JP2002522347A - Compositions, apparatus, methods, and articles made thereby for forming a selected color coating on a substrate - Google Patents

Abstract

Abstract: A copper-containing component and a manganese-containing component are applied onto the surface of a substrate to form a coating having a selected ratio of copper to manganese that produces the desired color. In addition, the discoloration of the multi-component coating due to the subsequent heat treatment determines the most mobile substance in the coating and places a concentration gradient layer of the oxide of the mobile substance between the substrate and the coating. Minimize or block. Subsequent heat treatment allows the mobile material in the gradient layer to diffuse into the substrate more easily than the mobile material in the coating. Further, discoloration due to, for example, a heat treatment such as a strengthening operation is minimized by adding calcium to the FeOx system to prevent darkening of the film after heating. An apparatus for forming a graded coating on a substrate has a coating location located along a conveyor. The coating location has a first coating dispenser rotatably mounted on a first support and at least one exhaust hood. The first coating dispenser is positioned such that the axis through the delivery end of the first coating dispenser has a predetermined angle with the substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

RELATED APPLICATIONS This application is filed on Dec. 18, 1997, entitled "Methods and Apparatus for Depositing Pyrolytic Coatings with Fade Regions on Substrates and Articles Formed Therewith". Apparatus for Depositing Pyrolytic Coatings Having a
US Patent Application Serial No. entitled Fade Zone Over a Substrate and Articles Prodused 08 / 992,484. This application was also filed on Aug. 13, 1998, entitled "Methods and Apparatus for Forming Graded Fade Areas on Substrates and Articles Formed Therewith" (Methods and Apparatus f.
or Forming a Graduated Fade Zone on a Substrate and Articles Prodused Th
ereby), provisional US patent application Serial No. 60 / 096,415. By reference to the above application, its disclosure is incorporated herein.

[0002] The present invention generally relates to forming a coating of a selected color on a substrate, in particular, changing the components in an aqueous suspension of an organometallic composition, wherein said suspension is coated on a glass substrate. Deposited on top,
The present invention relates to a composition, an apparatus and a method for pyrolyzing to form a stable coating film of a selected color (s) on the glass substrate. As one aspect of the present invention,
The coating may be graded on a surface of a substrate, for example, a float glass strip.
fade zone, gradually fading area).

BACKGROUND ART In various industrial applications, it is desirable to form a coating on a glass surface. For example,
Automotive windshields are known as "shade bands" or "fade zones".
) ". In many passenger car vehicles, the windows in the rear seats and the rear windows are coated with a uniform thickness of coating. These coatings reduce the transmission of visible, infrared or ultraviolet light, reduce glare, obscure the interior of the vehicle, and / or reduce the transmission of solar energy to reduce heating of the interior of the vehicle. Reduce. The term "fade area" generally refers to a zone adjacent to the edge of a transparent body, e.g., the top edge of an automotive windshield, where the visibility through the transparent body changes from a less transparent area to a more transparent area. Point to.

In US Pat. No. 3,660,061, an organic metal salt is dissolved in an organic solution and sprayed on a heated glass surface to form a metal oxide film. US Patent 4,71
No. 9,127, an aqueous suspension of an organometallic salt is sprayed onto a heated glass surface,
A metal oxide coating is pyrolytically formed on its surface (the contents of which are incorporated herein by reference to this specification).

[0005] Using currently available coating techniques, gray or dark gray coatings are formed, especially in the automotive industry, and the coated glass is treated with the greatest number of colors without "clashing" with the body color. It can be used with many body colors. In addition, many of the known coated substrates may change color or fade due to subsequent strengthening and heating during molding. The color change caused by this heat makes it difficult to produce coating materials with constant color stability. Furthermore, many known coated substrates do not have chemical durability when contacted with a solution containing, for example, citric acid.

US Pat. No. 2,676,114 teaches a series of different thicknesses of adjacent shields using a plurality of stationary shields geometrically arranged for a plurality of vapor deposition coating sources. The formation of a separate coating is described. The disadvantage of this technique is that its individual coated band gives the coated substrate an aesthetically undesirable band or striped appearance.

US Pat. No. 3,004,875 describes a plurality of spray guns positioned over a shield to apply a graded coating to the edge of a substrate. The resulting zone has a thicker area away from the spray gun and a thinner area adjacent to the spray gun. The disadvantage of this technique is that the device requires a complex shielded spraying mechanism, and the resulting zone has a speckled appearance due to the swirling that occurs near the edge of the shield under the shield during the coating operation That is.

[0008] US Patent No. 4,138,284 to Postupack includes:
The application of the dye composition along one edge of a glass substrate is described. The resulting zone has a relatively large area with a substantially uniform thickness and a narrow graded boundary located between the coated and uncoated portions of the substrate.

[0009] To reduce or eliminate disadvantages associated with currently known compositions and methods,
It will be appreciated that it would be advantageous to provide compositions, methods and apparatus for applying a coating or coatings that exhibit a selected transmission color on the surface of a substrate.

SUMMARY OF THE INVENTION The present invention provides a coating of a desired color, such as a copper and manganese-containing coating, on a substrate, such as a glass substrate, with a selected ratio of copper- and manganese-containing components on the substrate. Applying and forming a coating having a selected copper to manganese ratio. In particular, when the ratio of the copper-containing component to the manganese-containing component is 1, the coating has blue transmitted light. When the ratio of copper-containing component to manganese-containing component is less than about 1, the color of the transmitted light changes from gray-blue to amber as the ratio decreases. If the ratio of the copper-containing component to the manganese-containing component is greater than about 1, the transmission color changes from gray-blue to brown as the ratio increases.

The invention further relates to a composition for forming a coating of a selected color on a substrate. Coatings containing copper and manganese can be used to form coatings ranging from amber to blue or light brown depending on the copper to manganese ratio. The chromium, copper and manganese systems provide a dull gray coating in transmitted light. The addition of cobalt to the copper-manganese system can increase the chemical durability of the coating, for example, the resistance to citric acid. Iron oxide systems provide a golden coating for transmitted light. The addition of copper to this iron oxide system can provide a grey-brown coating with bright transmitted light. Addition of citric acid to the cuprous oxide system gives a dark brownish coating with dark transmitted light. The manganese oxide (Mn ₂ O ₃ ) coating gives a mauve / lavender color coating, while the film with the (Mn ⁺⁺ ) (Mn ⁺⁺⁺ ) ₂ O ₄ phase is light amber. Give the film. ^{(Mn ++) (Mn +++)} 2 O 4 is referred to as "Mn ₃ O _4".

The present invention provides a method for preventing the color of a multi-component or multi-layer coated substrate from changing by a subsequent heat treatment, determining the most mobile substance in the layer of the coating, and the oxide of the mobile substance. A method for preventing discoloration comprising the steps of arranging a layer having a concentration gradient of between a substrate such as a glass sheet and a coating. The concentration gradient layer is preferably applied directly on the glass substrate, but may be applied on a coating layer formed on the glass substrate. Subsequent heat treatment allows the mobile material in the concentration gradient layer to diffuse more readily into the substrate than the mobile material in the coating, which minimizes the disappearance of the mobile material from the coating and reduces permeation. Either reduce the rate increase or prevent it from occurring.

[0013] The invention further relates to an apparatus for forming a graded coating on a surface of a substrate, for example a piece of glass. The device has a coating location to facilitate the relative movement of the glass pieces.
The coating station has a coating dispenser mounted on the first support, preferably rotatably mounted. An exhaust hood is mounted on one or both sides of the coating dispenser. The coating material source and the pressurized fluid source are in flow with the coating dispenser. If more than one nozzle is used, the imaginary axis through the outlet, e.g. the nozzle or center line of the expected coating spray of the coating dispenser, intersects the glass moving device at a predetermined angle. Attach the coating dispenser to the glass moving device such that the coating spray exiting the discharge end of the coating dispenser provides a graded coating on the glass surface. The graded coating is thicker near the discharge end of the coating dispenser and thinner farther from the discharge end of the coating dispenser. Preferably, the thickness of the coating decreases uniformly as the distance from the discharge end of the coating dispenser or the edge of the glass piece near the coating dispenser increases.

