RU2287433C2 - Transparent article with protecting coating - Google Patents

Abstract

FIELD: automotive industry.

SUBSTANCE: article comprises substrate and covering pack provided with functional coating. The functional coating is applied at least to a part of the substrate. The protecting coating is applied at least to a part of the functional covering. The emitting factor of the covering pack covered with the protecting coating exceeds the emitting factor of the functional coating, and their reflection factor ranges from 1.4 to 2, with the thickness ranging from 100Å to 10 μm.

EFFECT: enhanced strength.

10 cl, 9 dwg, 2 ex

Description

FIELD OF THE INVENTION

This invention relates generally to coated products having a protective coating, for example, to the transparent elements of a coated car.

State of the art

A known method of reducing heating of the interior of a vehicle by creating a laminated windshield having two layers of glass with a control coating that attenuates the infrared or ultraviolet part of sunlight located between the layers. Layers of glass protect the layer that controls the passage of sunlight from mechanical and / or chemical damage. These conventional windshields are usually made by forming and annealing two flat glass preforms (one of which has a sunlight control coating applied thereto) to form two formed, annealed glass layers, followed by bonding the glass layers to each other using a plastic intermediate layer. Since conventional sunlight control coatings include metal layers that reflect heat, glass blanks are usually heated and formed into “doublets”, i.e. the blanks are placed one on top of the other during heating and molding, while the functional coating is located between the glass blanks to prevent uneven heating and cooling, which can affect the final shape of the layers. Examples of laminated automotive windshields and methods for their manufacture are disclosed in patents US 4820902, 5028759 and 5653903.

The heating of the doublet is usually limited by the ability of the functional coating to endure heat treatment without harmful degradation. By “heatability” is meant the maximum temperature and / or maximum time at a particular temperature to which the coated substrate can be heated without degradation of the functional coating. Such degradation may affect the physical and / or optical properties of the coating, such as reflection and / or transmission of solar energy. The considered degradation can be caused, for example, by the oxidation of various layers in a functional coating containing metal. For example, a functional coating containing metal layers may be sensitive to oxygen, so that some change is possible, for example, deterioration of optical properties or properties of regulating the passage of sunlight when the coated substrate is subjected to heat treatment, such as bending heat, hardening, or annealing , or vacation, for use in automotive transparent elements and windows, or for use in apartment or commercial windows, panels, doors or household electrical appliances.

It is preferable to provide other solar elements with a solar control coating, such as side windows, rear windows, sliding roofs, transparent roofs, etc. However, the manufacturing process of laminated windshields is not easy to adapt to the manufacture of other transparent automotive elements of a laminated or non-laminated type. For example, automobile side windows are usually made of a single glass billet, which is separately heated, formed and tempered with the desired curvature specified by the size of the hole in the car into which the side window is to be installed. A problem arising in the manufacture of side windows, which does not occur in the manufacture of windscreens, is the separate heating of glass blanks having a coating that regulates the reflection of the heat of sunlight.

In addition, if the side window is located so that the coating is on the outer surface of the side window of the car, then the coating is sensitive to mechanical damage, for example, from objects that hit it, and to chemical damage from acid rain or detergents used in car wash. If the coating is located on the inner surface of the side window of the car, the coating is sensitive to mechanical damage from the touch of people in the car or from moving up and down in the window opening and to chemical damage from contact with ordinary glass cleaning products. In addition, if the coating is a coating with a low coefficient of blackness, then it can contribute to the greenhouse effect, retaining heat inside the car. In this case, the blackness coefficient is defined as the ratio of the energy emitted by a given surface at a given temperature to the energy of an ideal emitter (absolutely black body) at the same temperature.

Although a method is known for reducing chemical damage or corrosion of a coating by using an external coating with a chemically resistant material, such coatings are usually applied as thin as possible to avoid negative effects on the optical characteristics (e.g. color, reflectance and transmittance) of the inner coating located underneath and for slight increase the blackness coefficient of the underlying coating. Such thin exterior coatings generally do not meet the requirements of durability during the molding, processing or end use of conventional coated automotive components that are easily damaged and constantly exposed to the environment. Additionally, such thin external coatings cannot mitigate the above greenhouse effect. Examples of conventional coatings are disclosed in US patents 4716086, 4 786 563, 5425861, 5344718, 5376455, 5584902 and 5532180.

Therefore, it would be preferable to create a product, for example, a laminated or non-laminated automotive transparent element, or a panel, or a sheet having a working coating that solves at least some of the above problems.

Disclosure of invention

The product according to the invention contains a substrate and a functional coating, not limited to the reflecting infrared portion of sunlight by a dielectric functional coating, located at least on a part of the substrate. A protective coating is applied to at least a portion of the functional coating. Functional coating and protective coating create a coating bag. The protective coating provides the emissivity of the coating bag in excess of the emissivity of the functional coating. The protective coating may have a thickness in the range from more than 100 Å to less than 10 microns and a reflection coefficient in the range from 1.4 to 2, for example, from 1.4 to 1.8. The protective coating may contain one or more layers. In one embodiment, the protective coating comprises a first layer formed at least in part of the functional coating and a second layer formed in at least part of the first layer. In one particular, non-limiting embodiment, the first layer may contain from 50 to 100 wt.% Alumina and from 50 to 0 wt.% Silicon dioxide, and the second layer contains from 50 to 100 wt.% Silicon dioxide and from 50 to 0 wt.% Alumina.

The monolithic transparent element according to the invention comprises a glass substrate and a functional coating applied to at least a portion of the glass substrate. A protective coating is applied to at least a portion of the functional coating to form a coating bag. The protective coating may contain alumina and may have a thickness in the range from 1 micron to 10 microns. The protective coating may contain one or more layers. In one embodiment, the protective coating comprises a first layer formed at least in part of the working coating and a second layer formed in at least part of the first layer. In one particular, non-limiting embodiment, the first layer may contain from 50 to 100 wt.% Alumina and from 50 to 0 wt.% Silicon dioxide, and the second layer from 50 to 100 wt.% Silicon dioxide and from 50 up to 0 wt.% alumina.

Brief Description of the Drawings

The drawings show:

figure 1 is a section of the edge of the layered automotive transparent element, such as side glass, including features of the invention, in side view (on an enlarged scale);

figure 2 - device (with parts removed for clarity) for the manufacture of glass blanks G according to the invention in isometric view;

figure 3 is a sectional view of a part of a monolithic product, including features of the invention, in side view (on an enlarged scale);

4 is a graph showing the results of the Taber abrasion test of substrates having a protective coating according to the invention compared to substrates without a protective coating;

Figure 5 is a graph of average haze for selected substrates according to figure 4;

6 is a graph of the magnitude of the coefficient of blackness versus coating thickness for substrates having a protective coating according to the invention;

7 is a graph showing the results of a Taber abrasion test of substrates having a protective coating according to the invention;

Fig. 8 is a histogram showing the effect of heat treatment and coating thickness on Taber abrasion for coated substrates having a protective coating according to the invention;

Fig. 9 is a graph showing the variation in visible light transmittance (Lta) as a function of heating for a coated working substrate having a protective coating according to the invention (line A) and for a coated working substrate without a protective coating (line B). A decrease in the curvature of the slope of line B indicates a deterioration in the performance of the coated substrate without protection as compared to the coated coated substrate under the same heating conditions.

The implementation of the invention

Used in this case, concepts relating to space or direction, such as left, right, inside, outside, top, bottom, top, bottom, etc., are used in accordance with the drawings in the figures. However, it should be understood that the invention allows for various alternative orientations, so that these concepts should not be understood as limiting the invention.

