CN101484309A - Aesthetic transparency - Google Patents

Abstract

A laminated transparency includes a first ply having a No. 1 and a No. 2 surface, a second ply having a No. 3 and a No. 4 surface, and an interlayer positioned between the first and second plies. An aesthetic coating is deposited over at least a portion of the first or second plies. The transparency has a color defined by |a*|>=10 and |b*|>=10 and, in one non-limiting embodiment, L*>=40.

Description

beautiful transparent body

Cross References to Related Applications

[0001] The application has claimed the priority of U.S. Provisional Application Serial No. 60/798,828 filed on May 9, 2006 and U.S. Provisional Application Serial No. 60/855,219 filed on October 30, 2006. These two applications Incorporated herein by reference in its entirety.

Background of the invention

1. Field of invention

[0002] The present invention relates generally to transparencies such as but not limited to vehicle windshields, side lights, rear lights, etc., and in a particular embodiment to laminated vehicles having a desired aesthetic appearance transparent body.

2. Technical issues

[0003] In today's automotive market, great emphasis is placed on automotive styling. When it comes to car sales, vehicle appearance can be as important as a vehicle's mechanical reliability or safety rating. Accordingly, automakers have gone to great lengths to improve vehicle styling. These styling improvements include offering more car color options to consumers as well as offering colors with metallic flakes to give cars a "multi-color effect".

[0004] Although these styling improvements have generally been well accepted by consumers, a problem that has remained heretofore is that even with a new vehicle paint finish, automotive transparencies (such as but not limited to windshields, front sidelights, etc.) , rear lights, sunroof and roof (sunroof)) are still usually green, gray or neutral color. It would therefore be desirable to provide a vehicle transparency having a color that is complementary to the color of the vehicle body to provide an improved overall aesthetic appearance of the vehicle.

[0005] However, considerations other than color must be addressed in attempts to introduce more color into automotive transparencies. For example in the United States, government regulations require that all passenger car windshields must have a light transmittance (Lta) of at least 70% of light (of visible light). In Europe, the minimum Lta required is 75%. Any tinted windshields will have to meet these standards.

[0006] Additionally, conventional automotive windshields typically provide a solar control function to reduce the amount of heat entering the vehicle through the windshield. It would be desirable to provide a tinted windshield that includes a solar control function.

[0007] It would therefore be advantageous to provide an aesthetically pleasing transparency that enables the color of the transparency to match the color of the vehicle body. It would further be advantageous if the transparency could also provide some solar control properties.

Summary of the invention

A kind of laminated transparent body comprises the first layer (ply) with No.1 and No.2 surface, has the second layer (ply) of No.3 and No.4 surface, and is positioned at the first layer and the first layer The middle layer between the two layers. An aesthetic coating is formed over at least a portion of the first layer or the second layer. The transparent body has a color defined by at least one of |a ^* | and |b ^* | greater than or equal to 10. In a non-limiting embodiment, L ^* > 40. In another non-limiting embodiment, C ^* may have a range of 15≦C ^* ≦90 and L ^* ≧40.

[0009] Another kind of laminated transparent body includes a first glass layer with No.1 and No.2 surfaces, a second glass layer with No.3 and No.4 surfaces, and a layer between the first glass layer and the second glass layer. Intermediate layer between layers. The transparency further includes an aesthetic coating deposited over at least a portion of the No. 2 surface of the first layer. The aesthetic coating comprises a coating stack comprising the following layer structure: H ¹ /M ¹ /H ² /M ² /H ³ , wherein H ¹ , H ² and H ³ denotes a layer comprising at least one high-refractive-index material (a material with a refractive index greater than 1.75), and M ¹ and M ² denote metal layers. The transparent body has a color defined by at least one of |a ^* |≥10 and |b ^* |≥10. In a non-limiting embodiment, L ^* > 40. In another non-limiting embodiment, C ^* may have a range of 15≦C ^* ≦90 and L ^* ≧40. A reflective coating, such as an antireflective coating, may be formed over at least a portion of the second glass layer, such as the No. 4 surface of the second layer.

[0010] Another kind of laminated transparent body includes a first glass layer with No.1 and No.2 surfaces, a second glass layer with No.2 and No.3 surfaces, and a layer between the first glass layer and the second glass layer. A polymer interlayer between the layers. An aesthetic coating is formed over at least a portion of the No. 2 surface. The aesthetic coating comprises a coating stack comprising the following layer structure: H/M/H/M/H, wherein H comprises zinc stannate and M comprises silver. The transparent body has a color defined by at least one ≥ 10 of |a ^* | and |b ^* |. In a non-limiting embodiment, L ^* > 40. In another non-limiting embodiment, C ^* may have a range of 15≦C ^* ≦90 and L ^* ≧40. A protective overcoat may be deposited over the aesthetic coating. The protective coating may comprise a multilayer coating stack comprising at least one of silica, alumina, zirconia, and mixtures or combinations thereof. A reflection coating such as an anti-reflection coating may be formed on at least a portion of the No. 4 surface. The antireflective coating may comprise a first layer having a refractive index greater than 1.75, a second layer deposited on the first layer and having a refractive index less than or equal to 1.75, a second layer deposited on the second layer and having a refractive index greater than 1.75. Three layers, and a fourth layer deposited over the third layer and having a refractive index less than or equal to 1.75.

[0011] Another laminated transparency includes a first layer, a second layer, an intermediate layer positioned between the first layer and the second layer, and an aesthetic coating positioned between the first layer and the second layer. The transparent body has a color defined by at least one of |a ^* | and |b ^* | ≥ 10 and L ^* ≥ 40.

Brief description of the drawings

[0012] The present invention will be described with reference to the following drawings, wherein like reference numerals refer to like parts throughout.

[0013] FIG. 1 is a side sectional view (not to scale) of a laminated automotive windshield incorporating features of the present invention;

[0014] FIG. 2 is a side cross-sectional view (not to scale) of a first exemplary aesthetic coating of the present invention;

[0015] FIG. 3 is a side sectional view (not to scale) of a second exemplary aesthetic coating of the present invention;

[0016] FIG. 4 is a side cross-sectional view (not to scale) of a third exemplary aesthetic coating of the present invention;

Fig. 5 is the side sectional view (not to scale) of antireflection coating of the present invention;

[0018] FIG. 6 is a graph of a ^* and b ^* values for one non-limiting embodiment of a coated article of the present invention; and

[0019] Figure 7 is a graph of a ^* and b ^* values for another non-limiting embodiment of a coated article of the present invention.

Description of the preferred embodiment

[0020] Spatial or directional terms such as "left", "right", "inner", "outer", "above", "below" etc. as used herein refer to this invention. It should be understood, however, that the invention may assume a variety of alternative orientations, and thus these terms are not to be regarded as limiting. Additionally, all numerical values expressing dimensions, physical properties, processing parameters, ingredient amounts, reaction conditions, etc. used herein in the specification and claims are to be understood as modified in all instances by the term "about". Accordingly, unless stated to the contrary, the numerical values described in the following specification and claims may vary depending upon the desired properties intended to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical value should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Moreover, all ranges disclosed herein are to be understood to include the starting and ending range values and any and all subranges subsumed therein. For example, a stated range of "1 to 10" should be considered to include any and all subranges between (and including) the minimum value of 1 and the maximum value of 10; that is, starting with the minimum value of 1 or greater All subranges that start and end with a maximum value of 10 or less, such as 1 to 3.3, 4.7 to 7.5, 5.5 to 10, etc. In addition, the term "formed on", "deposited on" or "provided on" as used herein means formed, deposited or provided on but not necessarily with The surfaces are in contact. For example, a coating "formed over a substrate" does not preclude the presence of one or more other coatings or films of the same or different composition located between the formed coating and the substrate. As used herein, the term "polymer, polymeric" includes oligomers, homopolymers, copolymers and terpolymers, such as polymers formed from two or more monomers or polymers. The term "visible region" or "visible light" refers to electromagnetic radiation having a wavelength in the range of 380nm to 800nm. The term "infrared region" or "infrared radiation" refers to electromagnetic radiation having wavelengths greater than the range of 800 nm to 100,000 nm. The term "ultraviolet region" or "ultraviolet radiation" refers to electromagnetic energy having a wavelength in the range of 300 nm to less than 380 nm. In addition, all references such as, but not limited to, published patents and patent applications mentioned herein are deemed to be "incorporated by reference" in their entirety. The term "aesthetic coating" refers to a coating provided to enhance the aesthetic properties of a substrate (eg, color, shade, tint, or visible light reflectance), but not necessarily the solar control properties of the substrate. However, aesthetic coatings may also provide properties other than aesthetics, such as ultraviolet (UV) radiation absorption or reflection and/or infrared (IR) absorption or reflection. Aesthetic coatings can also provide some solar control effect simply by reducing the transmittance of visible light through the article. In the following discussion, refractive index values are those for a reference wavelength of 550 nanometers (nm). The term "film" refers to a region of a coating having a desired or selected composition. A "layer" includes one or more "films." A "coating" or "coating stack" consists of one or more "layers". The absolute value of the number "N" is written herein as |N|. "Absolute value" refers to the numerical value of a real number independent of its sign. All quarter wavelength optical thickness values herein are defined relative to a reference wavelength of 550 nm.