[0014] The apparatus may have a second coating dispenser rotatably mounted on the second support. One or both coating dispensers may be capable of moving vertically and horizontally.

In yet another aspect of the invention, an apparatus includes a plurality of spaced coating dispensers arranged in a row or offset from one another on a surface of a substrate to be coated.
Each coating dispenser emits the coating material as a cone or fan, for example, an elliptical spray, on a surface portion of the substrate. The coverage area from one nozzle is
Overlapping the coating area from another nozzle, forming a coating having a central area of substantially uniform thickness, with graded areas on either side of the central area.

[0016] The present invention further provides a coating dispenser disposed adjacent one side of the substrate, wherein the coating dispenser is tilted toward the opposite side of the substrate so that the coating material released from the coating dispenser is applied to the substrate. A method of forming a fade region on a substrate surface, wherein the fade region is deposited as a graded fade region thereon. In practicing the present invention, it is preferred to use an organometallic material that forms a coating by pyrolysis.

The present invention further relates to an article of manufacture made using the above method and apparatus, for example, a building window or an automotive transparency.

Description of Preferred Embodiments For the purposes of further description, the terms “close”, “far”, “up”, “down”, “right”, “left”, “vertical”, “horizontal”, “Top”, “bottom”, “top”, “bottom”, and derivatives thereof, relate to the present invention in describing the present invention in the following specification. It is to be understood that this invention is capable of various other modifications and sequence of steps, unless specified to the contrary. It should also be understood that the specific methods, compositions, devices, and articles described in the following specification are merely exemplary embodiments of the present invention. Therefore, the particular dimensions and other physical characteristics associated with the embodiments disclosed herein should not be considered as limiting the invention.

When forming a light-shielding band or a fade region on a substrate, it is desirable to form a fade region of a selected transmission color. This is especially important in the case of automotive windows, so that the color of the automotive window is aesthetically pleasing to the color of the vehicle. In this regard, embodiments of the present invention include a selected transmission color (one or more) on a glass substrate.
Coating compositions and methods that can be used to form the coatings of the present invention. These compositions and methods can be used with conventional coating equipment such as, but not limited to, conventional chemical vapor deposition (CVD), PVD, MSVD, or pyrolysis coating equipment. An example of such a conventional coating device is disclosed in U.S. Pat.
Nos. 76,114, 3,004,875 and 4,138,284 (
The contents of those descriptions are incorporated herein by reference to these specifications. )It is described in.

Referring to FIG. 1, there is shown a coating apparatus 10 incorporating features of the present invention. The coating apparatus 10 has a coating station 14 for depositing a graded coating on a substrate. 1 and 2, the graded coating of the present invention is shown as spaced lines of decreasing thickness. However, it should be understood that this illustration is only symbolic, and that in practice the coating of the present invention has a non-striped gradual appearance. In discussing the present invention, a pyrolytic coating is deposited on, but not limited to, a heated substrate. Accordingly, in the following description, a heated chamber, such as a furnace 12, and a conveyor 16 will be used at the coating station 14. The conveyor 16 is moved from the furnace 12 to the coating station 14.
The substrate 18 to be coated, for example, a piece of flat glass, is configured to be transported from the furnace 12 through the coating station 14 at a selected speed. Conveyor 1
6 may be of a conventional type, such as a plurality of rotating metal or ceramic rolls.
Furnace 12 may be a chamber in which molten glass moves over a metal bath to form a flat glass of a type known in the art that is shaped to give a flat glass strip. . Conveyor 16 may be a conveyor that transfers the glass strip from the forming chamber to an annealing furnace of the type used in the art to anneal a flat glass strip.

The coating location 14 is a Binks-Sames type 95 for conventional air atomization.
It has a coating dispenser 20, such as a spray nozzle. The coating dispenser 20 is configured to spray as a fan or cone pattern toward the surface of the substrate 18 in the coating location 14 to form a mist of liquid material. Dispenser for coating 2
O is in flow through a flexible conduit 24 with a source 22 of an aqueous suspension of a coating material, preferably one or more metal acetylacetonates or other conventional coating materials. Suitable coating materials are described, for example, in U.S. Pat.
No. 19,127 (the contents of which are incorporated herein by reference to this specification). Cole-Parmer
A metering pump 26, such as a MasterFlex 07523-20 pump, is in communication with conduit 24. The coating dispenser 20 includes a flexible conduit 30.
Accordingly, the fluid is also circulated with the compressed fluid source 28 such as air.

The coating dispenser 20 is preferably mounted for rotation, lateral and vertical movement in a conventional manner on a support 34 such as a metal frame. The coating dispenser 20 has a imaginary axis or line L drawn through the center of the spray emitted from the nozzle or discharge end of the coating dispenser 20 against the glass piece or the support surface of the conveyor 16 to be coated. From about 0 to 90 °, preferably about 20 °, with a vertical axis V extending substantially perpendicular to the surface of the substrate 18 to be coated or the supporting surface.
It is mounted so that an angle α of ４０40 ° (only shown in FIG. 1) is formed. The coating dispenser 20 can move both vertically and horizontally, and therefore, besides the height of the coating dispenser 20 from the conveyor 16, the position of the dispenser 20 along the conveyor 16 and the coating dispenser 2 for the conveyor 16.
The position next to 0 can be selectively fixed. Although only one coating dispenser 20 is shown in FIG. 1, a plurality of such coating dispensers 2
0 can be located above the first support 34, for example beside, above, or below the first coating dispenser 20.

The first exhaust hood 40 is disposed upstream of the coating dispenser 20 with respect to the moving direction of the conveyor 16 as indicated by the arrow line indicated by the equation 41, and the second exhaust hood 42 is Is disposed downstream of the coating dispenser 20 with respect to the moving direction. Optionally, and preferably, a temperature sensor 43, such as a conventional infrared thermometer, is located on the conveyor 16 adjacent to the first exhaust hood 40 to detect the temperature of the substrate 18 for pyrolytic coating. Each exhaust hood 40 and 42 communicates with a respective exhaust conduit 44 or 45. An auxiliary exhaust hood 49 may be located near the side of the substrate 18 remote from the coating dispenser 20 to provide additional exhaust capability. To avoid unwanted overspray on the glass surface, a barrier 51 as shown in FIG. 2 may be arranged and / or a hood 49 may be used. In this manner, the spray material from the coating dispenser 20 does not come into contact with the spray material, preventing the spray from disturbing the spray material. Not to be.

With continued reference to FIG. 2, a coating apparatus 100 incorporating features of the present invention is shown. The coating apparatus 100 has a second coating station 114 having a second coating dispenser 120 rotatably mounted on a second support 134. Third exhaust hood 47
Is disposed downstream of the second exhaust hood 42. Although not shown in FIG. 2, the auxiliary exhaust hood 49 as shown in FIG.
May be arranged respectively. The second support 134 includes the second coating dispenser 120.
Is laterally separated from the first support 34 such that is disposed between the second exhaust hood 42 and the third exhaust hood 47. 2, additional coating dispensers 121 may be located at the second coating location 114, for example, beside, above, or below the second coating dispenser 120. In both devices 10 and 100,
There is no shield or deflector between the spray from the coating dispenser and the object to be coated.

The second coating dispenser 120 may flow through the compressed fluid source 28 and the coating material source 22 of the first coating dispenser 20 and spray the same coating material onto the substrate 18. Alternatively, as shown in FIG. 2, the second coating dispenser 120 communicates with another source of compressed fluid 128 via conduit 130 and with another source of coating material 122 via conduit 124 having a metering pump 126. The same or a different coating may be sprayed onto the substrate 18. Dispenser for additional coating 12
1 may also be in communication with the same or different sources of compressed fluid and coating material as coating dispensers 20 and 120.