In addition, all the numbers used in the description and in the claims expressing dimensions, physical characteristics, process parameters, amount of ingredients, reaction conditions, etc., should be understood in all cases as modified by the term "about". Accordingly, unless otherwise indicated, the numerical values indicated in the following description and in the claims may vary depending on the desired properties to be provided by this invention. Finally, but not as an attempt to limit the substitution of equivalent quantities in the claims, each numerical value should at least be construed in light of the number of decimal places presented and by applying the usual rounding rules. In addition, all presented ranges should be understood as covering the initial and final values of the range and any and all subranges included in it. For example, the indicated range “from 1 to 10” should be understood as including any and all subranges between (and including) a minimum value of 1 and a maximum value of 10; those. all subranges starting with a minimum value of 1 or more and ending with a maximum value of 10 or less, for example 5.5. The terms “flat” or “substantially flat” substrate refer to a substrate that is substantially flat in shape, i.e. a substrate lying primarily in one geometric plane, while the substrate, as is understood by those skilled in the art, may include slight bends, protrusions, or indentations. In addition, the terms “formed on”, “deposited on” or “created on” used in this case means “formed”, “applied”, “created”, but not necessarily in contact with the surface. For example, a coating layer “formed on” a substrate does not exclude the presence of one or more other coating layers or films of the same or different composition located between the formed coating layer and the substrate. For example, the substrate may include conventional coatings known in the art, such as glass or ceramic. All referenced documents should be understood as documents whose full contents are included in this description. Used in this case, the concept of "polymer" or "polymer" refers to oligomers, homopolymers, copolymers and terpolymers, for example, polymers formed from two or more types of monomers or polymers.

As follows from the following description, a protective (eg, barrier) coating according to the invention can be used in the manufacture of both laminated and non-laminated products, for example from one substrate. By “protective coating” or “barrier coating” is meant a film, layer or coating formed from a protective or barrier material and having a sufficient thickness to limit the transmission of oxygen-containing gases through the coating. By “protective material” or “barrier material” is meant a material having a low permeability to oxygen-containing gases such as air or water vapor. The material may have a high resistance to the passage of oxygen or air or water vapor through it. A more suitable barrier material has a limited tendency to crack when it is formed into a coating under the conditions of the invention and is substantially resistant to oxygen under such conditions. For specialists in the art it is clear that the permeability of the material is a function of the thickness of the material. The protective coating according to this invention exhibits a relatively high resistance together with both air and water vapor, however, in some applications it is not required to resist both of them. Therefore, low permeability to air or water vapor is sufficient to classify the coating as a “protective coating”. Embodiments of the protective coatings according to this invention, designed primarily as oxygen barriers, can have oxygen permeability, such as approximately less than 1.5, such as less than 1.0, such as less than 0.5, measured in cubic centimeters oxygen penetrating through a sample 1 mm thick on an area of 100 square inches for 24 hours with a difference of the partial pressure of oxygen in one atmosphere at a temperature of 23 ° C and a relative humidity of zero. The protective layer can be resistant to oxygen-containing gases, so that the coating can withstand heat treatment, such as heating for bending, bending, hardening, or annealing, with a minimum, if any, change in its barrier properties with respect to oxygen compared to those available before heat treatment stages.

For use in laminated products, the protective coating can usually be thinner than for non-laminated products. First, an exemplary description of structural components and a method for manufacturing a layered product according to the invention will be given, and then a construction description of an example of a monolithic product according to the invention will be given. By “monolithic” is meant the presence of a single structural support or structural element, for example, a single substrate. In the following, as an example of the product (laminated or monolithic), a description of automobile side glass is provided. However, the invention is not limited to automotive side windows, and it can be used for any products, such as insulating glass blocks, apartment or commercial laminated windows (e.g. overhead lights) or transparent elements for ground, air, space, surface and underwater vehicles means, for example, windshields, taillights, sliding roofs.

Figure 1 shows a laminated product in the form of a side window 10, including features of the invention. Laminated side glass 10 comprises a first substrate or layer 12 having an outer main surface 13 and an inner main surface 14. By “layer” is meant a substrate that is bent into a desired shape or curvature and / or processed by heating, such as annealing or hardening. The functional coating 16 may be formed at least in part or, preferably, on the entire inner main surface 14 by any conventional method, such as, for example, chemical vapor deposition, magnetron sputtering, vapor deposition, pyrolysis spraying. As will be described in more detail below, the protective or barrier coating 17 according to the invention can be formed at least in part or, preferably, on the entire working coating 16. The protective coating not only improves mechanical and chemical resistance, but also provides improved performance heating to bend and / or form the workpiece on which it is applied. The polymer layer 18 may be located between the first layer 12 and the second layer or substrate 20 having an inner main surface 22 and an outer main surface 23. In one embodiment, which is not restrictive, the outer main surface 23 may face the outside of the car, and the outer the main surface 13 may be facing inside the car. Conventional edge sealant 26 can be applied around the perimeter of the laminated side window 10 during and / or after lamination in the usual way. Decorative tape 90, for example, an opaque, transparent or colored tape, may be provided on the surface of at least one of the layers 12 and 20, for example, around the perimeter of one of the inner or outer main surfaces.

In the widespread practice of applying the invention, the substrates used for the first layer 12 and the second layer 20 may be of any material having any desired characteristics, such as opaque, translucent, or transparent to visible light. By "transparent" is meant a material having a transmittance through the substrate of more than 0% up to 100%. By "visible light" or "range of visible light" is meant electromagnetic radiation in the range from 395 nm to 800 nm. Alternatively, the substrate may be translucent or opaque. “Translucent” means a substrate that allows electromagnetic radiation (for example, visible light) to pass through the substrate, but dissipates energy so that objects from the side of the substrate opposite the observer are not clearly visible. By “opaque” is meant a substrate having a visible light transmittance of 0%. Examples of suitable substrates include, for example, plastic substrates (such as acrylic polymers: polyacrylates, polyalkyl methacrylates, polymethyl methacrylates, polyethyl methacrylates, polypropyl methacrylates and the like; polyurethanes; polycarbonates; polyacryl terephthalates: polyethylene terephthalate (PET); polypropylene terephthalate; polysiloxane-containing polymers; or copolymers of any monomers for their manufacture or any mixtures thereof); metal substrates, for example, such as galvanized steel, stainless steel and aluminum; ceramic substrates; tile substrates; glass substrates or mixtures or combinations of any of them. For example, the substrate may be ordinary unpainted sodium-calcium-silicate glass, i.e. “Transparent glass”, or it can be tinted glass, borosilicate glass, lead glass, tempered, non-tempered, annealed and heat-strengthened glass. Glass may be of any type, such as ordinary float glass or sheet glass, and may have any composition having any optical properties, for example, any amount of transmittance of visible radiation, ultraviolet radiation, infrared radiation and / or the full solar spectrum. Types of glass suitable for practicing the invention are described, for example, in US Pat. Nos. 4,746,347, 4,792,536, 5,240,886, 5,385,872 and 5,393,593. The invention is not limited to the thickness of the substrate. The substrate may be generally thicker for typical architectural applications than for typical automotive applications. In one embodiment, the substrate may be glass, having a thickness in the range from 1 to 20 mm, for example from about 1 to 10 mm, or from 2 to 6 mm, or from 3 to 5 mm. To form laminated automotive side glass, the first and second layers 12, 20 may have a thickness of approximately less than 3 mm, for example less than 2.5 mm, or in a thickness range of from about 1 to about 2.1 mm. As will be described below, the thickness of the monolithic products may be greater.

The substrate may have barrier properties with respect to oxygen, for example, may be made of a material that prevents or limits the diffusion of oxygen through the substrate. As an alternative solution, another oxygen-barrier coating (in addition to the barrier coating 17, which will be described below) can be formed over at least a portion of the substrate, and then a functional coating 16 can be formed over this other oxygen-barrier coating. The other oxygen barrier coating may be any material that prevents or limits the diffusion of oxygen, such as, but not limited to, the material used for the protective coating 17, which will be described below.

The functional coating may be of any desired type. In this case, the term "functional coating" refers to a coating that modifies one or more physical properties of the substrate on which it is applied, for example, optical, chemical or mechanical properties, and is not intended to be completely removed from the substrate during subsequent processing. The functional coating 16 may have one or more layers or films having the same or different properties or functions. Used in this case, the concept of "film" refers to a covered area with the desired or selected coating composition. A “layer” may contain one or more “films”, and a “coating” may contain one or more “layers”.