[0021] For purposes of the following discussion, the invention will be described with reference to the application of automotive transparencies, particularly laminated automotive windshields. However, it should be understood that the present invention is not limited to use with automotive windshields, but may be practiced in any desired field, such as, but not limited to, laminated or non-laminated residential and/or commercial windows, to name a few , insulating glass parts, and/or transparent bodies for land, aerospace, aviation, water and underwater vehicles, such as automotive windshields, front side lights, rear lights, canopies and sunroofs. Therefore, it should be understood that the specific disclosed exemplary embodiments are shown only to explain the general concept of the invention and that the invention is not limited to these specific exemplary embodiments. Additionally, while a typical automotive "transparency" may have sufficient visible light transmittance such that materials can be seen through the transparency, in the practice of the present invention the "transparency" need not be transparent to visible light but may be semi-transparent. Transparent or opaque (described below). The aesthetic coatings of the present invention can be used to make laminated or non-laminated, eg monolayer or monolithic articles. "Monolithic" refers to a substrate or primary ply, such as a glass ply, having a single structure. "Primary ply" means the main supporting or structural element. In the following discussion, the exemplified articles (whether laminated or monolithic) are described as automotive windshields.

[0022] A non-limiting transparent body 10 (eg, an automobile windshield) incorporating features of the present invention is depicted in FIG. 1 . The transparent body 10 may have any desired transmittance and reflectance of visible light, infrared radiation or ultraviolet radiation. For example, the transparent body 10 may have a visible light transmittance of any desired amount, such as greater than 0% up to 100%, such as greater than 70%. For the windshield area and front side light area in the United States, the visible light transmittance is generally greater than or equal to 70%. For privacy areas such as rear seat side lights and rear windows, the visible light transmittance may be less than that of the windshield, for example less than 70%.

[0023] The transparent body 10 comprises a first layer 12 having a first major surface and a second major surface. In the example described, the first major surface faces the vehicle exterior "E", namely the outer major surface 14 (No. .1 surface), and the opposite second or inner major surface 16 (No. 2 surface) faces the vehicle interior "I". The transparency 10 also comprises a second layer 18 having an outer (first) main surface 20 (No. 3 surface) and an inner (second) main surface 22 (No. 4 surface) facing the exterior E of the vehicle. This numbering of layer surfaces is consistent with conventional practice in the automotive field. The first layer 12 and second layer 18 may be bonded together in any suitable manner, such as by a conventional intermediate layer 24 . Although not required, a conventional edge sealant may be applied to the perimeter of laminated transparency 10 during and/or after lamination in any desired manner. A decorative band such as an opaque, translucent or colored band 26 (shown in FIG. 2 ), such as a ceramic band, may be provided on the surface of at least one of the layers 12, 18, such as around the perimeter of the inner major surface 16 of the first layer 12. . The aesthetic coating 30 is formed over at least a portion of one of the layers 12 , 18 , for example on at least a portion of the No. 2 surface 16 or the No. 3 surface 20 . A reflective coating 32 may be formed over at least one of the surfaces, for example over at least a portion of No. 4 surface 22 . “Reflective coating” refers to a coating that affects the visible light reflectance of the transparency 10 . For example, the reflection coating (reflection coating) may be an antireflective coating (antireflective coating) configured to reduce the visible light reflectance of the transparent body 10 or a reflective coating configured to increase the visible light reflectance of the transparent body 10. Layer (reflective coating).

[0024] In the broad practice of the invention, the layers 12, 18 of the transparency 10 may be of the same or different materials. Layers 12, 18 may comprise any desired material having any desired properties. For example, one or more of layers 12, 18 may be transparent or translucent to visible light. "Transparent" means having a visible light transmittance of greater than 0% to 100%. Alternatively, one or more of the layers 12, 18 may be translucent. "Translucent" means allowing electromagnetic energy (eg, visible light) to pass through but diffusing that energy so that objects on the side opposite the observer are not clearly visible. Examples of suitable materials include, but are not limited to, plastic substrates (e.g., acrylic polymers such as polyacrylates; polyalkylmethacrylates such as polymethylmethacrylate, polyethylmethacrylate, polymethacrylate; propyl acrylate, etc.; polyurethane; polycarbonate; polyalkylene terephthalate such as polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate esters, etc.; polysiloxane-containing polymers; or copolymers of any of the monomers used to make these, or any mixture thereof); ceramic substrates; glass substrates; or mixtures or combinations of any of the foregoing. For example, one or more of layers 12, 18 may comprise conventional soda lime silicate glass, borosilicate glass, or leaded glass. The glass may be clear glass. "Clear glass" means non-tinted or non-tinted glass. Alternatively, the glass may be tinted or tinted glass. The glass may be annealed or heat-treated glass. The term "heat treatment" as used herein means tempering or at least partial tempering. The glass can be of any type, such as conventional float glass, and can be of any optical property such as any value of visible light transmittance, ultraviolet light transmittance, infrared light transmittance and/or total solar transmittance. composition. "Float glass" refers to glass formed by the conventional float process in which molten glass is deposited on a bath of molten metal and cooled in a controlled manner to form a float glass strand. The strip is then cut and/or shaped and/or heat treated as desired. Examples of float glass processes are disclosed in US Patent Nos. 4,466,562 and 4,671,155. The first and second layers 12, 18 may each be, for example, clear float glass or may be tinted or tinted glass, or one layer 12, 18 may be clear glass and the other layer 12, 18 may be tinted glass . Although not limiting to the present invention, examples of glasses suitable for use in the first layer 12 and/or the second layer 18 are described in US Patent Nos. 4,746,347; 4,792,536; 5,030,593; 5,030,594; 5,240,886; The first and second layers 12, 18 may have any desired dimensions, such as length, width, shape or thickness. In an exemplary automotive transparency, the first layer and the second layer may each be 1 mm to 10 mm thick, such as 1 mm to 5 mm thick, or 1.5 mm to 2.5 mm thick, or 1.8 mm to 2.3 mm thick.

[0025] Intermediate layer 24 may be any desired material and may include one or more layers. Intermediate layer 24 may be a polymeric or plastic material, such as polyvinyl butyral, plasticized polyvinyl chloride, or a multi-layered thermoplastic material, including polyethylene terephthalate, among others. Suitable interlayer materials are disclosed, for example, but not limited to, in US Patent Nos. 4,287,107 and 3,762,988. The intermediate layer 24 holds the first and second layers 12, 18 together, provides energy absorption, reduces noise, and increases the strength of the laminate. Intermediate layer 24 may also be a sound absorbing or attenuating material, as described, for example, in US Patent No. 5,796,055. The intermediate layer 24 may have a solar control coating provided thereon or incorporated therein, or may include colored materials to reduce solar transmission.

