the laminated assembly without the first reflectance color-balance layer and the transmittance color-balance layer has a delta C of at least 5. Claim 19 A stacked assembly according to any one of claims 1 and 3 to 11, wherein the variable transmittance layer comprises one or more of a photochromic material, an electrochromic material, a thermochromic material, a liquid crystal material, or a suspended particle device. Claim 20 A laminated assembly according to any one of claims 1 and 3 to 11, wherein the variable transmittance layer is capable of transitioning from a faded state to a dark state when exposed to electromagnetic radiation, and capable of transitioning from a dark state to a faded state by the application of voltage. Claim 21 In any one of claims 1 and 3 through 11, the laminated assembly has an LT of less than 1%, or less than 2%, or less than 5%, or less than 10% in a dark state. A A stacked assembly having Claim 22 In any one of claims 1 and 3 through 11, the LT of the laminated assembly in a faded state exceeding 5%, or exceeding 10%, or exceeding 15%, or exceeding 20% A A stacked assembly having Claim 23 A laminated assembly according to any one of claims 1 and 3 to 11, wherein the transmission haze through the laminated assembly is 5% or less, 3% or less, 2% or less, or 1% or less. Claim 24 A laminated assembly according to any one of claims 1 and 3 to 11, wherein at least one of the first and second reflectance color-balance layers and the transmittance color-balance layer comprises a. a polymer substrate and b. a composite coating, wherein the composite coating comprises a first layer comprising a polyionic binder and a second layer comprising insoluble particles capable of absorbing electromagnetic energy, wherein each of the first layer and the second layer comprises a binder component and together form a complementary binder pair. Claim 25 i. a variable transmittance layer having first and second faces facing opposite sides; ii. a transmittance color-balance layer located on the first face of the variable transmittance layer; iii. a first reflectance color-balance layer located on the first face of the variable transmittance layer and located on the outer side of the transmittance color-balance layer; and iv. a second reflectance color-balance layer located on the second face of the variable transmittance layer, comprising a laminated assembly. Claim 26 In claim 25, i. the variable transmittance layer is variable between a dark state and a bright state; ii. the variable transmittance layer has a dark state transmittance spectrum when in a dark state and a different bright state transmittance spectrum when in a bright state; and iii. the dark state transmittance spectrum and the transmittance spectrum for the first and second reflectance color-balance layers and the transmittance color-balance layer are selected such that when the variable transmittance layer is in a dark state, the transmittance color of the laminated assembly has an a* value of -13 to +13 and a b* value of -20 to +3 in response to visible light incident on the first and second reflectance color-balance layers. Claim 27 In claim 25, i. the variable transmittance layer is variable between a dark state and a bright state; ii. the variable transmittance layer has a dark state transmittance spectrum when in a dark state and a different bright state transmittance spectrum when in a bright state; and iii. the bright state transmittance spectrum and the transmittance spectrum for the first and second reflectance color-balance layers and the transmittance color-balance layer are selected such that when the variable transmittance layer is in a bright state, the transmittance color of the laminated assembly in response to visible light incident on the first and second reflectance color-balance layers has an a* value of -6 to +10 and a* value of -4 to +24, or an a* value of -5 to +8 and a* value of -3 to +18, or an a* value of -4 to +4 and a* value of -2 to +8. Claim 28 A laminated assembly according to claim 26 or 27, wherein i. the variable transmittance layer is variable between a non-opaque dark state and a bright state; ii. the variable transmittance layer has a dark state reflectance spectrum when in a dark state and a different bright state reflectance spectrum when in a bright state; and iii. the dark state reflectance spectrum and the reflectance spectra for the first and second reflectance color-balance layers and the transmittance color-balance layer are selected such that when the variable transmittance layer is in a dark state, the reflective color of the laminated assembly has an a* value of -10 to +22 and a b* value of -9 to +9 in response to visible light incident on the first and second reflectance color-balance layers. Claim 29 A laminated assembly according to claim 26 or 27, wherein i. the variable transmittance layer is variable between a non-opaque dark state and a bright state; ii. the variable transmittance layer has a dark state reflectance spectrum when in a dark state and a different bright state reflectance spectrum when in a bright state; and iii. the bright state reflectance spectrum, and the reflectance spectra for the first and second reflectance color-balance layers and the transmittance color-balance layer are selected such that when the variable transmittance layer is in a bright state, the reflective color of the laminated assembly has an a* value of -10 to +23 and a b* value of -2 to +22 in response to visible light incident on the first and second reflectance color-balance layers.

Images