FIG. 3 illustrates a conventional float glass apparatus 46 embodying features of the present invention. As will be readily apparent to those skilled in the art of float glass manufacture, conventional float glass apparatus 46 has a furnace 48 in which molten glass is formed. The molten glass is then transferred onto a molten metal bath contained in a forming chamber 50, forming a glass band on the surface of the metal bath. The glass strip exits chamber 50 by conveyor 54 and travels into annealing furnace 52. As shown in FIG. 3, a coating station, for example, the coating station 14 of FIG. 1 or the tandem coating station 100 of FIG. 2, can be located between the chamber 50 and the annealing furnace 52.

The operation of the coating station 14 will now be described with particular reference to the embodiment shown in FIG. In the following description, the heating chamber or furnace 12 of FIG. 1 can be considered as a conventional furnace for the continuous glass, for example the chamber 50 of FIG. 3 for glass strips or individual pieces of glass.

A continuous substrate to be coated, such as a piece of flat glass, for example, a glass strip, or individual substrates 18 is heated in chamber 50 or furnace 12 to the desired temperature, respectively. Conveyor 16 transports heated substrate 18 into coating station 14. Dispenser for coating 2
0 is selectively positioned at a desired height and lateral position, i.e., at a desired distance from the edge of the conveyor 16, so that when the substrate 18 is moved through the coating location 14, the coating dispenser 20 is coated. At an angle α facing the upper surface of the base 18. This placement of the coating dispenser 20 can be done manually or automatically by a conventional automatic placement device attached to the coating dispenser 20.

As the substrate 18 moves through the coating station 14, the coating material is transferred from the coating material source 22 to the coating dispenser 20 and mixed with compressed air from a compressed fluid source 28,
The coating material is ejected from the nozzle of the coating dispenser 20 toward the heating substrate 18 as a conical spray pattern of the coating material. The first and second exhaust hoods 40 and 42 exhaust excess coating material from the coating location 14 and provide a uniform coating with essentially no defects or scratches. The auxiliary exhaust hood 49 may also be used to further facilitate exhaust from the coating location 14. As mentioned above, the barrier 51 shown in FIG. 2 may be used to prevent airborne coating particles from migrating and depositing on the glass strip farthest from the coating dispenser. As the substrate 18 moves through the coating station 14,
A coating dispenser 20 sprays the coating material onto the upper surface of the heated substrate 18 where the coating material pyrolyzes to form a substantially durable graded pyrolytic coating.

Fixing the size of the fan spray measured on the glass surface, the speed of the conveyor 16, and the distance between the nozzle of the coating dispenser 20 and the substrate 18, the spray pattern is desired on the upper surface of the substrate 18. To form a distribution or grading of The coating pressure and volume through the coating dispenser 20 is selectively controlled to deposit a desired coating gradient and thickness on the surface of the substrate 18. The coating dispenser 20 is angled toward the far side of the substrate 18 so that a thicker layer of coating material is deposited on the near side of the substrate 18, i.e., the side of the substrate closest to the coating dispenser 20. However, the thickness of the coating material deposited on the substrate 18 decreases as the distance from the opposite edge of the substrate (the edge furthest from the coating dispenser) decreases, with a substantially continuous thickness therebetween. As the thickness gradient occurs, i.e., as the distance from the coating dispenser 20 increases, the thickness of the coating decreases. In this manner, a smooth, substantially continuously graded coating material 60 is applied over the desired width of the upper surface of substrate 18. The resulting coating may give defects that form common streaks or spots when using conventional coating equipment, as conventional shields or deflectors are unnecessary for practicing the present invention. Instead, a smooth, continuous gradient is formed on the substrate 62. Also, by using a thermally decomposable coating material rather than a general dye in the conventional method,
The coated substrates obtained according to the invention can be used without the need for additional protective measures, such as protective outer coatings, or without the laminations generally required for conventional dye-coated substrates, for example for automotive transparent coatings. Can be used directly as a body.

It will be apparent to those skilled in the glass coating art that the parameters of the coating equipment will affect the resulting coating. For example, all other things being equal, the faster the substrate 18 moves through the coating location, the thinner the total thickness of the coating. As the angle increases, the coating closer to the coating dispenser 20 becomes thinner and the coating further away from the coating dispenser 20 becomes thicker. Base 18 of coating dispenser 20
As the height from the is increased, the total coating becomes thinner. The greater the flow of coating material through the coating dispenser 20, the thicker the total coating.

Example 1 A flat piece of glass having a thickness of about 4.0 mm (0.157 inches), a width of 60.1 cm (24 inches), and a length of 76.2 cm (30 inches), ie, a substrate [
Commercially available under the trade name SOLARBRONZE from PPG Industries, Inc. of Pittsburgh, PA] was coated at the coating site of the present invention shown in FIG. The substrates are washed with a diluted detergent solution, rinsed with distilled water,
Then it was air dried. The cleaned glass substrate was heated in a horizontal roller hearth electric furnace having a furnace temperature of about 1150 ° F (621 ° C). The heated substrate was moved by a conveyor from the furnace through the coating site at a linear speed of about 635 cm (250 inches) / min. The temperature of the substrate entering the coating site is measured by an infrared thermometer 43 located on a conveyor immediately upstream of the first exhaust hood 40 and is approximately 613-615.
° C (1135-1139 ° F). The coating material used was an aqueous suspension mixture of finely divided metal acetylacetonate in water, having a specific gravity of 1.025 as measured at 22 ° C. (72 ° F.) at 16.5% by weight. . Metal acetylacetonate mixture, and Future "second cobalt (cobaltic) acetylacetonate" _{Co (C 5 H 7 O 2} ) 3 referred as 95 wt%, the future "ferric (ferric) acetylacetonate" referred as _{Fe (C 5 H 7 O 2} ) was composed of _3, 5% by weight. 3
The aqueous suspension was placed in a vessel with a blade mixer operating at 52 rpm. The liquid suspension was pumped through a laboratory peristaltic metering pump (Cole Palmer Masterflex 07523-20) to a spray nozzle at a rate of 85 ml / min.
The spray nozzle is a conventional air spray type (Binks-Sames type 95), 3.5 k
Compressed air was used at a pressure of 50 g / cm ² (50 pounds / in ² ). The spray nozzle was located about 17.8 cm (7 inches) laterally from the near side of the substrate and about 27.9 cm (11 inches) vertically above the surface of the glass substrate to be coated. The spray nozzle was angled such that the centerline of the nozzle intersected the surface of the substrate at an angle α of about 25 °. This configuration formed a graded substantially bronze fade area on the glass substrate.

As shown in FIG. 2, a certain number of coating locations 14, 114 are
It may be arranged in series to apply the same or a different coating material on the substrate 18 at 14. For example, a pending U.S. patent application entitled "Compositions, Devices, Methods, and Articles Produced Thereof for Forming a Selected Color Coating on a Substrate" The compositions and methods described in US Pat. Nos. 6,064,098, 5,81,098, 5,867,898, 5,867,898, the contents of which are incorporated herein by reference, may be used to form a layered or laminated coating on a substrate, or to produce a selected color, or to provide multiple coatings on the same substrate. It is desirable to form a color of

Although the above description focuses on practicing the invention with a coating apparatus using a conventional spray nozzle with air, the invention is not limited to such a coating apparatus. , Other types of coating equipment, for example coating machines for depositing coatings (CV
D coating machine). It will be apparent to those skilled in the CVD coating art that the CVD coating machine is typically located on a moving substrate. The coating block has a delivery slot through which the coating material is released, and one or more exhaust slots arranged transverse to the direction of movement of the substrate. The bottom 138 of the CVD coating block 140 incorporating the principles of the present invention is shown in FIG. 5, for example, as shown by the dotted line in FIG.
Can be placed inside. As shown in FIG.
Has at least one tapered coating delivery slot 142 that tapers from a narrow width at one end to a wide width at the other end to pass coating material through the coating block 140 underneath. Can be sent in a conventional manner toward the surface of the substrate moving in the direction of arrow X. Exhaust slots 1 on both sides of delivery slot 142
44 are arranged. The exhaust slot 144 may be of a uniform width as shown in FIG. 5 or may be tapered, for example, in a manner similar to the delivery slot 142. Alternatively, the delivery slot 142 may have a uniform width and the exhaust slot 1
44 may be tapered. The substrate surface under the narrower portion of the delivery slot 142 is provided with a thicker coating than under the wider portion of the delivery slot 142, with a graded thickness deposition between them. Is done.