[0026] The aesthetic coating 30 provides the article 10 with aesthetic properties. As will be understood by those skilled in the art, the color of an object is highly subjective. Observed colors will depend on lighting conditions and observer preference. In order to evaluate color quantitatively, several color sequential systems have been developed. One such method of determining color adopted by the International Commission on Illumination (CIE) uses dominant wavelength (DW) and excitation purity (Pe). For a given color, the values of these two specifications can be determined by calculating the color coordinates x and y from the so-called tristimulus values X, Y, Z of the color. The color coordinates can then be plotted on the 1931 CIE Chromaticity Diagram and compared numerically to the coordinates of the CIE Standard Illuminant C, as determined in CIE publication 15.2. This comparison provides the color space location on the map to determine the excitation purity and dominant wavelength of the glass color.

[0027] In another color sequential system, colors are determined based on hue and lightness. This system is commonly known as the CIELAB color system. Hue distinguishes colors such as red, yellow, green, and blue. Brightness or value differentiates how bright or dark it is. The values of these features - denoted L ^* , a ^* and b ^* - are calculated from the tristimulus values (X, Y, Z). L ^* represents the lightness or darkness of a color and represents the lightness plane on which the color lies, a ^* represents the color's position on the red (+a ^* ) green (-a ^* ) axis, and b ^* represents the color's position on the Position on the yellow (+b ^* ) blue (-b ^* ) axis. When converting the Cartesian coordinates of the CIELAB system into cylindrical polar coordinates, the resulting color system is known as the CIELCH color system, which determines color in terms of lightness (L ^* ) and hue angle (H°) and chromaticity (C ^* ) . As in the CIELAB system, L ^* indicates the lightness or darkness of a color. Hue or Saturation or Intensity distinguishes the intensity or clarity of a color (ie vibrancy vs. haze) and is the vector distance from the center of the color space to the color being measured. The lower the chroma of a color, ie the less its intensity, the closer the color is to what is known as a neutral color. For the CIELAB system, C ^* = (a ^*2 +b ^*2 ) ^1/2 . The hue angle distinguishes colors such as red, yellow, green, and blue, and is a measure of the angle of a vector extending from the a ^* , b ^* coordinates through the center of the CIELCH color space measured counterclockwise to the red (+a ^* ) axis.

It should be understood that color can be characterized by any of these color systems, and those skilled in the art can calculate equivalent DW and Pe values by the transmittance curve of observed glass or composite transparent body; L ^* , a ^* , b ^* values; and L ^* , C ^* , H° values. A detailed discussion of color calculations is given in US Patent No. 5,792,559. In this document, color is characterized using the CIELAB system (L ^* a ^* b ^* ). However, it should be understood that this is for ease of discussion only, and that the disclosed colors may be defined by any conventional system, such as those described above.

[0029] In one non-limiting embodiment of the invention, the aesthetic coating 30 may not affect or may only slightly affect the solar control properties of the coated article 10. In a non-limiting embodiment, the aesthetic coating 30 can provide the transparent body 10 with a range of -40≤a ^* ≤50, such as -40≤a ^* ≤45, such as -40≤a ^* ≤40, such as -30≤ The reflection color in the color space defined by a ^* ≤40, eg -20≤a ^* ≤40, eg -20≤a ^* ≤30. In another non-limiting embodiment, |a ^* | is greater than or equal to 10. i.e. a ^* is greater than or equal to 10 units from the origin of a ^* . For example, a ^* can be 10~50 in the positive number area and -10~-50 in the negative number area, that is, 10≤|a ^* |≤50, for example 20≤|a ^* |≤50, for example 30≤ |a ^* |≤50, eg 40≤|a ^* |≤50.

[0030] In a non-limiting embodiment, the aesthetic coating 30 can provide -75≤b ^* ≤40, for example-60≤b ^* ≤30, for example-50≤b ^* ≤30, for example-40≤b ^* ≤ 25. b ^* such as -30≤b ^* ≤20, such as -20≤b ^* ≤10, such as -10≤b ^* ≤5. In another non-limiting embodiment, |b ^* | is greater than or equal to 10. i.e. greater than or equal to 10 units from b ^* original value. For example, 0≤|b ^* |≤80, such as 20≤|b ^* |≤80, such as 30≤|b ^* |≤80, such as 40≤|b ^* |≤80, such as 50≤|b ^* |≤80 , such as 60≤|b ^* |≤80, such as 70≤|b ^* |≤80.

[0031] In a non-limiting embodiment, the transparent body 10 has 15≤C ^* ≤90, such as 20≤C ^* ≤90, such as 30≤C ^* ≤90, such as 40≤C ^* ≤90, such as 50≤ C ^* ≤ 90, such as 60 ≤ C ^* ≤ 90, such as 70 ≤ C ^* ≤ 90, such as 80 ≤ C ^* ≤ 90 defines the color.

[0032] In another non-limiting embodiment, one of |a ^* | or |b ^* | has a value greater than or equal to 10, and the other of |a ^* | or |b ^* | value.

[0033] The aesthetic coating may provide an L* ^of 30≤L ^* ≤60, such as 40≤L ^* ≤60, such as 50≤L ^* ≤60, such as an L ^* of greater than or equal to 40.

[0034] In the foregoing non-limiting embodiments, the aesthetic coating 30 is formed over at least a portion of one of the layers 12,18. However, it should be understood that the aesthetic coating 30 is not necessarily limited to this location. In another non-limiting embodiment, aesthetic coating 30 may be formed on a plastic or polymer film (eg, PET), which may be embedded in intermediate layer 24 .

[0035] In one non-limiting embodiment, aesthetic coating 30 includes one or more metallic layers and one or more dielectric paint layers. In a non-limiting embodiment, the metal layer may include at least one metal selected from gold, copper, silver, aluminum, or mixtures, alloys, or combinations thereof.

[0036] Exemplary dielectric materials useful in the present invention include, but are not limited to, silicon dioxide, aluminum oxide, zinc oxide, tin oxide, niobium oxide, tantalum oxide, zirconium oxide, titanium oxide, carbon (those known in the art known to the skilled person as "diamond-like carbon" or DLC), and one or more metal oxides, nitrides or oxynitrides such as silicon oxynitride, zinc and tin materials (such as but not limited to zinc stannate), And silicon and aluminum materials, or any combination containing any one or more of the above materials.

[0037] Aesthetic coating 30 may also include one or more additives or dopants to affect properties of aesthetic coating 30, such as refractive index, photocatalytic activity, and other similar properties known to those skilled in the art. Examples of dopants include, but are not limited to, sodium, nickel, transition metals, and mixtures comprising any one or more of the foregoing.

[0038] Aesthetic coating 30 may be of any thickness to achieve the desired color and reflectance values described above. As will be appreciated by those skilled in the art, the particular thickness of the aesthetic coating 30 can vary depending on the materials selected to obtain the desired color and reflectivity. Additionally, the aesthetic coating 30 need not have a uniform thickness across the entire surface it is deposited on. For example, the aesthetic coating 30 may have a non-uniform or varying thickness (eg, having regions of higher and lower thickness) to provide a perceived color difference, such as a rainbow effect, on the coated surface.

[0039] For use in front automotive transparencies such as windshields and front side lights, the transparencies 10 may have an Lta of greater than or equal to 70%, such as greater than or equal to 72%, or greater than or equal to 75%. For non-front vision panels (eg "privacy glass"), Lta may be less than 75%, such as less than 70% or less than 65%.

[0040] In order to provide a desired luster or flash to the transparent body 10 (such as a laminated automobile transparent body), the transparent body 10 can have 8% to 50%, such as 8% to 30%, such as 8% to 25% , such as 8% to 20%, such as 15% to 25%, such as 16% to 20%, such as 9% to 19% visible light reflectance. As will be understood by those skilled in the art, for laminated articles, reflectivity is typically defined in terms of the external reflectance of the laminated article. "External reflectance" refers to the reflectance of an outer surface (No. 1 surface) having an aesthetic coating 30 provided on an inner surface such as a No. 2 or No. 3 surface.