Functional coating 16 may be an electrically conductive coating, such as, for example, the coating used for making heated windows, disclosed in US Pat. Nos. 5,653,903 and 5,028,759, or a coating with one or more films used as an antenna. Similarly, the working coating may be a coating that regulates the passage of sunlight. The term “sunlight control coating” as used herein refers to a coating containing one or more layers or films that affect the sunlight transmission properties of the coated article, including, but not limited to, the amount of sunlight emitted, for example, visible, infrared or ultraviolet radiation incident and / or passing through a coated article, absorption or reflection of infrared or ultraviolet radiation, shading coefficient, blackness coefficient, and .d. A sunlight control coating can block, absorb, or filter out selected parts of the sunlight spectrum, such as, for example, infrared, ultraviolet, and / or visible spectra. Examples of regulating the passage of sunlight of coatings that can be used for the practical implementation of the invention can be found, for example, in US Pat. US patent No. 09/058 440.

The functional coating may be a coating with a low black coefficient, which allows radiation with a wavelength of visible light, for example, from 395 to 800 nm, to pass through the coating, but reflects the infrared component of sunlight having longer waves. By "low black factor" is meant a black coefficient of less than 0.4, or less than 0.3, or less than 0.2, or less than 0.1, for example, less than or equal to 0.05. Examples of coatings with a low coefficient of blackness can be found, for example, in US Pat. compounds, composites, combinations, or mixtures thereof. For example, functional coating 16 may be a single layer of a metal oxide coating, a multi-layer coating of metal oxide, a coating of non-metal oxide, a coating of metal nitride or oxynitride, or a multi-layer coating.

Suitable functional coatings for use in the invention are commercially available from PPG Industries, Inc. of Pittsburg, PA under the name of the SUNGATE ^® and SOLARBRAN ^® coating families. Such functional coatings typically comprise one or more anti-reflective coating films containing dielectric or anti-reflective materials, such as metal oxides or metal alloy oxides, which are transparent to visible light. The functional coating may also include one or more infrared reflective films comprising a reflective metal, for example a noble metal such as gold, copper or silver, or combinations or alloys thereof, and may further comprise a primer film or a barrier film such as a titanium film, as is known in the art, located above and / or below a reflective metal layer. The functional coating can have any desired number of infrared energy reflecting films, such as 1 or more layers of silver, for example, 2 layers of silver or, for example, 3 or more layers of silver.

The functional coating 16 can be located, for example, on one of the inner main surfaces 14, 22 of the laminated product to provide less sensitivity of the coating 16 to environmental and mechanical wear than when it is located on the outer surface of the laminated product. However, a functional coating 16 may be provided on one or both of the outer main surfaces 13 or 23. As shown in FIG. 1, a portion of the coating 16, for example, an area with a width of about 1-20 mm, such as 2-4 mm, around the outer the perimeter of the covered area, can be removed or erased in the usual way, for example, by grinding before lamination or masking during lamination, to minimize damage to the functional coating 16 at the edge of the laminate due to weather or environmental influences emya use. In addition, the removal can be performed to ensure operating parameters, for example, for antennas, heated windshields or to improve the transmission of radio waves, while the removed part can be of any size. For aesthetic purposes, a colored, opaque or translucent strip 90 may be provided over any surface of the layers or coatings, for example, over one or both surfaces of one or both layers, for example, around the perimeter of the outer main surface 13 to cover the removed portion. The strip 90 may be made of ceramic material and may be burned onto the outer main surface 13 in any conventional manner.

The protective (barrier) coating 17 according to the invention can be formed at least on, for example, part, and preferably on the entire outer surface of the functional coating 16. The protective coating, among other things, can increase the black factor of the coating bag (for example, functional coating and protective coating) to a value greater than the blackness coefficient of one functional coating 16. For example, if the functional coating has a blackness coefficient of 0.2, the addition of a protective coating 17 may increase the blackness coefficient of the resulting coating packet to more than 0.2. In one embodiment, the protective coating can increase the black factor of the resulting coating bag by two or more times as compared to the black coefficient of one functional coating (for example, if the blackness coefficient of the functional coating is 0.05, then adding a protective coating can increase the blackness of the resulting coating bag up to 0.1 or more), for example, 5 times or more, for example, 10 times or more, for example, 20 times or more. The protective coating can increase the blackness of at least one functional coating and at least one applied protective coating when the functional coating has a blackness in the range from 0.02 to 0.30, more suitably from 0.03 to 0 , 15, at least from less than 10 to 3000%, or within this range by 50-200%, or 10-200%, or 200-1000%, or 1000-3000%. In another embodiment, the protective coating 17 may increase the black factor of the resulting coating bag substantially to the black factor of the coated substrate. For example, if the substrate is glass having a black factor of about 0.84, then the protective coating 17 can provide a black coefficient of the coating bag in the range from 0.3 to 0.9, such as, for example, more than 0.3, more than 0.5 , more than 0.6 or in the range from 0.5 to 0.9. As will be shown below, an increase in the black coefficient of the working coating 16 by applying a protective coating 17 improves the heating and cooling characteristics of the coated layer 12 during processing. The protective coating 17 also protects the functional coating 16 from mechanical and chemical influences during handling, storage, transportation and processing.

In one embodiment, the protective coating 17 may have a refractive index substantially the same as that of the layer 12 on which it is laminated. For example, if layer 12 is glass having a refractive index of 1.5, then the protective coating 17 may have a refractive index of less than 2, such as 1.4-1.8, or 1.3-1.8, or 1.5 ± 2.

The protective coating 17 may have any desired thickness. In one exemplary embodiment of the laminate, the protective coating 17 may have a thickness in the range from 100 Å to 50,000 Å, or from 500 Å to 50,000 Å, or from 500 Å to 10,000 Å, or such as from 100 Å to 2,000 Å. In other non-limiting embodiments, the protective coating 17 may have a thickness in the range from 100 Å to 10 microns, for example, from 101 Å to 1000 Å, or from 1000 Å to 1 micron, or from 1 μm to 10 μm, or from 200 Å to 1000 Å. In addition, the protective coating 17 may have an uneven thickness on the surface of the functional coating 16. By “uneven thickness” it is meant that the thickness of the protective coating 17 can vary over a predetermined unit area, for example, the protective coating 17 can have high or low points or zones.

The protective coating 17 may be made of any desired material or mixture of materials. In one embodiment, the protective coating 17 may include one or more materials of metal oxides, such as, for example, alumina, silica, or mixtures thereof. For example, the protective coating may be the only coating layer containing alumina in the range from 0 to 100 wt.% And / or silica in the range from 0 to 100 wt.%, Or containing from 5 to 100 wt.% Aluminum dioxide and from 95 to 0 wt.% Silicon dioxide, or containing from 10 to 100 wt.% Aluminum dioxide or from 90 to 10 wt.% Silicon dioxide, or containing from 15 to 90 wt.% Aluminum dioxide and from 85 to 10 wt.% silica, or containing from 50 to 75 wt.% alumina or from 50 to 25 wt.% silica, or containing from 50 to 70 wt.% alumina I and from 50 to 30 wt.% silicon dioxide, or containing from 35 to 100 wt.% aluminum dioxide and from 65 to 0 wt.% silicon dioxide, for example, from 70 to 90 wt.% aluminum dioxide and from 10 to 30 wt.% silicon dioxide, for example, from 75 to 85 wt.% aluminum dioxide and from 15 to 25 wt.% silicon dioxide, for example, 88 wt.% aluminum dioxide and 12 wt.% silicon dioxide, for example, from 65 to 75 wt.% aluminum dioxide and from 25 to 35 wt.% silicon dioxide, for example, 70 alumina and 30 wt.% silicon dioxide, for example, from 60 to less than 75 wt.% aluminum dioxide and from more than 25 to 40 wt.% silica. Other materials such as aluminum, chromium, hafnium, yttrium, nickel, boron, phosphorus, titanium, zirconium and / or their oxides may also be present to control the refractive index of the coating 17. In one embodiment, the refractive index of the protective coating may be in the range from 1 to 3, for example, from 1 to 2, or from 1.4 to 2, or from 1.4 to 1.8.

Alternatively, the protective coating 17 may be a multilayer coating formed using separately formed layers of materials from metal oxides, such as, for example, a two-layer material formed by one layer containing metal oxides (for example, containing silicon dioxide and / or alumina first a layer) formed over another layer containing metal oxides (for example, containing silicon dioxide and / or alumina second layer). The individual layers of the multilayer protective coating 17 may have any desired thickness.