FIG. 6 illustrates yet another embodiment of a coating location 148 of the present invention. Covering location 14
8 has a first exhaust hood 40 and a second exhaust hood 42 remote therefrom, with a plurality of alternatingly spaced coating dispensers 200 therebetween, for example,
A conventional spray nozzle with air is arranged. Although three such coating dispensers 200 are shown in the embodiment shown in FIG. 6, the present invention should not be considered as limited thereto. The coating dispenser 200 is preferably movably or rotatably mounted on a stationary frame above the conveyor 16 used to carry the substrate 18 to be coated to the coating location 148. Of course, alternatively, the coating dispenser 200 may be
It may be mounted on a movable frame or gantry to move the zero. The coating dispenser 200 is in communication with one or more sources of coating material and / or pressurized fluid.

As shown in FIG. 6, the coating dispenser 200 is preferably directed downward toward the substrate 18 to form a spray pattern on the substrate 18, such as an elliptical or elongated spray pattern 150. Each elongated pattern 150 as shown in FIG.
It has a main shaft 152 with the outer periphery or edge 156. Dispenser for coating 2
00 are arranged so that the spray pattern from one coating dispenser 200 does not interfere with the spray pattern from another coating dispenser 200. For example,
The coating dispensers 200 may be staggered such that the major axes 152 are all substantially parallel and spaced. As shown in FIG. 7, each coating dispenser 200 forms a coating area 158 on the substrate 18 as the substrate 18 moves through the coating location 148. The coating dispensers 200 are preferably arranged such that the coating area 158 formed by one coating dispenser 20 does not extend beyond the pattern center 154 of an adjacent coating dispenser 200. In this way, the covering region 158 overlaps and has a substantially uniform thick central region 162 with tapered or graded side regions 164 on both sides of the covering, as shown in FIG. Form a coating. If desired, the coated substrate 18 may be cut into two or more pieces. For example,
The substrate 18 is cut in half along the vertical axis Z shown in FIG. 8 to form two separate coated pieces, each having a gradual side area 164 or dividing the piece 18 into three parts. It may be cut into a central part with a uniform coating and two outer parts with graded regions.

In the embodiment described above, the coating dispenser 20 forming an elliptical coating pattern
Although 0 has been discussed, the present invention is not limited to such an elliptical covering pattern. For example, the covering pattern may have any shape such as a circle, an oval, and the like. Furthermore,
A plurality of such coating locations 148 may be arranged in series and the same or different coating materials may be sprayed on the substrate.

FIG. 9 shows the reflectance (%) from the coated surface (R ₁ ); the reflectance (%) from the uncoated surface.
) (R ₂ ); and transmittance (%) for a glass substrate coated at a coating site using the principles of the present invention. The coating location used was coating location 1 as shown in FIG.
48, but with two coating dispensers 200, one coating dispenser 200 offset laterally by a distance of about 12.7 cm (5 inches) from the other. About 4.0 mm (0.157 inch) thick, 60.1 cm (24 inch) width, and 76.2 cm (30 inch) to 101.6 cm (40 inch)
An aqueous suspension of a mixture of acetylacetonate of copper, cobalt, and manganese on a flat piece of glass having a length of The material was sprayed and the coating was pyrolytically deposited on the glass surface. The deposited coating is about 400
It had a maximum thickness of Å600 ° and had tapered regions on both sides of the coated piece of glass. Reflectances R ₁ and R ₂ , and transmittance were measured at selected locations across the coated glass from one tapered side or edge to the other tapered side. The position “0” on the abscissa in FIG. 9 corresponds to one edge of the coated glass sheet, for example, the left side, and the other portion of the horizontal axis indicates the distance from the edge, where the reflectances R ₁ and R ₂ and the transmittance values were measured. The coating has a high transmittance region located on the sides of the substrate, i.e., the tapered region, and a low transmittance region near the central portion of the substrate 18, i.e., the thicker central region. Has a region where the transmittance changes smoothly. In contrast, the coating had low reflectivity R ₁ and R ₂ on both sides of the substrate, and had high reflectivity near the center of the substrate. The value of R ₁ is than the value of R _2, it was higher in any measurement.

As mentioned above, adjacent coating dispensers 200 should be positioned such that the spray pattern 150 from one coating dispenser 200 does not interfere with the spray pattern 150 from another coating dispenser 200. It is. FIG. 10 shows reflectance R ₁ and R ₂ and transmittance values for a coating applied as described above, but with adjacent sprays causing interference between the two spray patterns. To give the result, a spray is used from each of two adjacent coating dispensers 200 arranged on a line perpendicular to the edge of the glass. Interference between the two spray patterns from the coating dispenser 200 formed a coating having a very speckled, non-uniform thickness center. The reflectance% and the transmittance% are based on the standard C.I. I. E. FIG. And C light source at an observation angle of 2 °.

FIG. 11 generally shows a vehicle 210. The vehicle 210 has a windshield 212, a rear window 214, and side windows 216, 218, and 220. For descriptive purposes, these are collectively referred to simply as "windows". Side windows 216 and 21
8 shows a graded fade region 222 that gradually changes from a thinly coated substantially transparent first region 224 near the bottom to a thicker coated less transparent second region 226 near the top in accordance with the present invention. It is formed from glass that has been coated to form. As shown in the preferred embodiment with respect to side windows 216 and 218, fade region 222 is mounted to vehicle 210 such that it is vertically oriented. But,
As shown with respect to side window 220, if desired, fade region 222 may be horizontally oriented. Fade region 222 may be oriented so that first region 224 is at the top of the window, if desired. Further, as described above with respect to the coating device 100, the fade region 222 may be formed of adjacent coatings such that the first region 224 has a first color and the second region 226 has a different second color. It can be formed by applying a different coating material while forming the fade region 222 at the location.

Specific coating compositions and methods for achieving a selected transmission color coating are described below. These compositions and methods are generally categorized according to the colors produced for ease of description. However, it should not be considered that the invention is limited to these particular classes.

Copper-Manganese Oxide Coating Coatings formed with suspensions having copper-containing and manganese-containing components, especially pyrolytically deposited coatings, are based on the molar ratio of copper to manganese in the applied suspension. It has been found to give excellent coatings with transmission colors ranging from amber or light brown to blue-grey or blue. In particular, manganese-containing acetylacetonates [eg, Mn (C _5, hereinafter referred to as “manganous acetylacetonate”)
H ₇ O ₂ ) ₂ , or Mn (C ₅ H ₇ O ₂ ) ₃ ], referred to as “manganic acetylacetonate”, and copper-containing acetylacetonate [eg, “cupric acetylacetonate” mixture aqueous suspension containing the _{Cu (C 5 H 7 O 2} ) 2 ] mentioned as "the light brown when a high copper content, or manganese content is high amber, copper in the coating It has been found that a manganese-to-manganese molar ratio of 1 results in a coating of transmission color ranging from blue to gray when the molar ratio is slightly greater than or less than 1 to blue-grey. The color changes as the copper to manganese molar ratio increases or decreases are listed in Table 1 and shown in FIG. 7, which are discussed in more detail below.