[0041] Aesthetic coating 30 may be deposited by any conventional method, such as, but not limited to, conventional chemical vapor deposition (CVD) and/or physical vapor deposition (PVD) methods. Examples of CVD methods include spray pyrolysis. Examples of PVD methods include electron beam evaporation and vacuum sputtering (eg, magnetron sputtering vapor deposition (MSVD)). Other coating methods such as, but not limited to, sol-gel deposition may also be used. In one non-limiting embodiment, conductive coating 30 may be deposited by MSVD. Examples of MSVD coating apparatus and methods will be well understood by those of ordinary skill in the art and are described, for example, in US Patent Nos. 4,379,040; 4,861,669; 4,898,789; 4,898,790; 4,900,633;

[0042] Exemplary coating stacks 34a-34c that may be incorporated into aesthetic coating 30 for the practice of the present invention are shown in FIGS. 2-4.

例如

或

或

或

或者的厚度。可用作第一介电层40的其他材料可以具有类似的厚度范围。在另一个非限定实施方案中，所述底层可以是多层结构。例如，底层40可以包括如上所述的锡酸锌层和其它层，例如锡酸锌层上的氧化锌层。该氧化锌层可以具有

例如或或

或

或者

的厚度。[0043] The exemplary non-limiting coating stack 34a shown in FIG. ) on at least a portion of the bottom (base layer) or first dielectric layer 40. The first dielectric layer 40 may comprise one or more films of antireflective material and/or dielectric material such as, but not limited to, metal oxides, metal alloy oxides, nitrides, oxynitrides, or mixtures thereof. The first dielectric layer 40 may be transparent to visible light. In the practice of the present invention, first layer 40 comprises at least one high refractive index material. The terms "low" and "high" used herein with respect to refractive index may be relative terms with respect to the materials of the coating stack. For example, in a coating stack, a "high" index material can be one that has a greater index of refraction than a "low" index material (i.e., the material that has the lowest relative refractive index value for the materials in the stack). of any material. In one non-limiting embodiment, a "low" index material is a material having an index of refraction less than or equal to 1.75, and a "high" index material is a material having an index of refraction greater than 1.75. Non-limiting examples of low refractive index materials include silica, alumina, and mixtures or combinations thereof. Non-limiting examples of high refractive index materials include zirconia, titanium oxide, zinc stannate, and zinc oxide. In one non-limiting embodiment, first layer 40 comprises zinc/tin alloy oxide. The zinc/tin alloy oxide may be the one obtained by magnetron sputtering vacuum deposition from a cathode of zinc and tin which may contain zinc and tin in a ratio of 10wt%-90wt% zinc and 90wt%-10wt% tin. One suitable metal alloy oxide that can be used in the bottom layer 40 is zinc stannate. "Zinc stannate" refers to a composition of Zn _x Sn _1-x O _2-x (Formula 1), where "x" ranges from greater than 0 to less than 1. For example, "x" may be greater than 0 and may be any fraction or decimal between greater than 0 and less than 1. For example in the case of x=2/3, Formula 1 is Zn _2/3 Sn _1/3 O _4/3 , which is more commonly described as "Zn ₂ SnO ₄ ". The zinc stannate-containing film may have one or more forms of Formula 1 in a major amount in the film. In one non-limiting embodiment, bottom layer 40 comprises zinc stannate and has

For example

or

or

or

or thickness of. Other materials that may be used as the first dielectric layer 40 may have similar thickness ranges. In another non-limiting embodiment, the bottom layer may be a multilayer structure. For example, bottom layer 40 may include a zinc stannate layer as described above and other layers, such as a zinc oxide layer on the zinc stannate layer. The zinc oxide layer can have

For example or or

or

or

thickness of.

或

或

或或者

或的金属银层。可用作第一反射层46的其他材料可以具有类似的厚度范围。[0044] A first thermal and/or radiation reflective film or layer 46 may be deposited over the first dielectric layer 40. The first reflective layer 46 may include a reflective metal such as, but not limited to, gold, copper, silver, or mixtures, alloys, or combinations thereof. In one non-limiting embodiment, the first reflective layer 46 comprises a thickness of For example

or

or

or or

or metallic silver layer. Other materials that may be used as the first reflective layer 46 may have a similar thickness range.

例如

或或者

的钛。可用作底膜48的其他材料可以具有类似的厚度范围。A first primer film 48 may be deposited over the first reflective layer 46 . The first bottom film 48 may be an oxygen trapping material such as titanium, which may be sacrificed during the deposition process to prevent decomposition or oxidation of the first reflective layer 46 during the sputtering process or subsequent heating process. The oxygen-trapping material may be selected so as to oxidize before the material of the first reflective layer 46 . If titanium is used as the first base film 48, the titanium will preferably oxidize to titanium dioxide before the underlying layer 46 is oxidized. In one non-limiting embodiment, the first bottom film 48 is a thickness of

For example

or or

of titanium. Other materials that may be used as base film 48 may have a similar thickness range.

例如

或

或

或者

的厚度。可用作第二介电层50的其他材料可以具有类似的厚度范围。在另一个非限定实施方案中，第二介电层50可以是多层结构。例如，第二介电层50可以包括如上所述的锡酸锌层和至少一个其它层例如在锡酸锌层之上和/或之下的氧化锌层。该氧化锌层(一个或多个)可以具有

例如

或

或

或

或者

的厚度。[0046] A second dielectric layer 50 may be deposited over the first reflective layer 46 (eg, over the first base film 48). The second dielectric layer 50 may comprise one or more metal oxide or metal alloy oxide-containing films, such as those described above with respect to the first dielectric layer 40 . In the depicted non-limiting embodiment, the second dielectric layer 50 comprises at least one high refractive index material such as, but not limited to, zinc stannate (Zn _0.95 Sn _0.05 O _1.05 ), and has

For example

or

or

or

thickness of. Other materials that may be used as the second dielectric layer 50 may have similar thickness ranges. In another non-limiting embodiment, the second dielectric layer 50 may be a multilayer structure. For example, the second dielectric layer 50 may include a zinc stannate layer as described above and at least one other layer such as a zinc oxide layer above and/or below the zinc stannate layer. The zinc oxide layer(s) may have

For example

or

or

or

or

thickness of.

或

或

或

或

或者

的银。可用作第二反射层58的其他材料可以具有类似的厚度范围。[0047] A second thermal and/or radiation reflective layer 58 may be deposited over the second dielectric layer 50. The second reflective layer 58 may comprise any one or more reflective materials described above with respect to the first reflective layer 46 . In one non-limiting embodiment, the second reflective layer 58 comprises a thickness of For example

or

or

or

or

or

of silver. Other materials that may be used as the second reflective layer 58 may have a similar thickness range.

例如

或

或者

的钛。可用作第二底膜60的其他材料可以具有类似的厚度范围。[0048] A second base film 60 may be deposited over the second reflective layer 58. The second base film 60 may be any of the materials described above with respect to the first base film 48 . In a non-limiting embodiment, the second base film comprises a thickness of

For example

or

or

of titanium. Other materials that may be used as the second base film 60 may have a similar thickness range.

例如

或

或

或

或

或或或者的厚度。在另一个非限定实施方案中，第三介电层62可以是多层结构。例如，第三介电层62可以包括如上所述的锡酸锌层和至少一个其它层例如在锡酸锌层之上和/或之下的氧化锌层。该氧化锌层(一个或多个)可以具有

例如或

或

或

或者

的厚度。[0049] A third dielectric layer 62 may be deposited over the second reflective layer 58 (eg, over the second base film 60). The third dielectric layer 62 may also include one or more metal oxide or metal alloy oxide-containing layers, such as those described above with respect to the first and second dielectric layers 40 , 50 . In one non-limiting embodiment, the third dielectric layer 62 comprises at least one high refractive index material such as a layer containing a metal alloy oxide, such as a zinc stannate layer (Zn ₂ SnO ₄ ), and has

For example

or

or

or

or

or or or thickness of. In another non-limiting embodiment, the third dielectric layer 62 may be a multilayer structure. For example, the third dielectric layer 62 may include a zinc stannate layer as described above and at least one other layer such as a zinc oxide layer above and/or below the zinc stannate layer. The zinc oxide layer(s) may have

For example or

or

or

or

thickness of.

[0050] Accordingly, coating 34a may be generally described as H ¹ /M ¹ /H ² /M ² /H ³ , wherein H ¹ , H ² and H ³ represent layers comprising at least one high refractive index material, And M ¹ and M ² represent metal layers. As will be understood, H ¹ , H ² and H ³ may be the same or different layers, and M ¹ and M ² may be the same or different layers.