In one embodiment, the protective coating 17 may comprise a first layer formed above the functional coating and a second layer formed above the first layer. In one non-limiting embodiment, the first layer may comprise alumina or a mixture or alloy containing alumina and silica. For example, the first layer may comprise a mixture of silica and alumina having more than 5 wt.% Alumina, such as having more than 10 wt.% Alumina, such as having more than 15 wt.% Alumina, such as having more than 30 wt. wt.% alumina, such as having more than 40 wt.% alumina, such as having from 50 to 70 wt.% alumina, such as having from 70 to 100 wt.% alumina and from 30 to 0 wt.% dioxide silicon. In one non-limiting embodiment, the first layer may have a thickness in the range of more than 0 Å to 1 μm, such as 50 Å to 100 Å, such as 101 Å to 250 Å, such as 100 Å to 150 Å, such as from more than 100 Å to 125 Å. The second layer may comprise silica or a mixture or alloy containing silica and alumina. For example, the second layer may comprise a mixture of silica and alumina having more than 40 wt.% Silica, such as having more than 60 wt.% Silica, such as having more than 60 wt.% Silica, such as having more than 70 wt. % silica, such as having more than 80 wt.% silica, such as having 80 to 90 wt.% silica and 10 to 20 wt.% alumina, for example 85 silica and 15 wt.% oxide aluminum. In one non-limiting embodiment, the second layer may have a thickness in the range of more than 0 Å to 2 μm, such as 50 Å to 5000 Å, such as 50 Å to 2000 Å, such as 100 Å to 1000 Å, such from 300 Å to 500 Å, such as from 350 Å to 400 Å. As will be shown below, the presence of a protective coating 17 can improve the heatability of the functional coated substrate.

The polymer layer may include any polymer material. A "polymeric material" may contain a single polymer component or may contain a mixture of various polymeric components, such as, for example, one or more plastic materials or one or more thermoset or thermoplastic materials. The polymer layer 18 can adhere the layers. Used thermoset components include polyesters, epoxides, phenols and polyurethanes, such as thermoset urethane with injection molding of the reaction liquid components (RIM), or mixtures thereof. Used thermoplastic materials include thermoplastic polyolefins such as polyethylene and polypropylene, polyamides such as nylon, thermoplastic polyurethanes, thermoplastic polyesters, polyacrylates, vinyl polymers, polycarbonates, copolymers of acrylonitrile, butadiene and styrene (ABS), propylene-based rubber, copolymer and diene monomer (EPDM), copolymers and mixtures thereof.

Suitable polyacrylates include copolymers of one or more acrylic acid, methacrylic acid and their acrylates such as methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, butyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate. Other acrylates and methods for their preparation are disclosed in US Pat. No. 5,196,485.

Useful polyesters and alkyds can be prepared in a known manner by condensation of polyhydric alcohols, such as ethylene glycol, propylene glycol, butylene glycol, 1,6-hexylene glycol, neopentyl glycol, trimethylopropane and pentaerythritol, with polycarboxylic acids such as adepinic acid, fumeic acid acid, trimellitic acid, or drying butyric fatty acids. Examples of suitable polyester materials are disclosed in US Pat. Nos. 5,739,213 and 5,811,198.

Useful polyurethanes include reaction products of polymeric polyols, such as oligoester polyols or acrylic polyols with a polyisocyanate, including aromatic diisocyanates, such as 4,4'-diphenylmethanediisocyanate, aliphatic diisocyanates, such as 1,6-hexamethylene diisocyanate, and cycloaliphatic diisocyanates 4,4'-methylene bis (cyclohexyl isocyanate). The term "polyurethane" as used in this description means the inclusion of polyurethanes, as well as polyureas and copolymers of polyurethane and urea.

Suitable epoxy working materials are disclosed in US Pat. No. 5,820,987.

Useful vinyl polymers include polyvinylacetyl, polyvinyl formal and polyvinyl butyral.

The polymer layer 18 may have any thickness, for example, in one non-limiting embodiment of the invention for polyvinyl butyral, the thickness may be in the range from 0.50 mm to about 0.80 mm, such as 0.76 mm. The polymeric material may have any refractive index. In one embodiment, the polymeric material has a refractive index in the range of 1.4 to 1.7, such as 1.5 to 1.6.

The protective coating 17 may have a refractive index that is substantially the same as the refractive index of the material of the polymer layer 18. By “substantially the same refractive index” is meant that the refractive index of the protective coating material and the material of the polymer layer are the same or close enough so that small or no unwanted optical effects, such as unwanted changes in color, reflectance or transmittance due to the presence of Indeed protective coating 17. Protective coating 17 behaves as a continuation of the polymeric layer material. The presence of the protective coating 17 preferably does not result in an optically undesirable interface between the protective coating 17 and the polymer layer 18. In one embodiment, the protective coating 17 and the polymer layer 18 may have refractive indices that differ by ± 0.2, or ± 0, 1, or ± 0.05. By providing the same or substantially the same refractive indices of the protective coating material and the polymer layer material, the presence of the protective coating 17 does not adversely affect the optical properties of the laminated product as compared to the optical properties of the laminated material without the protective coating 17. For example, if the polymer layer 18 contains polyvinyl butyral having a refractive index of 1.7, the protective coating 17 can be selected or formed with a refractive index of less than 2, such as from 1.3 to 1, 8, for example, 1.5 ± 0.2.

The following is an example of a description of a method of manufacturing a laminated side window 10 using features of the invention.

Create the first substrate and the second substrate. The first and second substrates may be flat glass preforms having a thickness of from about 1.0 mm to 6 mm, typically from about 1.0 mm to about 3.0 mm, or such as from about 1.5 mm to about 2.3 mm The coating 16 can be formed at least on a portion of the main surface of the first glass substrate, for example, the main surface 14. The coating 16 can be formed by any conventional method, such as, but not limited to, magnetron sputtering by vapor deposition ( MSVD), pyrolysis deposition, such as chemical vapor deposition (CVD), spray pyrolysis, atmospheric vapor deposition (APCVD), low pressure chemical vapor deposition (LPCVD), accele plasma-assisted chemical vapor deposition (PECVD), plasma-supported chemical vapor deposition (PACVD), or thermal evaporation by resistive heating or electron beam heating, cathodic arc deposition, plasma deposition of molten powder, wet chemical deposition (e.g. sol-gel, silvering mirrors, etc.) or any other desired method. For example, the working coating 16 can be formed above the first substrate after cutting the first substrate to the desired size. Alternatively, a working coating 18 may be formed over a glass sheet before processing and / or over a float glass ribbon supported by a bath of molten metal, such as tin, in a conventional float chamber using one or more conventional coating devices by vapor deposition located in the float chamber. After exiting the float chamber, the tape can be cut to form the first coated substrate.

As an alternative solution, the working coating 16 can be formed over a strip of float glass after the tape exits the float chamber. For example, in US patents 4,584,206, 4,900,110 and 5,714,199 disclose methods and devices for applying a metal-containing film to the lower surface of a glass ribbon. Such a known device can be located downstream of a bath of molten tin during the manufacture of float glass to create a functional coating on the lower surface of the glass ribbon, i.e. on the side of the tape that was in contact with molten metal. In addition, the functional coating 16 can be formed over the first substrate by magnetron sputtering by vapor deposition after cutting the substrate to a desired size.

A protective coating 17 may be formed over at least part of the functional coating 16. The protective coating 17 provides several advantages during processing in the manufacturing process of the laminated product. For example, the protective coating 17 may protect the functional coating 16 from mechanical and / or chemical attack during transportation, storage and processing. In addition, as will be described below, the protective coating 17 can facilitate the separate heating and cooling of the workpiece with the working coating by increasing the emissivity of the resulting coating package. Although functional coatings were previously coated with topcoats to protect the functional coating from chemical and mechanical stress during processing, these topcoats were made as thin as possible so as not to adversely affect the aesthetic and solar control properties, such as the coefficient black coating. In contrast, in the present invention, the protective coating 17 can be made thick enough to increase the black factor of the overpack. In addition, by substantially matching the refractive index of the protective coating 17 with the refractive index of the material of the polymer layer 18 (and / or the substrate on which it is laminated), the presence of the protective coating 17 has little or no effect on the aesthetic and / or optical properties of the laminate products 10.