An aqueous suspension of acetylacetonate containing copper and manganese, such as cupric and manganous acetylacetonate, is cut into 4 inch × 4 inch squares. A coated substrate was formed by hand spraying on the transparent float glass substrate. The substrate was washed with a diluted detergent solution, rinsed with distilled water, and then air dried. Cupric _{acetylacetonate, Cu (C 5 H 7 O} 2) 2, and the first manganese acetylacetonate, and _{Mn (C 5 H 7 O 2} ) 2 of the aqueous suspension, prepared by conventional wet grinding method The copper and manganese containing acetylacetonates were then mixed in the desired proportions with deionized water and a chemical wetting agent to disperse, degas, and suspend the metal acetylacetonate particles. Heating the substrate in a conventional tabletop muffle furnace to a temperature sufficient to ensure pyrolysis of the applied suspension, e.g.
Next, it was sprayed by hand using a Binks-type 95 spray gun equipped with a naturally falling supply tank.

The range of transmitted and reflected colors of the coated substrate is shown in Table I as a function of composition, and the colors of the samples are shown in FIG. The reflected and transmitted colors of the coated substrate were measured in standard fashion using standard chromaticity coordinates, Y,
It is described using x and y. The coated substrate was analyzed using X-ray diffraction. Samples A6-A8 in Table I were determined by X-ray fluorescence spectroscopy (XRF) and typically occur in cubic Cu _1.4 Mn _1.6 O _{4 with} a Cu / Mn molar ratio in the coating in the range of 0.8-1.1. It was found to contain a spinel-type phase as the main phase. The Cu-rich coatings of Samples A1 and A2 exhibited a brown transmission color, and the Mn-rich colored coatings exhibited an amber transmission color as in Samples A13 and A14.

[0045]

Example 2 In this example, a substrate was prepared and coated as follows. 10.2cm x 10.2c
m (4 inch x 4 inch) square, 4 mm thick float glass substrates are cleaned by passing the substrates through a diluted detergent solution, rinsing the substrates with distilled water, and then air drying the substrates. did. The cleaned glass substrates were sprayed with a 50/50% by volume solution of 2-propanol and distilled water and wiped dry with a cellulose polyester cloth to remove dirt, unwanted films, fingerprints and / or debris.
Aqueous suspensions of cupric acetylacetonate and sec-acetylacetonate were prepared by conventional wet milling techniques. These single metal acetylacetonate suspensions were mixed together to form a binary suspension having a Cu / Mn molar ratio ranging from 9.09 to 0.43. The glass substrate was transferred into a tabletop muffle furnace and heated to a temperature of about 600 ° C. The heated substrate was sprayed by hand using a spray gun equipped with a gravity drop supply reservoir to apply the aqueous suspension onto the substrate. The spray gun used in this experiment was a Binks type 6
3PB air cap, Binks type 63SS fluid nozzle, and Binks type 663
Had a needle. The gun air pressure was set at 50 psi. The aqueous suspension was sprayed onto the substrate for about 8 seconds from a distance of about 25.4 cm (10 inches) from the glass surface.

As shown in Table II, high Cu / is equal to or greater than about 15.13.
Films with a Mn molar ratio resulted in a coated substrate with a brown transmission color. XR in the membrane
As the Cu / Mn ratio determined by F decreases, sample No. For B1 to B9, the transmission color changed from light brown to gray blue, deep blue, and bright blue. table
Sample No. II The clear-light, deep-blue coating of B6 to B8 is determined by XRF analysis and typically results in cubic C with a Cu / Mn molar ratio in the film in the range of 0.8 to 1.2.
It was determined by XRF analysis containing a large amount of u _1.4 Mn _1.6 O ₄ spinel phase. After deposition, the coated substrate was heated at 650 ° C. for about 10 minutes. This heating causes a change in luminous transmittance (%) (ΔY) and a change in color, which are shown in Table II as ΔE (FM
CII). For ease of description, the increase in transmittance that occurs after heat treatment is referred to herein as "bleaching." ΔE (FMCII) in Table II is defined as the difference in color of the coated substrate before and after heating. ΔE (FMCII) was determined according to a conventional formula established by the CIE Chromaticity Committee.

Sample No. in Table I It should be noted that a Cu _1.4 Mn _1.6 O ₄ blue spinel-type phase can be produced by using a Cu (II) / Mn (II) acetylacetonate suspension as in A6-A8. The same spinel-type phase was obtained from Sample B in Table II.
Also observed in the case of the Cu (II) / Mn (III) acetylacetonate suspension used in 6-B8. Table I shows sample no. Although the results after heat treatment of A6 to A8 are not shown, these samples are shown in Table II as sample Nos. It is expected that the color will be bleached in the same manner as in B6 to B8.

[0049]

Diffusion Bonding Experiment In the Cu-Mn system, copper is the most mobile substance. This decision was made based on the following experiment. A CuO film was formed on the surface of the first heated quartz substrate by spraying.
In the following description, when coated, the substrate was at about 600 ° C. An Mn ₃ O ₄ film was formed on the surface of the second heated quartz substrate by spraying. The two substrates were then superposed face-to-face such that a portion of the coating surface was in contact with one another and the remainder of the coating surface was separated from one another, ie, that portion of the coating surface was not in contact with one another. 6
Heated to 50 ° C. for 16.2 hours. Upon separation, the coated surface portion of the second substrate, which was in direct contact with the CuO film on the coated surface of the first substrate, showed a dark blue color to the naked eye. This is considered due to the fact that Cu ions from the CuO film is moved to the Mn ₃ O ₄ film was formed dark blue coating of Cu _1.4 Mn _{1 .6} O ₄ spinel phase. The corresponding region of the CuO film became much brighter by heating, indicating that the Cu ions had disappeared. The portion of the Mn ₃ O ₄ film on the second substrate that was not in contact with the CuO film changed from amber to a magenta / light purple Mn ₂ O ₃ film by heating.

In yet another experiment, a CuO film was deposited on a heated quartz substrate and M
It was deposited n ₃ O ₄ film. The substrates are then brought into contact with portions of the coating surface,
The surfaces were overlapped so that the rest did not touch each other. 65
Heat at 0 ° C. for 30 minutes. Upon separation, the coated surface portion of the second substrate, which was in direct contact with the CuO film on the coated surface of the first substrate, exhibited a dark blue transmission color to the naked eye. It is considered that this is because copper ions migrated from the copper oxide (CuO) film to the Mn ₃ O ₄ film and formed a dark blue Cu _1.4 Mn _1.6 O ₄ spinel phase. The corresponding film on the quartz substrate became very bright, indicating that the Cu ions had disappeared. The remaining area of the film remains almost unchanged and copper ions do not readily diffuse into the quartz, but preferentially diffuse into the Mn ₃ O ₄ film deposited on the glass substrate, resulting in a dark blue Cu _1.4
Mn _1.6 O ₄ spinel-type phase was formed. This also indicates that Mn ions do not diffuse preferentially into the glass, but that they diffuse much more slowly than Cu ions.

A CuO film was deposited on a heated glass substrate, and a Mn ₃ O ₄ film was deposited on a heated quartz substrate. Then, the two substrates were heated face to face at 650 ° C. for 30 minutes. Upon separation, the surface of the amber Mn ₃ O ₄ film on quartz, which was not in contact with the copper oxide film on glass, had changed to a light purple Mn ₂ O ₃ film. A small portion of the quartz substrate showed a blue region, indicating the presence of a dark blue Cu _1.4 Mn _1.6 O ₄ spinel phase. But,
Most of the Cu diffused into the glass rather than towards the Mn ₃ O ₄ film deposited on the quartz. Therefore, from these experiments, it was concluded that Cu ions are a more mobile substance in the CuMnOx system and a main substance that must be prevented from diffusing into the glass substrate.