例如

或

或或

或

或或者的厚度。可用作第三反射层70的其他材料可以具有类似的厚度范围。[0051] The coating 34b shown in FIG. 3 is similar to that in FIG. 2, but further includes a third thermal and/or radiation reflective layer 70 deposited over the third dielectric layer 62. The third reflective layer 70 can be any material described above with respect to the first and second reflective layers. In a non-limiting embodiment, the third reflective layer 70 includes silver and has

For example

or

or or

or

or or thickness of. Other materials that may be used as the third reflective layer 70 may have a similar thickness range.

例如

或者

的厚度。可用作第三底膜72的其他材料可以具有类似的厚度范围。[0052] A third base film 72 may be deposited on the third reflective layer 70. The third bottom film 72 may be the bottom film material described above with respect to the first or second bottom film. In a non-limiting embodiment, the third base film is titanium and has

For example

or

thickness of. Other materials that may be used as the third base film 72 may have a similar thickness range.

例如

或

或

或

或者

的厚度。可用作第四介电层74的其他材料可以具有类似的厚度范围。[0053] A fourth dielectric layer 74 may be deposited over the third reflective layer (eg, over the third base film 72). The fourth dielectric layer 74 may consist of one or more metal oxide or metal alloy oxide-containing layers such as those described above with respect to the first, second or third dielectric layers 40, 50, 62. In one non-limiting embodiment, fourth dielectric layer 74 comprises at least one high refractive index material, such as a metal alloy oxide layer, such as a zinc stannate layer (Zn ₂ SnO ₄ ). The zinc stannate layer can have

For example

or

or

or

or

thickness of. Other materials that may be used as fourth dielectric layer 74 may have similar thickness ranges.

[0054] Accordingly, the coating 34b can be generally expressed as H ¹ /M ¹ /H ² /M ² /H ³ /M ³ /H ⁴ , wherein H ¹ , H ² , H ³ and H ⁴ represent at least A layer of high refractive index material, and M ¹ , M ² and M ³ represent metal layers. As will be understood, H ¹ , H ² , H ³ and H ⁴ may be the same or different, and M ¹ , M ² and M ³ may be the same or different.

例如

或

的厚度。可用作层76的其他材料可以具有类似的厚度范围。第四高折射率层78形成在低折射率层76之上。在一个非限定实施方案中，第四高折射率层78包含锡酸锌并且具有

例如

或

的厚度。可用作层78的其他材料可以具有类似的厚度范围。[0055] The coating 34c shown in FIG. 4 is also similar to that of FIG. 2, but includes a low index layer 76 deposited over the third dielectric layer 62. In one non-limiting embodiment, low refractive index layer 76 comprises silica and/or alumina and has

For example

or

thickness of. Other materials that may be used as layer 76 may have a similar thickness range. The fourth high refractive index layer 78 is formed on the low refractive index layer 76 . In one non-limiting embodiment, the fourth high refractive index layer 78 comprises zinc stannate and has

For example

or

thickness of. Other materials useful for layer 78 may have a similar thickness range.

[0056] Accordingly, the coating 34c can be generally expressed as H ¹ /M ¹ /H ² /M ² /H ³ /L ¹ /H ⁴ , wherein H ¹ , H ² , H ³ and H ⁴ represent at least one A layer of a high refractive index material (which may be the same or different); L ¹ represents a layer comprising at least one low refractive index material; and M ¹ and M ² represent metal layers and may be the same or different.

[0057] As shown in FIG. 1, a protective coating 80 may be deposited over the outermost dielectric layer of the aesthetic coating 30 to help protect underlying layers, such as anti-reflective layers, from mechanical and chemical attack during processing. . The protective coating 80 may be an oxygen barrier coating to prevent or reduce atmospheric oxygen from entering the underlying layers of the aesthetic coating 30, for example, during heating or bending. The protective coating 80 may be any desired material or mixture of materials. In a non-limiting exemplary embodiment, the protective coating 80 may include a layer having one or more metal oxide materials such as, but not limited to, oxides of aluminum, silicon, or mixtures thereof. For example, protective coating 80 may be a single coating comprising 0% to 100% by weight of alumina and/or 100% to 0% by weight of silica, or 5% to 95% by weight of alumina and 95% to 5wt% of silica, or 10wt% to 90wt% of alumina and 90wt% to 10wt% of silica, or 15wt% to 90wt% of alumina and 85wt% to 10wt% of silica, or 50wt% ~75wt% alumina and 50wt%~25wt% silica, or 50wt%~70wt% alumina and 50wt%~30wt% silica, or 35wt%~100wt% alumina and 65wt%~ 0wt% of silica, or 70wt% to 90wt% of alumina and 30wt% to 10wt% of silica, or 75wt% to 85wt% of alumina and 25wt% to 15wt% of silica, or 88wt% alumina and 12wt% silica, or 65wt% to 75wt% alumina and 35wt% to 25wt% silica, or 70wt% alumina and 30wt% silica, or 60wt% to less than 75 wt% alumina and greater than 25 wt% to 40 wt% silica. Other materials such as aluminum, chromium, hafnium, yttrium, nickel, boron, phosphorus, titanium, zirconium, and/or oxides thereof may also be present, for example to adjust the refractive index of protective coating 80 . In a non-limiting embodiment, the protective coating 80 may have a refractive index of 1-3, such as 1-2, such as 1.4-2, such as 1.4-1.8.

[0058] In one non-limiting embodiment, protective coating 80 is a combined silica and alumina coating. The protective coating 80 can be sputtered from two cathodes (eg, one silicon and one aluminum) or from a single cathode containing both silicon and aluminum. The silicon/aluminum oxide protective coating 80 can be written as Six _{Al 1-x} O _1.5+x/2 , where x can be greater than zero and less than one.

[0059] Alternatively, the protective coating 80 may be a multi-layer coating formed from a layer of a metal oxide material formed separately, such as, but not limited to, a layer formed on top of another metal oxide-containing layer (e.g., containing silicon dioxide and/or or a second layer of alumina) formed on a metal oxide-containing layer (eg, a first layer containing silica and/or alumina) to form a bilayer. The individual layers of the multilayer protective coating can have any desired thickness.

例如

或

或

或或

或者

的硅/铝氧化物涂层(Si_xAl_1-xO_1.5+x/2)。另外，保护涂层80可以具有非均匀的厚度。“非均匀的厚度”是指保护涂层80的厚度可以在给定的单位面积内变化，例如保护涂层80可以具有高和低的点或面积。[0060] Protective coating 80 may have any desired thickness. In one non-limiting embodiment, protective coating 80 is a thickness of

For example

or

or

or or

or

Silicon _/ aluminum oxide coating (Six Al _1-x O _1.5+x/2 ). Additionally, protective coating 80 may have a non-uniform thickness. "Non-uniform thickness" means that the thickness of the protective coating 80 can vary within a given unit area, eg, the protective coating 80 can have high and low spots or areas.