If the functional coating 16 is a low black coefficient coating having one or more infrared reflective metal layers, then adding a protective coating 17 to increase the blackness of the coating package reduces the reflection characteristics of the thermal infrared radiation of the functional coating 16. However, the coating package still reflects infrared solar radiation.

The protective coating 17 can be formed using any conventional method, for example, one of the methods described above for applying a functional coating, for example, a method of chemical vapor deposition in the bath or outside the bath, magnetron sputtering by vapor deposition, or salt gel. For example, a functional coated substrate can be sent to a conventional vapor deposition magnetron sputtering device having one or more metal electrodes, for example cathodes (targets), which can be sprayed in an oxygen-containing atmosphere to form a protective coating of metal oxides. In one non-limiting embodiment, the vapor deposition magnetron sputtering device may comprise one or more cathodes containing aluminum, silicon and / or mixtures or alloys of aluminum and silicon. The cathodes may have a content, for example, from 5 to 100 wt.% Aluminum and from 95 to 0 wt.% Silicon, such as from 10 to 100 wt.% Aluminum and from 90 to 0 wt.% Silicon, such as from 35 to 100 wt.% Aluminum and from 0 to 65 wt.% Silicon, for example, from 50 to 80 wt.% Aluminum and from 20 to 50 wt.% Silicon, for example, 70 aluminum and 30 wt.% Silicon. In addition to this, other materials or additives may also be present, such as aluminum, chromium, hafnium, yttrium, nickel, boron, phosphorus, titanium, zirconium to facilitate sputtering of the cathode (s) and / or to influence the refractive index or strength of the resulting coating .

According to one particular aspect of the invention, the protective coating can be applied using a vapor deposition magnetron sputtering system having an AC power source and one or more cathode targets. The cathode target may, as an example, include aluminum in the range from 5 to 100 wt.% And silicon in the range from 0 to 95 wt.%, For example, aluminum in the range from 20 to 80 wt.% And silicon in the range from 20 to 80 wt. wt.%, for example, aluminum in the range from 20 to 70 wt.% and silicon in the range from 30 to 80 wt.%, for example, aluminum in the range from 35 to 100 wt.% and silicon in the range from 0 to 65 wt.% for example, aluminum in the range from 40 to 90 wt.% and silicon in the range from 10 to 60 wt.%, for example, aluminum in the range from 50 to 80 wt.% and silicon in the range from 20 to 50 wt.%, for example aluminum in in the range from 50 to 70 wt.% and silicon in the range from 30 to 50 wt.%, for example, aluminum in the range from 60 to 70 wt.% and silicon in the range from 30 to 40 wt.%. In one embodiment, the aluminum content may be 60 wt.%, And silicon - 40 wt.%. In another embodiment, the aluminum content may be 70 wt.%, And silicon - 30 wt.%. An aluminum and silicon containing target may be selected from mixtures or alloys thereof, and one or more additives may be further included. Additives can be selected, for example, from chromium, hafnium, yttrium, nickel, boron, phosphorus, titanium, zirconium, tantalum, niobium, and mixtures and combinations thereof.

The cathode may be a cylindrical magnetron type target (C-mag type), such as described in US Pat. No. 5,814,195. The cathode may also be flat or double flat. Power supply can be in the range from 50 to 500 kW. The cathode target may be a plasma spray target containing aluminum in the range from 5 to 100 wt.% And silicon in the range from 0 to 95 wt.%, Or in any other ranges indicated above for the target. A system with an AC power source and a cathode target may have a cathode target with optical monitoring of plasma radiation. A system with an alternating current power source and a cathode target may also have an alternating current power source with an automatic feedback loop with voltage feedback. A system with an AC power source and a cathode target may have an AC power source operating at a frequency in the range between 10 and 100 kHz. Additionally, a system with an AC power source and a cathode target may have an AC power source operating at a frequency in the range between 10 and 100 kHz, such as from 30 to 70 kHz. On the market, such devices are offered by Advanced Energy of Fort Collins, Colorado (e.g. Crystal and Asterol models) or BOC Coating Tech, or Von Ardenne of Fairfield, California or Dresden, Germany (e.g. plasma radiation device, model No.REM-05 ) A system with an AC power source and a cathode target can be used with at least one of the gases selected, for example, from argon, oxygen, nitrogen, nitroxide and mixtures, including any two or more gases. In one embodiment, the gas may include argon and at least one other gas selected from oxygen, neon, helium, nitroxide, ozone, or any mixture of two or more of these gases.

As mentioned above, the protective coating 17 can be formed as a single layer containing one or more materials with metal oxides, or as a multilayer coating having two or more separate layers, each individual layer containing one or more materials with metal oxides . The protective coating 17 can be applied in sufficient quantity or with sufficient thickness to increase the black factor of the overpack, exceeding the black factor of only one functional coating. In one embodiment, the protective coating can be applied with a thickness in the range from 100 Å to 50,000 Å to increase the black factor of the coating bag to or above 0.3, or above 0.4, or above 0.5.

The functional coating 16 and / or the protective coating 17 can be applied to a flat substrate or to a substrate after it is bent and formed with the desired contour.

The coated first substrate and the uncovered second substrate can be cut to obtain a first coated layer and a second uncoated layer, respectively, with each layer having a desired shape and size. The coated and uncoated layers can be folded, washed, bent and molded in accordance with the desired contour in order to form the first and second layers 12 and 20, respectively, for lamination. As is understood by those skilled in the art, the general shapes of coated and uncoated preforms and layers depend on the particular vehicle in which they are to be installed, since the final shape of the side windows differs between different car manufacturers.

Coated and uncoated preforms can be shaped using any desired method. For example, preforms can be molded using the RPR method described in US Pat. No. 5,286,271 or the modified RPR method disclosed in US patent application No. 09/512852. Figure 2 shows an additional RPR device 30 suitable for the practical implementation of the invention and comprising a furnace 32, for example, a heat radiation furnace or a Lera tunnel furnace having a furnace conveyor 34 containing a plurality of spaced apart rollers 36 of the furnace conveyor. Heaters, such as heat-emitting coils, can be located above and / or below the furnace conveyor 34 along the length of the furnace 32, and they can be controlled to form heating zones with different temperatures along the length of the furnace 32.

The molding portion 50 may be located near the outlet end of the furnace 32 and may include a lower mold 51 having a vertically movable elastic ring 52 and a molding section conveyor having a plurality of rollers 56. An upper vacuum mold 58 having a removable or variable molding surface 60 of a predetermined molds, can be located above the lower mold 51. The vacuum mold 58 is mounted to move using the shuttle system 61.

The transfer section 62 having a plurality of shaped transfer rollers 64 may be located near the output end of the molding section 50. The transfer rollers 64 may have a transverse height curvature corresponding to the substantially transverse curvature of the molding surface 60.

The tempering or cooling section 70 may be located near the output end of the transfer section 62 and may include a plurality of rollers 72 for moving the workpieces through the cooling, tempering and / or quenching section 70. The rollers 72 may have a transverse curvature in height, which essentially corresponds to the curvature of the transfer rollers 64.

In the past, heating blanks (substrates) with a working coating has led to difficulties due to heat reflection by the functional coating 16, which led to uneven heating of the coated and uncoated sides of the blank. U.S. Patent Application No. 09/512852 discloses a method for resolving this problem by modifying a method of heating RPR by supplying heat first in the direction of the surface of a workpiece without a functional coating. In the present invention, this problem is eliminated by applying a protective coating 17 that increases the coefficient of blackness, which ensures the use of the same or essentially the same method of heating the workpieces with a functional coating and without it.