[0053] As described in connection with Example 2 of the bleaching prevention, thin film as deposited on a glass substrate tends to change the color in the heat treatment after such as strengthening or annealing. This is believed to be due to ion exchange of mobile substances between the coating layer and the glass substrate. It is known to include an inert layer (s) between the glass substrate and the coating to serve as a barrier layer to help prevent such diffusion. However, these diffusion layers are not always effective. Accordingly, alternative methods have been developed to stop or slow such diffusion by using a concentration gradient layer disposed between the coating layer and the substrate. This concept could be generally described as follows.

For the purpose of discussion, for example, A, B and C may be AB
Discoloration, i.e. decolorization, of a single-layer oxide coating, expressed as COx, after heat treatment by diffusion into the glass substrate by B ions, e.g. by exchange with D ions, e.g. alkali ions coming from the glass substrate Is known, a thin film of BOx is deposited between the glass substrate and the ABCOx coating. It will be appreciated that the invention can be practiced with a single-layer oxide coating containing two or more metal ions. The BOx layer provides a layer with a sacrificial or concentration gradient that prevents such bleaching. B ions from the sacrificial layer diffuse into the glass more easily than B ions from the ABCOx coating. Thus, by placing the BOx layer between the ABCOx layer and the glass, the B ions in the underlying BOx coating layer diffuse partially or entirely into the glass. The BOx layer acts as an overlayer, a deterrent layer with a concentration gradient that prevents or slows the diffusion of B ions from the ABCOx layer into the glass substrate. Thus, while the B ions from the lower BOx coating will diffuse little into the glass and probably only slightly into the upper coating, the B ions in the upper coating ABCOx will diffuse at all. If so, it diffuses more slowly into the underlying BOx coating, thereby minimizing degradation of the ABCOx layer. Thus, the transmission color of the coated glass can be controlled by the thickness and composition of the BOx layer, as well as the thickness and composition of the coating layer ABCOx above. This is a function of time, temperature, and film thickness,
This is due to the fact that even if most or all of the BOx layer fails, only the desired ABCOx top coating remains substantially intact. The BOx layer is preferably deposited directly on the glass substrate, but may be coated on another coating layer deposited on the substrate.

For the purpose of acting as a concentration-grading deterrent layer, the BOx layer is deposited both to minimize discoloration in the coated glass and to minimize diffusion of B ions from the top coating layer into the glass. Should. For example, the aforementioned Cu _1.4 Mn _1.6 O ₄ blue film is decolorized by heat treatment (eg, 650 ° C. for 16 hours), the color no longer exists, and the chromophores up to the point where Cu and Mn ions diffuse into the glass. This results in the destruction of the crystal structure. As discussed above, copper is the most mobile substance in this system. Therefore, to form a two-layer structure consisting of glass _{/ CuO / Cu 1.4 Mn 1.6 O} 4.

The experimental results of depositing CuO layers with various thicknesses are shown in Table III below. The coating was deposited on a heated piece of float glass, on a surface that was not supported on a tin bath during glass production. Unsupported surfaces were coated, similar to what is currently done online to perform pyrolysis or CVD coatings on float glass strips. The tin-rich surface of a piece of glass cut from the float glass strip
Can be coated during laboratory experiments. However, it has been determined that the tin-rich surface of the glass acts as a barrier to the diffusion of ions from the coating into the glass during the heat treatment, and that the tin ions act as a barrier. A CuO layer was deposited on the glass, and then a Cu _1.4 Mn _1.6 O ₄ layer was deposited on the CuO layer. The thickness of the CuO layer was varied by changing the spray time of applying the copper acetylacetonate suspension on the glass substrate. That is, the thickness of the CuO layer obtained with a spray time of 2 seconds is smaller than that obtained with a spray time of 8 seconds. The thickness of the CuO layer is about 50 ° with a spray time of 2 seconds.
To about 200 ° with a spray time of 8 seconds. It will be appreciated that the present invention is not limited to the thickness of the copper oxide layer, but that thicknesses in the range of 25 ° to 260 ° are acceptable in the practice of the present invention. The thickness of the Cu _1.4 Mn _1.6 O ₄ layer was unchanged and had a thickness of about 300 °. 0.54 molar ratio of copper (II) and depositing the Cu _1.4 Mn _{1. 6} O _1.4 film by manganese (III) spraying acetylacetonate 8 seconds, depositing a layer having a thickness of about 300Å Was. The present invention is not limited to the thickness of the Cu _1.4 Mn _1.6 O _1.4 film, but is
It will be appreciated that thicknesses in the range of Å are acceptable. The thickness of the sample film is
Determined by polarization spectroscopy.

A clear bleaching effect was observed for coatings deposited on glass, for example glass produced by the float process. However, for coatings deposited on quartz, the bleaching effect was not as pronounced as the glass substrate. This is because the ions present in the quartz substrate are on the order of ppm and the ion exchange is small, so that little or no ion exchange occurs between the quartz substrate and the coating.

[0058]

The two-layer structure (glass / CuO / Cu _1.4 Mn _1.6 O ₄ ) has a light brown CuO
The presence of the bottom layer did not give the typical blue color associated with the Cu _1.4 Mn _1.6 O ₄ spinel type phase. The two-layer structure was heat-treated at 650 ° C. for 10 minutes to obtain Cu _1.4 M
A comparison was made with an as-deposited unheated monolayer sample having an n _1.6 O ₄ spinel type phase coating. Cu / M in top coating, leaving bottom layer (close to glass) the same CuO layer
Table IV shows the results of comparing the two-layer structure subjected to the same heat treatment with the as-deposited two-layer structure while changing the nmol ratio from 0.82 to 1.49. After heating each of the two-layer structures, Cu ions from the concentration-gradation-suppressing CuO layer diffused into the glass and were transmitted because the desired Cu _1.4 Mn _1.6 O ₄ blue spinel-type top layer was left intact. The color turned blue again. The change in transmitted color (decolorization) ΔY before and after the heat treatment in the case of the two-layer structure decreases from 11% to 0.75% at a Cu / Mn ratio of 0.82, and decreases to Cu of 1.00. In the case of the / Mn ratio, the ratio decreases from 6.4% to 0.26%.
In the case of a Cu / Mn ratio of 49, it decreased from 3.4% to -0.32% (darkening after heat treatment). In addition, ΔE (FMCII) (color change in Mac Adam Units for the three samples referred to above) is due to Cu on the supported surface of the glass.
As a result of the presence of the O layer, 18.1 to 3.4, 17.8 to 3.7, respectively.
And 15.1 to 4.9.

[0060]

The addition of other metal-containing components, such as transition metal-containing acetylacetonates,
It changes the reflectivity and transmission of the coating and changes the color and absorption of the coating. For example, Mn
CuCr oxide films tend to be dark gray.

In the above example, copper-containing acetylacetonate and manganese-containing acetylacetonate were sprayed as a mixture onto the heated substrate, but individual acetylacetonate suspensions could also be sprayed onto the heated substrate sequentially. The same desired color can be achieved. For example, a suspension of a copper-containing material, such as cupric acetylacetonate, is sprayed onto a heated glass substrate, the substrate is cooled, reheated, and then treated with manganous or manganese acetylacetonate. Spraying such a manganese-containing material,
For example, the blue color of the Cu-Mn chromophore described above can be generated using, for example, the coating apparatus shown in FIG. Manganese or manganese acetylacetonate may be sprayed on the substrate first, followed by another coating of cupric acetylacetonate. Again, regardless of the deposition order, the desired color is achieved. Further, it is recognized that the present invention is not limited to that temperature of the substrate during coating, and that any temperature at which pyrolytic coating occurs, such as 400 ° C and 900 ° C, can be tolerated. Will be. Furthermore, for _{example, A x B y (C 5} H 7 O 2) l membranes (
Where A or B is a metal ion, such as copper or manganese, and x, y and l are moles that balance the formula for the desired binary acetylacetonate compound). It will also be appreciated that binary or ternary metal acetylacetonates can be used.

Although the manganese or manganese and cupric acetylacetonate systems described above have been successful in forming blue chromophores, the resulting blue coating is relatively poor in acid resistance.