或

或

或

或者大于

至

的厚度。第二层可以包含二氧化硅或者包含二氧化硅和氧化铝的混合物或合金。例如，第二层可以包含具有至少40wt％二氧化硅、例如至少50wt％二氧化硅、或至少60wt％二氧化硅、或至少70wt％二氧化硅、或至少80wt％二氧化硅、或80wt％～90wt％二氧化硅和10wt％～20wt％氧化铝、或者85wt％二氧化硅和15wt％氧化铝的二氧化硅/氧化铝混合物。在一个非限定实施方案中，第二层可以具有大于

至2微米、例如

或

或或

或者的厚度。合适的保护涂层的非限定例子描述于例如美国专利申请Nos.10/007,382；10/133,805；10/397,001；10/422,094；10/422,095和10/422,096中。[0061] In another non-limiting embodiment, protective coating 80 may include a first layer and a second layer formed over the first layer. In a specific non-limiting embodiment, the first layer may comprise alumina or a mixture or alloy comprising alumina and silica. For example, the first layer may comprise at least 5wt% alumina, such as at least 10wt% alumina, or at least 15wt% alumina, or at least 30wt% alumina, or at least 40wt% alumina, or 50wt% to 70wt% alumina , or a silica/alumina mixture of 70wt%-100wt% alumina and 30wt%-0wt% silica, or 90wt%-100wt% alumina and 10wt%-0wt% silica. In a non-limiting embodiment, the first layer may have a value greater than to 1 micron, e.g.

or

or

or

or greater than

to

thickness of. The second layer may comprise silica or a mixture or alloy of silica and alumina. For example, the second layer may comprise at least 40 wt% silicon dioxide, such as at least 50 wt% silicon dioxide, or at least 60 wt% silicon dioxide, or at least 70 wt% silicon dioxide, or at least 80 wt% silicon dioxide, or 80 wt% A silica/alumina mixture of -90 wt% silica and 10 wt% -20 wt% alumina, or 85 wt% silica and 15 wt% alumina. In a non-limiting embodiment, the second layer can have a value greater than

to 2 microns, e.g.

or

or or

or thickness of. Non-limiting examples of suitable protective coatings are described, for example, in US Patent Application Nos. 10/007,382; 10/133,805; 10/397,001; 10/422,094; 10/422,095 and 10/422,096.

[0062] The transparency 10 may further include a reflective coating 32, for example on the No. 4 surface 22 of the second layer 18. In one non-limiting embodiment, reflective coating 32 is an antireflective coating comprising alternating layers of relatively high and low refractive index materials. As noted above, a "high" index material may be any material having a higher index of refraction than said "low" index material. In one non-limiting embodiment, a low refractive index material is a material with a refractive index less than or equal to 1.75. Antireflective coating 32 may be, for example and without limitation of the present invention, a multilayer coating as shown in FIG. layer), a second metal oxide layer 88 (second layer) deposited on said first layer and having a refractive index greater than 1.75, a second metal oxide layer 88 (second layer) deposited on said second layer and having a refractive index less than or equal to 1.75 A tri-metal alloy oxide layer 90 (third layer), and a metal oxide top layer 92 (fourth layer) deposited over the third layer and having a refractive index greater than 1.75. Alternatively, antireflective coating 32 may be, for example and without limitation of the present invention, a multilayer coating as shown in FIG. 5 having a first metal alloy oxide layer 86 with a refractive index greater than 1.75 ( first layer), a second metal oxide layer 88 (second layer) deposited on said first layer and having a refractive index less than or equal to 1.75, a metal oxide layer 88 (second layer) deposited on said second layer and having a refractive index greater than 1.75 A third metal alloy oxide layer 90 (third layer), and a metal oxide top layer 92 (fourth layer) deposited over the third layer and having a refractive index less than or equal to 1.75. In one non-limiting embodiment, fourth layer 92 (upper low index layer) comprises silica or alumina or a mixture or combination thereof and third layer 90 (upper high index layer) comprises zinc stannate or zirconia or a mixture or combination thereof, the second layer 88 (bottom low index layer) comprising silica or alumina or a mixture or combination thereof and the first layer 86 (bottom high index layer) comprising zinc stannate or zirconia or mixtures or combinations thereof.

[0063] As will be understood by those skilled in the art, the thickness of the coating can be specified in different ways. For example, the actual physical thickness of the layer may be specified. Alternatively, the optical thickness of the layer can be specified. As is common in the art and used herein, the "optical thickness" of a material is defined as the thickness of the material divided by the refractive index of the material. Therefore, relative to a reference wavelength of 550nm, the 1 quarter wavelength optical thickness (QWOT) of a material with a refractive index of 2 will be 0.25 x (550nm÷2), which equals 68.75nm. As another example, 0.33 QWOT for a material with a refractive index of 1.75 relative to a reference wavelength of 550nm would equal 0.33 x [0.25 x (550nm÷1.75)] or 25.93nm. Conversely, based on a wavelength of 550nm, a material with a refractive index of 2.2 and a thickness of 50nm would equal [(50nm÷550nm) x 2.2]÷0.25 or 0.8 QWOT. As will be appreciated, although the quarter wave optical thickness of the two materials may be the same, the actual physical thickness of the layers may be different due to the different refractive indices of the materials. The QWOT values used herein and in the following examples are those defined relative to a reference wavelength of 550 nm.

[0064] In a non-limiting embodiment, top layer 92 comprises a material such as silicon dioxide and has a QWOT of 0.7 to 1.5, such as 0.71 to 1.45 QWOT, or 0.8 to 1.3 QWOT. One wavelength, or a thickness of 0.9 to 1.1 quarter wavelengths. As mentioned above, "quarter wavelength" refers to: [(physical layer thickness)·4·(refractive index)]/(reference light wavelength). In this discussion, the reference light wavelength is 550 nm. In this non-limiting embodiment, the thickness of the upper high index layer 90 is defined by the following formula: [-0.3987·(quarter-wavelength value of top layer) ² ]-[1.1576·(quarter-wavelength value of top layer )]+2.7462. Thus, if the top layer 92 is 0.96 quarter wavelengths, the upper high index layer 90 will be [-0.3987·(0.96) ² ]-[1.1576·(0.96)]+2.7462=1.2675 quarter wavelengths. The bottom low index layer 88 is defined by the formula: [2.0567·(quarter wavelength value of top layer) ² ]−[3.5663·(quarter wavelength value of top layer)]+1.8467. The bottom high index layer 86 is defined by the formula: [−2.1643·(quarter wavelength value of top layer) ² ]+[4.6684·(quarter wavelength value of top layer)]−2.2187. In a specific non-limiting embodiment, the antireflective coating 32 includes a 0.96 quarter wavelength (88.83 nm) silicon dioxide top layer 92, a 1.2675 quarter wavelength (84.72 nm) zinc stannate layer 90, 0.3184 quarter wavelength (29.46 nm) silicon dioxide layer 88 , and 0.2683 quarter wavelength (17.94 nm) zinc stannate layer 86 . In another non-limiting embodiment, the quarter wavelength values of layers 86, 88 and 90 may vary by ±25%, such as ±10%, such as ±5%, from the above formula values.

[0065] Other suitable anti-reflective coatings are disclosed in U.S. Patent No. 6,265,076, column 2, line 53 to column 3, line 88; and Examples 1 to 3, U.S. Patent No. 6,570,709, column 2, line 64 to line 5 Column, 22 rows; 8 columns, 12-30 rows; 10 columns, 65 rows to 11 columns, 11 rows; 13 columns, 7 rows to 14 columns, 46 rows; 16 columns, 35-48 rows; 19 columns, 62 rows ~column 21, row 4; Examples 1-13; and Tables 1-8.

[0066] In one practice of the invention, the decorative band 26 is a ceramic enamel material having a color that enhances or enhances the color of the transparency 10. As will be understood by those skilled in the automotive arts, traditional blackout strips are typically black. However, in the practice of the present invention, the trim strip 26 may be of any desired color to complement the color of the transparency 10 . Materials used to prepare decorative strip 26 may include oils, glazes (eg, borosilicate glazes), and pigments of a desired color. The material may be placed on the surface of one of the ply and heated to melt and bond the material to that ply to form the decorative band 26 . Exemplary colors for trim strip 26 include, but are not limited to, white, yellow, blue, red, brown, gold, silver, and green, to name a few. Additionally, designs or other decorative symbols such as, but not limited to, company logos, sports team names, personal names, or decorative designs may be formed in the decorative band 26 .

[0067] The following non-limiting examples illustrate the invention.