As shown in FIG. 2, the first blank 80 with a coating bag (e.g., functional coating 16 and protective coating 17) and the second blank 82 without functional coating can be individually heated, molded and cooled before lamination. By “separate heating” is meant that blanks are not stacked on top of each other during heating. In one embodiment, the first preform is placed on the conveyor 34 of the furnace with a protective coating 17 directed downward, i.e. in contact with the rollers 36 of the furnace conveyor, during the heating process. The presence of the protective coating 17 with a higher black factor reduces the problem of heat reflection by the metal layers of the functional coating 16 and contributes to a more even heating of the coated and uncoated sides of the first preform 80. This helps to prevent the first preform 80 from twisting, which usually happened in previous heating processes. In one embodiment, the preforms were heated to a temperature of about 640 ° C.-704 ° C. over a period of time from about 10 minutes to about 30 minutes.

At the end of the furnace 32, softened glass preforms (both coated preform 80 and uncoated preform 82) are transferred from the furnace 32 to the molding portion 50 and to the lower mold 51. The lower mold 51 moves upward, raising the glass preform to press the heat-softened glass preform to the molding the surface 60 of the upper mold 58 in order to shape the glass preform, for example curvature, to the molding surface 60. The upper surface of the glass blank comes into contact with the molding surface 60 of the upper mold 58 and holds vacuum in place.

The shuttle system 61 is driven to move the upper vacuum mold 58 from the molding portion 50 to the transfer portion 62, where the vacuum is broken to release the molded glass blank onto the curved transfer rollers 64. The transfer rollers 64 move the molded glass blank to the rollers 72 and to the cooling section 70 for hardening or increasing strength by heating using a conventional method. In the cooling section 70, air is directed from above and below to the molded glass preform to temper or increase the strength by heating to form the first and second layers 12 and 20. The presence of a protective coating 17 with a high black factor also contributes to a more uniform cooling of the coated preform 80 in the cooling section 70.

In another embodiment, the coated and uncoated preforms can be heated and / or molded in the form of doublets. In one embodiment, the coated and uncovered preforms can be positioned so that the functional coating 16 with the protective coating 17 is located between the two preforms. The preforms can then be heated and / or molded in any conventional manner. It is believed that the protective coating 17 acts as an oxygen barrier to reduce or eliminate the passage of oxygen to the functional coating 16, where oxygen can react with the components of the functional coating 16, such as, for example, metals (e.g. silver), which leads to degradation functional coating 16. In one conventional method, a doublet can be placed on a support and heated to a sufficient temperature to bend or mold the blanks into the desired final shape. In the absence of a protective coating 17, preforms with a functional coating usually cannot withstand a heating cycle with heating above about 1100 ° F (593 ° C) for more than 2 minutes (when heated above 900 ° F (482 ° C) for more than 6 minutes heating cycle time) without degradation of the functional coating 16. Such degradation may result in clouding or the appearance of yellowness with a decrease in the transmittance of visible light by 10% or more. Metal layers in the functional coating 16, such as silver layers, may react with oxygen diffusing into the functional coating 16, or with oxygen present in the functional coating. However, it can be considered that the use of a protective coating 17 ensures that the coated preform maintains the heating cycle with heating to a temperature of 1100 ° F (593 ° C) or higher for 5-15 minutes, for example, 5-10 minutes or, for example, 5-6 minutes (when heated above 900 ° F (482 ° C) for 10-20 minutes or, for example, 10-15 minutes, 10-12 minutes) without significant degradation of the functional coating 16, for example, with less than 5% loss of visible light transmission, for example, less than 3% loss, for example, less than 2% loss, for example, less than 1% loss, for example, without loss of pass niya visible light.

In order to form the laminate product 10 according to the invention, the coated glass layer 12 is provided with a coated inner main surface 14 in a direction substantially complementary to the inner main surface 22 of the uncoated layer 20, separated by a polymer layer 18. Part of the functional coating 16 and / or protective coating 17 (for example, a strip about 2 mm wide) can be removed around the perimeter of the first layer 12 before lamination. On one or both layers 12 or 20, for example, on the outer surface 13 of the first layer 12, a ceramic strip 90 may be provided to hide the uncovered peripheral edge zone of the laminated side window and / or to provide additional shading for passengers inside the car. The first layer 12, the polymer layer 18 and the second layer 20 can be laminated together in any conventional manner, for example, as disclosed in US Pat. Nos. 3281296, 3769133 and 5250146, to form the side window 10. An edge sealant can be applied to the edge of the side window 10 as shown in figure 1.

Although the above method for forming laminated side glass 10 according to the invention uses an RPR device and method, the side glass 10 according to this invention can be formed using other methods, such as bending methods by horizontal pressing, disclosed, for example, in patents US 4661139, 4197108, 4272274, 4265650, 4508556, 4830650, 3459526, 3476540, 3527589 and 4579577.

Figure 3 shows a monolithic product 100, in particular a monolithic transparent element of a car, having the features of the present invention. The article 100 includes a substrate or layer 102 having a first major surface 104 and a second major surface 106. The protective coating 110 may be formed at least in part, such as a main part, or on the entire surface area of the functional coating 108. Functional coating 108 and the protective coating 110 can be formed by any desired method, for example, as described above. The functional coating 108 and the protective coating 110 form a coating bag 112. The coating package 112 may include other coating layers or films, such as, but not limited to, a sodium ion diffusion barrier layer. An optional polymer layer 113, such as containing one or more of the polymeric materials mentioned above, can be applied in addition to the protective coating 110 in any way desired.

Layer 102 may be of any desired material, such as those described above for layers 12, 20, and may have any desired thickness. In one non-limiting embodiment, for use as a monolithic automotive side glass, the layer 102 may have a thickness equal to or less than 20 mm, for example, about less than 10 mm, such as from about 2 to about 8 mm, for example, from about 2 , 6 to about 6 mm.

Functional coating 108 may be of any desired type and have any desired thickness, such as that described above for functional coating 16. In one embodiment, functional coating 108 is a solar energy-controlling coating having a thickness of from about 600 Å to about 2400 Å.

The protective coating 110 may be of any desired material and have any desired structure, such as those described above for the protective coating 17. The protective coating 110 according to the invention can be formed with a thickness sufficient to increase, in particular, a significant black factor of the coating bag 112 compared to the blackness coefficient of one functional coating 108. In one embodiment of a monolithic product, the protective coating 110 may have a thickness equal to or more than 1 micron, for example, in the range from 1 to 5 microns. In one embodiment, the protective coating 110 increases the black factor of the overpack by 2 times compared to the black factor of one functional coating 108 (i.e., if the black coefficient of the functional coating 108 is 0.05, then adding a protective coating 110 increases the black factor of the resulting coating bag 112, at least up to 0.1). In another embodiment, the protective coating 110 increases the black factor by at least 5 times, for example, 10 times or more. In another embodiment, the protective coating 110 increases the black factor of the coating bag 112 to 0.5 or more, for example, to more than 0.6, for example, in the range of from about 0.5 to about 0.8.

An increase in the black factor of the coating packet 112 retains the reflection of the solar energy functional coating 108 (e.g., the reflection of electromagnetic radiation in the range from 700 to 2100 nm), but reduces the ability of the functional coating 108 to reflect thermal energy (e.g., the reflection of electromagnetic radiation in the range from 5000 nm to 25 000 nm). An increase in the black factor of the functional coating 108 by forming the protective coating 110 also improves the heating and cooling characteristics of the coated substrate during processing, as mentioned above with respect to the laminate. The protective coating 110 also protects the functional coating 108 from mechanical and chemical influences during handling, transportation, storage and processing.

The protective coating 110 may have a refractive index that is equal to or substantially equal to the refractive index of the layer 102 on which it is applied. For example, if the layer 102 is glass having a refractive index of 1.5, then the protective coating 110 may have a refractive index of less than 2, such as 1.3-1.8, such as 1.4-1.8, for example 1, 5 ± 0.2. Alternatively, or in addition to this, the protective coating 110 may have a refractive index that is substantially the same as that of the polymer layer 113.

The protective coating 110 may have any thickness. In one monolithic embodiment, the protective coating 110 may have a thickness of 1 micron or more to reduce or eliminate the color change of the product 100. The protective coating 110 may have a thickness of less than 5 microns, such as in the range from 1 to 3 microns. In one embodiment, the protective coating 110 may be thick enough to pass the usual ANSI / SAE 26.1-1996 test with a gloss loss of less than 2% for more than 1000 cycles for use as a transparent vehicle element. The protective coating 110 should not have a uniform thickness on the surface of the functional coating 108, but may have high or low points and zones.