The following experiment was performed to find the molar ratio of the copper / manganese system to give the desired color with durability. The substrate was cleaned as described above for the substrate of Example 1. The coating material was a finely divided mixture of manganese, cupric, and cobaltous acetylacetonates. The milled material was suspended as an aqueous suspension. The starting composition of the suspension is listed in Table V. The different Cu (II) / Mn (III
Table 8 shows the results of the eight samples for the molar ratio. The composition of the starting mixture and the resulting membrane are described in D.W. C. Analyzed by plasma analysis. Films with a blue-grey transmission color were found to have a Cu / Mn molar ratio in the range of about 1. Other compositions were amber in appearance. The right column of Table V gives the results of the coatings tested according to the conventional ASTM 282-67 test (standard test method for acid resistance of enamel, citric acid spot test). “Yes” indicates that there is acceptable durability.

[0065]

It has now been found that the addition of cobaltous acetylacetonate, Co (C ₅ H ₇ O ₂ ) _3, to a manganese and copper containing acetylacetonate system produces the desired blue-gray pyrolytic coating. Can be. This Cu / Mn / Co mixture also provides significantly improved acid resistance. When the cobalt content of the mixture is higher than about 50% by weight,
Acid resistance increases to a maximum. As mentioned above, this increase in acid resistance is similar to the conventional A
Determined visually according to the STM 282-67 test (standard test method for acid resistance of enamel, citric acid spot test). This increase in acid resistance is due to Cu / Mn
It is believed that this was caused by the higher stability of the Co / Cu / Mn matrix compared to the stability of the matrix.

The iron oxide coating formed pyrolytically on the iron oxide composition glass generally produces a bronze or gold film upon transmission of light, absorbing, inter alia, the portion of the solar spectrum in the visible range, and the amount of heat entering through the glass. By improving the solar performance of the glass. Iron oxide can be applied to the heated glass by spray pyrolysis or chemical vapor deposition. In the case of a pyrolytic coating, the preferred method is to spray an iron-containing material, such as an aqueous suspension of ferric acetylacetonate, onto the glass to form an iron oxide coating.

The color of the iron-containing chromophore can be changed by adding additional metal ions to form a binary or ternary metal oxide thin film. For example, binary C
u-Fe oxide coatings, when formed on transparent glass substrates, tend to have a light gray amber color in transmitted light. Ternary oxide compounds formed from Cu, Cr and Fe materials, such as acetylacetonate, produce a dark gray amber color on a transparent glass substrate.
Further, the color of the deposited film can be changed using a compound having acetylacetonate of cobalt, manganese, aluminum, cerium, calcium, titanium, yttrium, zinc, zirconium, and tin.

A problem with typical iron oxide coatings is that they have a tendency to darken when subjected to further heat treatments such as strengthening or bending. This darkening is believed to be caused by the crystallization and grain size increase that occur at the temperatures required for strengthening or bending. It is also possible to add a barrier layer between the iron oxide and the glass to help prevent such darkening, but this darkening causes the iron oxide system to select a second component, such as Ca. , Cu, Al, Ce, Mg, Mn, Ti, Y, Zn, and Zr can be reduced, but the present invention is not limited thereto.

The anti - darkening calcium acetylacetonate suspension was combined with the iron acetylacetonate suspension in various molar ratios and pyrolyzed onto a heated glass substrate to form an iron calcium oxide thin film. The substrate was cleaned as previously described. 10.2cm (4in
2.) The two clear glasses on each side were sprayed with the same molar solution listed in Table VI for the time listed in Table VI. One glass was heat-treated. The film thickness was not measured. Sample F2 had a luminous transmittance LT _A of 66.94% as measured previously. After heat treatment, LT _A was 66.85% and the change in LT _A was less than 1%. The sample F1 in which the FeOx film was deposited on the glass piece and then heat-treated (at 650 ° C. for 10 minutes) was −7.65% (transmittance before heating 63.32%, transmittance after heating 5
The coating that darkened at LT _A change 5.67%) gives resulted. Similar results are shown for Fe-Mg oxides and Fe-Zr oxides (samples F4 to F6), where the binary metal oxide is less than the single metal oxide FeOx (F1). The change in luminous transmittance was much smaller.

[0071]

Additional Colored Oxide Permeable Film The Mn ₂ O ₃ oxide film formed on the transparent glass substrate can form a violet / light purple colored permeable film. A Mn ₃ O ₄ oxide film formed on a transparent glass or quartz substrate produces a bright amber transmission color. This amber colored film, by heating,
For example, by heating the coated substrate at 650 ° C. for 8 to 30 minutes, it can be converted into a magenta / light purple film. To improve the aesthetic appearance, silicon-containing barrier layers can be used to produce more uniform colors. For example, a silicon oxide layer is first deposited on a transparent float glass substrate, and then a manganese-containing acetylacetonate suspension is sprayed onto the clear float glass. The silicon-containing layer can be as thin as about 20 nm. The coating having a transmission color of magenta / light purple was found to contain almost Mn ₂ O ₃ by X-ray diffraction. The citric acid resistance was tested by the ASTM 282-67 test described above and was found to be durable to citric acid.

In the practice of the present invention, a Co—Mn oxide system [Co (II), Co (III)
, Mn (II) and Mn (III)]. The two systems used were the Co (II) / Mn (II) system and the Co (III) / Mn (III) system. These systems show from brown to grey-brown, bright green, bright yellow when the molar ratio of Co to Mn in the suspension changes from 9.0 to 0.1 when viewed visually with transmitted light under fluorescent lighting conditions. It has been found to produce coatings with transmission colors ranging up to green (see Table VII).

In preparing some of the suspensions described above, a surfactant was used. It will be appreciated by those skilled in the art that the use of a surfactant has minimal, if any, effect on the results obtained.

[0075]

It will be readily appreciated by those skilled in the art that modifications may be made to the present invention without departing from the concepts disclosed above. Such modifications are to be considered within the scope of the present invention. Accordingly, the specific embodiments described in detail above are merely illustrative and do not limit the scope of the invention. It is intended that the present invention cover the full scope of the appended claims and any equivalents thereto.

[Brief description of the drawings]

FIG. 1 is a perspective view of a coating location embodying features of the present invention.

FIG. 2 is a perspective view of another embodiment of the coating location of the present invention.

FIG. 3 is a block diagram of a float glass manufacturing apparatus having a coating place according to the present invention.

FIG. 4 is a cross-sectional side view of a substrate coated with a coating site of the present invention to form a graded fade region.

FIG. 5 is a bottom view of a CVD coater incorporating the teachings of the present invention.

FIG. 6 is a perspective view of another embodiment of the coating apparatus of the present invention.

FIG. 7 is a plan view of a covering pattern formed by the apparatus shown in FIG. 6;

FIG. 8 is a sectional end view of a substrate coated by the coating apparatus of FIG. 6;

9 is a graph of% reflectance and% transmittance across the width of a coated piece of glass produced by the coating apparatus of FIG.

FIG. 10 is a graph of% reflectance and% transmittance across the width of a piece of coated glass produced by the coating apparatus of FIG.

FIG. 11 is a perspective view of a vehicle having a window formed by a glass substrate coated according to the present invention.

FIG. 12 is a plan view of Samples A1 to A14 in Table I.