Example 1

玻璃，其可从PPG Industries，Inc.of Pittsburgh，Pennsylvania商购获得。通过传统的MSVD技术施加涂层。参照表I，应理解的是Si₈₅Al₁₅O_x涂层表示由其溅射该涂层的阴极的组成。更具体地，Si₈₅Al₁₅O_x是指在氧气氛中溅射由85wt％Si和15wt％Al组成的阴极以形成所述硅铝氧化物涂层。ZnO涂层由具有10wt％Sn的锌阴极溅射以提高溅射特性。所有的TiO₂层由Ti阴极溅射并且作为Ti金属层沉积，随后其在加热期间被氧化而使玻璃弯曲形成风挡。[0068] Laminate articles having the structures listed in Table 1 were prepared. glass is

Glass, commercially available from PPG Industries, Inc. of Pittsburgh, Pennsylvania. The coating is applied by conventional MSVD techniques. _Referring to Table I, it should be understood that the _Si85Al15Ox coating represents the composition of the cathode from which the coating was sputtered _. More specifically, Si ₈₅ Al ₁₅ O _x refers to sputtering a cathode composed of 85 wt % Si and 15 wt % Al in an oxygen atmosphere to form the silicon aluminum oxide coating. The ZnO coating was sputtered from a zinc cathode with 10 wt% Sn to improve sputtering characteristics. All _TiO2 layers were sputtered from Ti cathodes and deposited as Ti metal layers, which were subsequently oxidized during heating to bend the glass to form the windshield.

Table 1

material thickness

Glass 2.3mm

PVB 0.75mm

Si ₈₅ Al _{15 Ox}

Zn ₂ SnO ₄

ZnO

TiO ₂

Ag

ZnO

Zn ₂ SnO ₄

ZnO

TiO ₂

Ag

ZnO

Zn ₂ SnO ₄

Glass 2.3mm

[0069] Six preparations were prepared and the color properties were measured. The results for the 6 preparations are listed in Table II below.

Table II

Parameter value range

L ^* 51～54

a ^* -5.1～7.6

b ^* -31～-33.1

[0070] These articles have an aesthetically pleasing blue color.

Example 2

[0071] In this example, a computer-generated laminate was designed using WINFILM software commercially available from FTG Software Associates of Princeton, New Jersey.

[0072] The article had the structure described in Table III.

Table III

material thickness

Si ₈₅ Al _{15 Ox}

ZnSnO ₄

Glass 2.3mm

PVB 0.75mm

Si ₈₅ Al _{15 Ox}

Zn ₂ SnO ₄

TiO ₂

Ag

ZnSnO ₄

TiO ₂

Ag

ZnSnO ₄

Si ₈₅ Al _{15 Ox}

Zn ₂ SnO ₄

Glass 2.3mm

[0073] The computer-generated articles had color properties as determined by WINFILM software as described in Table IV.

Table IV

Parameter value range

L ^* 45

a ^* 35

b ^* -7

[0074] The article has an aesthetically pleasing red color.

Example 3

[0075] Laminate articles having the structures listed in Table V were prepared. The glass is 2.1 mm CLEAR glass commercially available from PPG Industries, Inc. of Pittsburgh, Pennsylvania. The coating is applied by conventional MSVD techniques. The ZnO coating was sputtered from a zinc cathode with 10 wt% Sn to improve sputtering characteristics. All _TiO2 layers were sputtered from Ti cathodes and deposited as Ti metal layers, which were subsequently oxidized during heating to bend the glass to form the windshield.

Table V

material thickness

Glass 2.1mm

PVB 0.75mm

TiO ₂

Zn ₂ SnO ₄

ZnO(10%wt.Sn)

TiO ₂

Ag

Zn ₂ SnO ₄

ZnO(10%wt.Sn)

TiO ₂

Ag

ZnO(10%wt.Sn)

Zn ₂ SnO ₄

Glass 2.1mm

[0076] Six preparations were prepared and the color properties were measured. The results for the 6 preparations are listed in Table VI below.

Table VI

Parameter value range

L ^* 51～54

a ^* -5.1～7.6

b ^* -31～-33.7

[0077] The article has an aesthetically pleasing blue color.

[0078] Figures 6 and 7 illustrate the color spaces achievable by the aesthetic coating 30 of the present invention. In particular, the area in line A of FIG. 6 represents the color space achievable by the aesthetic coating 30 of the present invention incorporating two silver reflective layers, and the area in line A of FIG. 7 represents the color space of the present invention incorporating three silver reflective layers. Aesthetically pleasing 30 achievable color spaces. Figures 6 and 7 also illustrate the change in reflected color, ie color shift, of the coatings of the present invention when the viewing angle is changed. More specifically, the color coordinates shown in Figures 6 and 7 are based on a viewing angle normal to the coating surface. The normal viewing angle used here is expressed as a 0° viewing angle. As the viewing angle of the coating changes, the chromaticity (C ^* ) and/or hue angle (H°) will change, and as the viewing angle approaches 90°, C ^* will approach 0, as discussed in further detail below. Coatings falling between lines A and B in Figures 6 and 7 will exhibit the greatest color shift, and are especially characterized by a color shift with a change in H° greater than 30° (large color shift). Coatings falling between lines B and C will exhibit less color shift and be characterized by a change in H° of 15° to 30° (medium color shift). Coatings falling within line C will exhibit the least amount of color shift and be characterized by a change in H° of less than 15° (small color shift). Continuing to refer to FIG. 6, line D represents the change in color coordinates of a non-limiting double silver coating of the present invention as the viewing angle increases from 0° and approaches 90°. More particularly, for this particular coating, it can be seen that the coating has a blue-green color and a C ^* of about 32 at a viewing angle of 0°. When the viewing angle changes, the chromaticity and hue angles change. More specifically, when the viewing angle increases, the coating color becomes magenta (hue angle changes over 30°) and C ^* approaches 0.

Example 4

[0079] In this example, a computer-generated laminate was designed using WINFILM software commercially available from FTG Software Associates of Princeton, New Jersey.

[0080] The article had the structure described in Table VII.

Table VII

material thickness

Glass 2.1mm

PVB 0.75mm

Top Oxide See Table VIII

TiO ₂

Top layer Ag see Table VIII

Intermediate oxide See Table VIII

TiO ₂

Bottom Ag See Table VIII

Bottom oxide See Table VIII

Glass 2.1mm

[0081] The computer-generated article had color properties as determined by WINFILM software as described in Table VIII. The values listed in Table VIII for the oxide are in QWOT and the values for the silver layer are in nanometers.

Table VIII

Top Oxide Top Silver Middle Oxide Bottom Silver Bottom Oxide H° C ^*

1.47803405 7.3010605 1.45469155 10.0393406 0.449228424 -172.31163 22.83959

0.42894311 11.6696038 1.39721165 7.15281918 1.638595781 -157.43957 25.00694

1.05994611 9.07784624 1.54035006 7.2 1.605890288 -142.37952 31.87471

0.86221636 11.2781957 1.53174193 7.70131957 1.540585939 -127.41194 31.76128

0.60170621 12.1828347 1.52150696 10.1238893 1.1921954 -112.2562 31.2927

0.76662165 15.2552864 1.50746268 11.5033085 0.832109277 -97.496836 34.16264

0.85154085 15.8474899 1.44771742 9.31801635 0.827105069 -82.524191 33.02236

1.00681752 14.7034473 1.3849677 7.28385626 0.993421761 -67.620033 37.83522

0.96962323 14.4647907 1.29607388 7.49877319 0.991320057 -53.85359 38.27008

1.10469792 7.49926791 1.14634744 9.27903996 1.658826436 -38007388 33.59996

1.10758961 7.49790471 1.12520224 9.86205429 1.917205213 -22.710844 26.31427

0.91478606 7.49749251 1.20037453 14.7366175 0.461404822 -22.819872 24.10925

0.88542716 7.49565361 1.15341349 13.9987259 0.441673945 -7.6680225 21.70998

0.84622418 7.49508375 1.11996693 13.5361031 0.441591017 7.4141969 20.22717

0.82156413 7.49488149 1.08275396 13.0439915 0.441550423 22.489675 19.76049

0.82962032 7.49478527 1.01566837 12.0480034 0.441389357 37.57715 20.61959

0.77256356 7.49468338 0.93531471 11.1335855 0.441367213 52.621502 207844

0.62337519 7.25092896 0.87462608 11.3117515 0.441335923 62.934711 20.19332

0.92324817 7.49916012 0.99928502 7.49861915 0.962219848 82.624968 18.33789

0.8548692 7.49583053 0.93287294 7.49488161 0.886488435 97.16284 16.97084

1.97133787 7.49984555 1.43271422 7.47935997 0.475872629 112.90986 21.60134

1.87024787 7.49143564 1.37901846 7.47044243 0.446790429 127.20813 22.32101

1.88387557.49077073 1.38012854 9.11905986 0.44679516 142.44026 22.78468

1.844462037.49405669 1.37420613 10.3472094 0.447664001 157.43855 24.38749

1.685074727.39322332 1.39606639 10.4505774 0.448256997 172.53919 23.80216

[0082] Those skilled in the art will readily appreciate that modifications may be made to the invention without departing from the concepts disclosed in the foregoing description. Therefore, the specific embodiments described in detail herein are illustrative only and do not limit the scope of the invention, which is to give the full breadth of this disclosure and any and all equivalents thereof. The following claims describe various aspects of the invention and form a part of this disclosure. However, as will be understood, the invention is not limited by the following claims.