The protective coating 110 may be a single layer containing one or more materials with metal oxides. Alternatively, the protective coating 110 may be a multilayer coating having two or more coating layers, as described above. Each coating layer may contain one or more materials with metal oxides. For example, in one embodiment, the protective coating 110 may include a layer containing alumina and a second layer containing silica. The individual coating layers may have any desired thickness indicated above.

The substrate with the coating bag 112 can be heated and / or molded in any desired manner, such as those described above for heating the coated preform of the laminate.

The optional polymer layer 113 may include one or more polymer components, such as those described above for polymer layer 18. The polymer layer 113 may have a thickness of more than 100 Å, such as more than 500 Å, such as more than 1000 Å, such as more than 1 mm, such more than 10 mm, such as in the range from 100 Å to 10 mm. The polymer layer 113 may be a permanent layer (i.e., not intended to be removed) or may be a temporary layer. By “temporary layer” is meant a layer to be removed, such as, for example, a layer to be removed by burning or rinsing with a solvent in a subsequent processing step. The polymer layer 113 can be formed using any conventional method.

The monolithic article 100 is particularly suitable as an automotive transparent element. Used in this case, the term "automotive transparent element" refers to automotive side glass, rear window, transparent roof, sliding roof, etc. A “transparent element” can have visible light transmission of any desired magnitude, for example, from 0 to 100%. For viewing areas, visible light transmission is preferably greater than 70%. For other areas, visible light transmission may be less than 70%.

If only a functional coating 108 is used as an automotive transparent element, such as side glass, a low coating coefficient 108 of the working coating 108 can reduce the amount of solar energy passing into the car, but can also contribute to the greenhouse effect by retaining thermal energy inside a car. The protective coating 110 according to the invention eliminates this problem by creating a coating bag 112 having a functional coating 108 with a low black coefficient (e.g., 0.1 or less) on one side of the coating bag 112 and a protective coating 110 with a high black coefficient (e.g. 0, 5 or more) on the other side. Solar-reflecting metal layers in the functional coating 108 reduce the passage of solar energy into the vehicle, and the high-black coating 110 reduces the greenhouse effect and removes thermal energy from the vehicle. Additionally, layer 110 (or layer 17) can absorb solar energy in one or more of the ranges of ultraviolet, infrared, and / or visible radiation of the electromagnetic spectrum.

As shown in figure 3, the product 100 can be placed in the car with a protective coating in the direction of the first side 114 of the car, and the layer 102 in the direction of the second side 116 of the car. If the first side 114 is facing the outside of the car, then the coating bag 112 will reflect solar energy due to the reflection layers present in the functional coating 108. However, due to the large black factor, for example, greater than 0.5, the coating bag will absorb at least a portion thermal energy. The higher the black factor of the overburden 112, the more thermal energy is absorbed. The protective coating 110 in addition to providing an increased black factor of the coating bag 112 also protects the less stable functional coating 108 from mechanical and chemical damage. The optional polymer layer 113 also provides mechanical and chemical resistance.

Alternatively, if the first side 114 is directed inside the car, then the product 100 still provides reflection of solar energy through metal layers in the functional coating 108. However, the presence of a protective coating 110 reduces the reflection of thermal energy by absorbing thermal energy to prevent heating of the interior of the car thermal energy to elevated temperatures and reduces the greenhouse effect. Thermal energy from the interior of the vehicle is absorbed by the protective coating 110, and not reflected back into the interior of the vehicle.

Although the coating bag according to the invention is particularly useful for transparent parts of an automobile, it is not limited to being used only in automobiles. For example, the coating bag can be used in a conventional insulating glass block, for example, it can be provided on the inner or outer surface of one of the glass sheets forming the insulating glass block. When located on the inner surface in airspace, the covering coating should not have the mechanical and / or chemical resistance that it should have when placed on the outer surface. Additionally, the overpack can be used in seasonally adjustable windows, such as those disclosed in US Pat. No. 4,081,934. When located on the outside of the window, the protective coating must be thick enough to protect the functional coating from mechanical and / or chemical damage. The invention can also be used as a monolithic window.

To illustrate the invention, the following examples are described below, which, however, should not be construed as limiting the invention. All parts and percentages in the examples below, as well as in the entire description are indicated in percent by weight, unless otherwise indicated.

Example 1

Several functional coating samples were prepared with various protective coatings according to the invention and tested for resistance to light scattering, dullness occurring after Taber abrasion, and blackness coefficient. Functional coatings were not optimized for mechanical or chemical properties, but were used only to illustrate the relative properties, for example, durability, blackness and / or dullness, of a functional coated substrate having a protective coating according to the invention. Methods for preparing such functional coatings are described, for example, in patents US 4898789 and 6010602, which, however, should not be construed as limiting the invention.

The test samples were made by applying various functional coatings in the following manner (to ordinary transparent sodium-calcium-silicate glass) with a protective coating of aluminum oxide, incorporating the features of the invention and having a thickness in the range from 300 Å to 1.5 microns. The protective coatings used for the tests have a high reflectivity for the infrared part of sunlight and a characteristic small black coefficient and consist of multilayer interference thin films formed by alternately applying zinc and silver stannate layers using magnetron sputtering by vapor deposition (MSVD). For the samples discussed below, two layers of silver and three layers of zinc stannate are usually present in the functional coating. Functional coatings also used thin primer metal layers of titanium over silver layers to protect the silver layers from oxidation during MSVD deposition of zinc layers of zinc stannate and to withstand heat to bend the glass substrate. The two functional coatings used in the following examples differ mainly in the outermost thin layer of the multilayer coating, one of which consists of Ti metal and the other of TiO ₂ oxide. The thickness of the outer layer of both Ti and TiO ₂ is in the range from 10 Å to 100 Å. Alternative examples that are also applicable, but which have not been prepared, include functional coatings without a thin outer layer of Ti or TiO ₂ or other metal or oxide outer layers. The functional coatings used for the examples and having a thin outer layer of titanium have a blue reflected color after heating, and the outer layer of titanium oxide has a green reflected color after heating. Other reflected colors of functional coatings after heating, which can be protected by a protective coating, according to the invention can be obtained by changing the thickness of the individual layers of silver and zinc stannate in the functional coating.

For the following examples, thin or thick alumina protective coatings were applied using mid-frequency, bipolar, double-pulse magnetron reactive sputtering of aluminum in an Airco ILS 1600 device specially modified to power two or three targets. Power was supplied by an Advanced Energie (AE) Pinnacle® Dual DC power supply and Astral® switching equipment that converts the supplied DC power to bipolar switching power. The functional coated glass substrates were placed in an Airco ILS 1600 MSVD coating apparatus having an oxidizing reactive atmosphere of oxygen / argon. Two aluminum cathodes were sprayed at different times to obtain alumina coatings of various thicknesses on functional coatings.

The following three test samples were made and tested (samples A-C):

Sample A — 4 by 4 inch (10 by 10 cm) pieces of 2 mm thick clear float glass commercially available from PPG Industries, Inc., of Pittsburgh, PA.

Sample B - 4 by 4 inch (10 by 10 cm) pieces of 2 mm thick clear float glass having an experimental functional coating with a low black factor with a thickness of approximately 1600 Å with green reflected color, made using the MSVD method (see above ), and without a protective coating of alumina, used as a control sample.

Sample C - pieces 4 by 4 inches (10 by 10 cm) 2 mm thick clear float glass having an experimental coating with a low black factor with a thickness of about 1600 Å with blue reflected color, made using the MSVD method, but having additionally a protective coating of aluminum oxide (Al ₂ About ₃ ), according to the invention, with a thickness of 1.53 microns deposited on the functional coating.

Similar AC samples were then tested in accordance with the Taber standard abrasion test (ANSI / SAE 26.1-1996), and the results are shown in FIG. 4. Taber sclerometric hardness (SD) measurements for a given number of cycles were carried out by measuring with a microscope the total length of all scratches over an area of one square micron using digitalization and image analysis software. Test samples C (with a protective coating) showed lower sclerometric hardness than test samples B (with a functional coating). Samples C have almost the same resistance with uncoated glass samples A. Taber measurement results were obtained for the protective coating in the application state, which means that the coated glass samples were not subsequently heated after the protective coating was applied using the MSVD method. It is expected that the results of measuring sclerometric hardness should improve (i.e., sclerometric hardness for fewer Taber cycles should decrease) after heating the coated substrate by increasing the density of the heated coating packet. For example, coated substrates can be heated from ambient temperature to a maximum temperature in the range of 640 to 704 ° C. and cooled over a period of time from about 10 minutes to about 30 minutes.