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] November 14, 2000 (2000.11.14)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

────────────────────────────────────────────────── ─── Continuation of the front page (31) Priority claim number 09/270, 702 (32) Priority date March 17, 1999 (March 17, 1999) (33) Priority claim country United States (US) ( 81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW) , EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU , CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR , LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, VN, YU, ZA, ZW (72) Inventor Scriben, Roger, El United States of America Pennsylvania, Gibsonia, Globe Road 3850 (72) Inventor Asey, Patricia, Ruzakowskiy United States of America Pennsylvania, Pitz Burg, Matiah Drive 104 (72) Inventor Greenberg, Charles, Bee United States of America Pennsylvania, Marylisville, Windgate Eve 3268 (72) inventor Surobodoniku, John, Bee United States Pennsylvania, New Kensington, Martin Avenue 1105 F-term (reference) 4G059 AA15 AB05 AC08 CA01 CA08 CB09

Claims (45)

[Claims] Providing a first component, providing a second component, and applying the first and second components on a surface of a substrate in a selected ratio of the first component to the second component. Forming a coating of a desired color on the surface. 2. Providing a mixture having a copper-containing component and a manganese-containing component in a selected ratio of copper to manganese to provide a coating of the desired transmission color, and providing said copper and manganese-containing component on a substrate surface. Applying the mixture having the composition to form a coating having a selected ratio of Cu / Mn on the surface. 3. The method of claim 2, wherein the ratio is a molar ratio. 4. The method of claim 2, wherein the selected ratio is about 1 and the coating has a blue transmission color. 5. The method of claim 2, wherein the selected Cu / Mn molar ratio in the coating is greater than one, and the desired color of the transmitted coating changes from gray-blue to brown as the ratio increases. Method. 6. The method of claim 2, wherein the selected Cu / Mn molar ratio in the coating is less than 1, and the desired color of the transmitted coating changes from gray-blue to amber as the ratio decreases. the method of. 7. The method according to claim 2, wherein the copper component is copper-containing acetylacetonate, and the manganese component is manganese-containing acetylacetonate, and the substrate is heated to thermally decompose the coating during the application step. the method of. 8. The method of claim 2, wherein the coating is Cu _1.4 Mn _1.6 O ₄ with a spinel-type layer to provide a coating having a blue transmission color. 9. The method of claim 2 including providing a layer having CuO between the coating and the substrate to prevent heating of the coated substrate from decolorizing the coating. 10. The method of claim 1, further comprising adding a chromium-containing component to the coating to provide a gray coating with transmitted light. 11. The method of claim 2, comprising adding a cobalt-containing component to the coating to improve acid resistance. 12. The method according to claim 11, comprising adding sufficient cobalt-containing component so that the amount of cobalt in the coating is greater than 50% by weight. 13. Selecting the desired coating mixture having two or more components to be deposited on the surface of the substrate, determining the component having the most mobile material, and providing the most mobile material on the surface of the substrate. Depositing a concentration gradient inhibiting layer of an oxide of a neutral material and applying a coating mixture over said concentration gradient inhibiting layer. 14. The method of claim 13, further comprising heating the substrate having the coating and layer to diffuse at least a portion of the most mobile material in the concentration gradient layer into the substrate to prevent decolorization of the coating. The described method. 15. Ca, Al, Ce, Mg, Mn, Ti, Y, Zn and Zr
Providing the coating with an iron-containing component having at least one component having at least one component to prevent the coating from darkening in subsequent heat treatment of the coated article substrate; and to provide a two-component component on the surface of the heated substrate. Forming an oxide coating on the surface of the substrate by applying the method. 16. A mixture having a copper-containing component and an iron-containing component is provided, and said component is applied to a substrate surface to form an iron and copper-containing oxide coating, and to provide a bright ash / amber color in transmitted light. A coating method comprising the steps of providing a coated substrate having: 17. A chromium-containing component, wherein the copper-containing component and the chromium-containing component are applied on a substrate surface to form an iron, copper and chromium-containing oxide coating and have a dark gray amber color in transmitted light. Providing a coated article, providing the coating with at least one component having at least one of Ca, Al, Ce, Mg, Mn, Ti, Y, Zn and Zr, wherein the heat treatment subsequent to the coated article substrate darkens the coating. 17. The method of claim 16, comprising the steps of: 18. An article made by the method of claim 1. 19. The article according to claim 18, wherein the substrate is a glass substrate. 20. A coating method comprising the steps of providing a manganese-containing component, applying the manganese component to a heated substrate surface, and forming a manganese-containing oxide coating on the substrate. 21. The method of claim 20, further comprising the step of mixing the cobalt-containing component and the manganese-containing component and applying the mixture onto the surface of a heated substrate. 22. The method of claim 20, wherein the manganese-containing oxide coating comprises manganese oxide and the color of the coating is magenta / light purple in transmitted light. 23. The method of claim 20, wherein the manganese-containing oxide coating comprises Mn ₃ O ₄ oxide and the transmission color of the coating is amber. 24. The method of claim 22, wherein the manganese-containing oxide coating is Mn ₃ O ₄ , further comprising heating the substrate having the Mn ₃ O ₄ coating to form a manganese oxide coating. . 25. The method according to claim 20, comprising applying a silicon-containing barrier layer between the substrate and the coating. 26. The method according to claim 25, wherein the silicon-containing barrier layer contains silicon oxide. 27. The method of claim 1, wherein the first component comprises copper, the second component comprises manganese, and the components are applied separately. 28. The method of claim 27, wherein the color of the coating is blue in transmitted light. 29. The method of claim 27, wherein the copper-containing component is applied before the manganese-containing component. 30. The method according to claim 29, wherein the substrate is heated before applying the manganese-containing component. 31. The method according to claim 27, wherein the manganese-containing component is applied before the copper-containing component. 32. The method according to claim 31, wherein the substrate is heated before applying the copper-containing component. 33. A method of forming a graded coating on a surface of a substrate having a first end and a second end, wherein at least one first coating dispenser is disposed relative to the first end of the substrate. Directing the first coating dispenser toward a substrate such that an axis extending through a discharge end of the first coating dispenser has a predetermined angle with the substrate, and the first coating dispenser. Supplying a first coating material to the substrate and depositing the coating material on the substrate to form a gradual coating on the substrate. 34. The method of claim 33, comprising heating the substrate to pyrolyze the first coating material on the substrate. 35. The method of claim 33, comprising disposing a first exhaust hood on one side of the first coating dispenser and disposing a second exhaust hood on the other side of the first coating dispenser. the method of. 36. The method according to claim 33, comprising placing at least one second coating dispenser remote from the first coating dispenser and supplying the second coating dispenser with a second coating material. The described method. 37. An article of manufacture formed by the method of claim 33. 38. A method of forming a graded coating on a surface of a substrate, the method comprising: providing a plurality of coating dispensers each configured to provide a spray pattern having a center on the substrate; Feeding the coating material through the coating dispenser, and disposing the coating dispenser to form a plurality of overlapping coating areas on the substrate while moving the substrate relative to the coating dispenser; Forming a gradual coating. 39. Arranging the coating dispensers such that the coating area formed by one coating dispenser on the substrate does not extend beyond the center of the spray pattern of an adjacent coating dispenser. Item 39. The method according to Item 38. 40. An article of manufacture formed by the method of claim 38. 41. An apparatus for forming a graded coating on a surface of a substrate, comprising: a support surface; at least one first coating dispenser having a discharge end; a source of coating material in flow with the first coating dispenser; At least one exhaust hood mounted at a predetermined distance to the first coating dispenser, and means for mounting the first coating dispenser to the support surface; No shield is disposed between the coating dispenser and the support surface, an axis extending through the discharge end has a predetermined angle with the support surface, and the coating material is disposed at the discharge end. A graded coating forming device, wherein the graded coating is sent from the substrate to the substrate surface to form a graded coating on the substrate surface. 42. The apparatus of claim 41, wherein the predetermined angle is between about 20 and 40. 43. An apparatus for forming a graded coating on a surface of a substrate, comprising: a coated release slot with paper having a first end and a second end, wherein the width of the release slot is the first end. A discharge slot decreasing from the first end to the second end;
And a at least one exhaust slot spaced from the discharge slot with paper. 44. A manufacturing method comprising: a substrate having a surface; and a graded coating pyrolytically deposited on the surface of the substrate, the coating varying in thickness along a predetermined length of the coating. Goods. 45. The article of manufacture of claim 44, wherein the glass substrate is a building window or an automotive transparency.