Claims (32)

1. A laminated transparent body comprising: First layer with No.1 and No.2 surfaces; Second layer with No.3 and No.4 surfaces; an intermediate layer located between the first layer and the second layer; and an aesthetic coating deposited over at least a portion of said first or second layer, where the transparent body has a color defined by: At least one of |a ^* | and |b ^* | is greater than or equal to 10. 2. The transparency of claim 1, wherein said transparency has a color defined by: L ^* ≥44. 3. The transparency of claim 1, wherein said transparency has a color defined by: 40≤L ^* ≤60; 10≤|a ^* |≤50; and 10≤|b ^* |≤80. 4. The transparency of claim 1, wherein said transparency has a color defined by: 40≤L ^* ≤60; and 15≤C ^* ≤90. 5. The transparency of claim 1, wherein said transparency has a color defined by: 40≤L ^* ≤60; |a ^* | ≥ 10, and |b ^* |≥10. 6. The transparency of claim 1, further comprising a reflective coating deposited over at least a portion of one of the layers. 7. The transparency of claim 1, wherein said aesthetic coating comprises a coating stack comprising: H ¹ /M ¹ /H ² /M ² /H ³ , where H ¹ , H ² and H ³ represent layers comprising at least one high refractive index material, and M ¹ and M ² represent metal layers. 8. The transparency of claim 1, wherein said aesthetic coating comprises a coating stack comprising: H ¹ /M ¹ /H ² /M ² /H ³ /M ³ /H ⁴ , where H ¹ , H ² , H ³ and H ⁴ denote layers comprising at least one high refractive index material, and M ¹ , M ² and M ³ denote metal layers. 9. The transparency of claim 1, wherein said aesthetic coating comprises a coating stack comprising: H ¹ /M ¹ /H ² /M ² /H ³ /L ¹ /H ⁴ , Where H ¹ , H ² , H ³ and H ⁴ denote layers comprising at least one high refractive index material, M ¹ and M ² denote metal layers, and L ¹ denote layers comprising at least one low refractive index material. 10. The transparency of claim 1, wherein said transparency has an Lta of at least 70%. 11. The transparency of claim 1 wherein said aesthetic coating is on a No. 2 surface. 12. The transparency of claim 6, wherein said reflective coating is an antireflective coating on a No. 4 surface. 13. The transparency of claim 12, wherein said antireflective coating comprises a first layer having a refractive index greater than 1.75, a second layer deposited over said first layer and having a refractive index less than or equal to 1.75, deposited over said a third layer having a refractive index greater than 1.75 on the second layer, and a fourth layer deposited on the third layer and having a refractive index less than or equal to 1.75. 14. The transparency of claim 1 comprising a protective coating deposited over said aesthetic coating, said protective coating comprising at least one of silica, alumina, zirconia, and mixtures thereof. 15. The transparency of claim 7, wherein the metallic layers each comprise a metal selected from the group consisting of gold, copper, silver, or a mixture, alloy, or combination comprising at least one thereof. 16. The transparency of claim 7, wherein said high refractive index materials are each selected from the group consisting of zirconia, titanium oxide, zinc oxide, zinc stannate, and mixtures or combinations thereof. 17. The transparency of claim 9, wherein the low refractive index materials are each selected from the group consisting of silica, alumina, and mixtures or combinations thereof. 18. The transparency of claim 1, further comprising a decorative band disposed about at least a portion of the perimeter of at least one of said layers, said decorative band having a color selected to complement the color of said transparency. 19. The transparency of claim 18, wherein the decorative band includes at least one decorative symbol and/or decorative design. 20. A laminated transparency comprising: (a) a first glass layer with No. 1 and No. 2 surfaces; (b) a second glass layer with No. 3 and No. 4 surfaces; (c) an interlayer between said first glass ply and said second glass ply; (d) an aesthetic coating deposited over at least a portion of said No. 2 surface, said aesthetic coating comprising a coating stack comprising: H ¹ /M ¹ /H ² /M ² /H ³ , where H ¹ , H ² and H ³ denote layers comprising at least one material with a refractive index greater than 1.75, and M ¹ and M ² denote metal layers, where the transparent body has a color defined by: |a ^* | ≥ 10; and |b ^* |≥10 (e) An antireflection layer formed on at least a part of the surface of said No. 4. 21. The transparency of claim 20, wherein said transparency has a color defined by: L ^* ≥40. 22. The transparency of claim 20, wherein Hi ^{, H2} , and ^H3 are each selected from the group consisting of zirconia, titania, zinc stannate, and mixtures or combinations thereof. 23. The transparency of claim 20, wherein ^M1 and ^M2 are each selected from gold, silver, copper, or a mixture, alloy, or combination comprising at least one of them. 24. The transparency of claim 20, wherein said antireflective coating comprises a first layer having a refractive index greater than 1.75, a second layer deposited over said first layer and having a refractive index less than or equal to 1.75, deposited over said a third layer having a refractive index greater than 1.75 on the second layer, and a fourth layer deposited on the third layer and having a refractive index less than or equal to 1.75. 25. The transparency of claim 20, wherein said transparency has an Lta of at least 70%. 26. The transparency of claim 20 comprising a protective coating deposited over said aesthetic coating, said protective coating comprising at least one of silica, alumina, zirconia, and mixtures thereof. 27. The transparency of claim 20, further comprising a decorative band disposed about at least a portion of the perimeter of at least one of said layers, said decorative band having a color selected to complement the color of said transparency. 28. The transparency of claim 27, wherein said decorative band includes at least one decorative symbol and/or decorative design. 29. A laminated automotive transparency comprising: (a) a first glass layer with No. 1 and No. 2 surfaces; (b) a second glass layer with No. 2 and No. 3 surfaces; (c) a polymeric interlayer positioned between said first glass ply and said second glass ply; (d) an aesthetic coating deposited over at least a portion of said No. 2 surface, said aesthetic coating comprising a coating stack comprising: H ¹ /M ¹ /H ² /M ² /H ³ , wherein H ¹ , H ² and H ³ each comprise zinc stannate, and M ¹ and M ² each comprise silver, where the transparent body has a color defined by: L ^* ≥40; |a ^* | ≥ 10; and |b ^* |≥10 (e) a protective coating deposited over said aesthetic coating, said protective coating comprising a multilayer coating stack comprising silica, alumina, zirconia, and mixtures thereof or at least one of the combinations; and (f) an antireflection coating formed over at least a portion of said No. 4 surface, Wherein the antireflective coating comprises a first layer having a refractive index greater than 1.75, a second layer deposited on the first layer and having a refractive index less than or equal to 1.75, deposited on the second layer and having a refractive index A third layer greater than 1.75, and a fourth layer deposited over the third layer and having a refractive index less than or equal to 1.75. 30. An aesthetic transparency comprising: at least one substrate having a first major surface and a second major surface; an aesthetic coating formed over at least a portion of the first major surface; and a reflective coating formed over at least a portion of the second major surface, wherein the transparent body has a color defined by |a ^* |≥10 and |b ^* |≥10. 31. The transparency of claim 30, wherein said transparency has a color defined by: L ^* ≥40. 32. A laminated transparency comprising: level one; Second floor; an intermediate layer between said first and second layers; and an aesthetic coating located between said first and second layers, Wherein the transparent body has a color defined by at least one of (a) |a ^* |≥10 and |b ^* |≥10 and (b) L ^* ≥40.

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