Figure 5 shows the average haze of light scattering depending on the number of Taber cycles (in accordance with ANSI / SAE 26.1 - 1996) for similar samples A and C above. Sample A is uncoated glass used as a control sample. The results show that the haze formed in sample C after 1000 cycles is close to 2%, i.e. to the minimum permitted by ANSI for the protection of automotive windows. It is expected that a slight improvement in the durability of the protective coating will lead to a reduction in haze after 1000 Taber cycles to less than 2%, which will exceed ANSI requirements for the protection of automotive windows.

Figure 6 shows the effect of the protective coating according to the invention applied using the MSVD method with different discharge pressures on two different functional coatings. The samples shown in Fig.6 consist of a transparent float glass 2 mm thick with the following coatings applied on them:

Sample D - control sample; blue reflective functional coating with a nominal thickness of 1600 Å, not having a protective coating.

Sample E is a control sample; green reflective functional coating with a nominal thickness of 1600 Å, not having a protective coating.

Sample F (HP) —functional coating of sample D plus a protective alumina coating sprayed by the MSVD method at an oxygen and argon discharge pressure of 8 microns.

Sample F (LP) is the functional coating of sample D plus a protective alumina coating sprayed by the MSVD method at an oxygen and argon discharge pressure of 4 microns.

Sample G (HP) —functional coating of sample B plus a protective alumina coating sprayed using the MSVD method at an oxygen and argon discharge pressure of 8 microns.

Sample G (LP) is the functional coating of sample E plus a protective alumina coating sprayed by the MSVD method at an oxygen and argon discharge pressure of 4 microns.

As shown in FIG. 6, as the thickness of the protective coating increases, the black factor of the overpack also increases. With a protective coating thickness of about 1.5 μm, the coating bag has a black factor of approximately more than 0.5.

7 shows the results of measuring sclerometric hardness after 10 cycles of abrasion according to Taber for samples F (HP), F (LP), G (HP) and G (LP) indicated above. Control samples D and E with a functional coating, but without a protective coating, have an initial sclerometric hardness of the order of about 45 mm ^-1 to 50 mm ^-1 . As shown in FIG. 7, applying a protective coating according to the invention (even with a thickness of the order of less than 800 Å) improves the durability of the resulting coating bag.

On Fig shows the results of measuring sclerometric hardness after 10 cycles of abrasion according to Taber for the following samples of blue or green reflective functional coatings with protective coatings of aluminum oxide with a thickness of 300 Å, 500 Å and 700 Å:

Sample H is the functional coating of sample D plus an alumina protective coating sprayed using the above MSVD method.

Sample I is a functional coating of sample E plus a protective coating of aluminum oxide, spray applied using the above MSVD method.

As shown in the right part of FIG. 8, heating the coating bag according to the invention improves the durability of the coating bag. The coatings on the right side of FIG. 8 were heated by being placed in a 1300 ° F (704 ° C) oven for 3 minutes, then removed and placed in a 400 ° F (204 ° C) oven for 5 minutes, after which the samples coated coated and left to cool under ambient conditions.

Example 2

This example illustrates the effect of the protective coating of the invention on the transmission of visible light to a coated substrate after heating.

A piece of glass (sample J) having the usual infrared regulating reflection of the solar energy coating without a protective coating according to the invention was prepared, and another piece of glass (sample K) having the same conventional reflecting infrared of the solar energy coating, but with a protective coating was prepared coating according to the invention. The protective coating in this example was a mixture of silica and alumina (70 wt.% Alumina and 30 wt.% Silica with a thickness of 600 Å to 700 Å). Two samples were heated in a conventional oven and the visible light transmittance (Lta) of the two samples was measured for different percent heating. The “percent heating” values in FIG. 9 represent the thermal budget of heated substrates based on a reference value (0%). By “heat budget” is meant the highest temperature achieved and the total heating time. The higher the percentage of heating, the hotter the samples were heated. As follows from curve B in Fig. 9, when a sample J without a protective coating is heated above a reference value, the transmission of visible light decreases and falls below 75% with a heating percentage of about 20%. As understood by those skilled in the automotive art, transmittance of visible light below about 75% is undesirable for most windscreens. However, as also follows from Fig. 9, a sample K with a protective coating under the same heating conditions preserves the transmission of visible light in excess of 75% even with a heating percentage of 40% (curve A). Thus, the protective coating according to the invention allows the substrate with the functional coating to be heated to higher temperatures and / or for a longer time without adversely affecting the transmission of visible light. This feature is preferred for operations such as deep deflection, or similar operations in which prolonged heating is desired.

For specialists in the art it is clear that it is possible to modify the invention without departing from the ideas disclosed in the above description. For example, although in the preferred embodiment of the laminated product, only one layer includes a functional coating, it is understood that the invention can be practiced with both layers having a functional coating, or with one layer having a functional coating and with another layer having an inoperative coating. e.g. photocatalytic coating. In addition, it will be understood by those skilled in the art that the aforementioned preferred operating parameters can, if necessary, be adjusted for various materials and / or thicknesses of the substrate. Accordingly, the embodiments described in detail are for illustrative purposes only and do not limit the scope of the invention, which is determined by the appended claims and all and any equivalents thereof.

Claims (10)

1. An article comprising a substrate and a coating bag containing a functional coating applied to at least a portion of the substrate and a protective coating applied to at least a portion of the functional coating providing an emissivity of the coating package in excess of the emissivity of the functional coating and having a reflection coefficient of 1.4 to 2 and a thickness of more than 100 Å to less than 10 μm, the protective coating comprising a first layer formed at least on a part of the functional coating, and secondly a swarm layer formed at least on a part of the first layer, the first layer containing from 50 to 99 wt.% alumina and from 50 to 1 wt.% silica, and the second layer containing from 50 to 99 wt.% silicon dioxide and from 50 to 1 wt.% alumina. 2. The product according to claim 1, which is a transparent element of a vehicle with an engine. 3. The product according to claim 1, in which the first layer of the protective coating contains from 70 to 99 wt.% Alumina and from 30 to 1 wt.% Silicon dioxide. 4. The product according to claim 1, in which the first layer of the protective coating has a thickness of from 50 Å to 1 μm. 5. The product according to claim 1, in which the first layer of the protective coating has a thickness of from 100 to 250 Å. 6. The product according to claim 1, in which the second layer of the protective coating contains from 70 to 99 wt.% Silicon dioxide and from 30 to 1 wt.% Alumina. 7. The product according to claim 1, in which the second layer of the protective coating has a thickness of from 50 to 2000 Å. 8. The product according to claim 1, in which the second layer has a thickness of from 300 to 500 Å. 9. A monolithic transparent element containing a glass substrate and a coating bag containing a functional coating applied to at least a portion of the substrate and a protective coating applied to at least a portion of the functional coating, the protective coating having a thickness of 1 up to 10 μm and contains a first layer formed at least on part of the functional coating, and a second layer formed on at least part of the first layer, while the first layer contains from 50 to 99 wt.% aluminum oxide and from 50 to 1 wt.% D silicon oxide and the second layer comprises from 50 to 99 wt.% silica and 50 to 1 wt.% alumina. 10. An article comprising a substrate, at least one reflecting infrared portion of solar energy, a dielectric functional coating applied to at least a portion of the substrate, and a protective coating applied to at least a portion of the functional coating, wherein the protective coating has a refractive index of 1.4 to 1.8 and a thickness of more than 100 Å to less than 10 μm and contains a first layer formed at least in part of the functional coating and a second layer formed in at least part of the first layer at this first layer contains from 50 to 99 wt.% alumina and from 50 to 1 wt.% silicon dioxide, and the second layer contains from 50 to 99 wt.% silicon dioxide and from 50 to 1 wt.% alumina.

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