Low-e matchable coated articles and methods of making same

Description of the invention

The present invention relates to a coated article and an IG insulating glass assembly. These coated articles exhibit a low E-value and have approximately the same color characteristics when viewed with the naked eye both before and after heat treatment (e.g., after annealing). Such coated articles can be used as IG units, vehicle windshields, and other appropriate applications.

Layered coatings that characterize sunlight are known. For example, US Patent No. 5,688,585 discloses a sunlight-characterized coating article comprising a glass / Si3N4 / NiCr / Si3N4 system. One of the objects of this patent is to provide a sputter coated layered system which, after heat treatment, is of equal color to its untreated counterpart. While the coating systems of this document are excellent for this purpose, they have some drawbacks. In particular, they usually have high emissivity values ​​since no silver (Ag) layer is disclosed.

Low emissivity (low E) coating systems are also known in the art. For example, US Patent No. 5,376,455 discloses the system: glass / Si3N4 / NiCr / Ag / NiCr / Si3N4. Such as this, low emissivity coating systems are typically designed to provide maximum visible transmission. For this reason, the NiCr layers are quite thin. This allows high transmission and low E, but less solar control than desired (for example, shading coefficient). Thus, the low E value coating system according to US Patent No. 5,376,455 after heat treatment, unfortunately does not match the color of the untreated counterpart - it does not have better solar control properties than the shading coefficient (SC).

Thus, when it is desired to develop an insulating glass (IG) unit with both low emissivity (low E) and solar control properties, it is often necessary to combine the solar control coating of U.S. Patent No. 5,688,585 with the coating in a single IG unit. in U.S. Patent No. 5,376,455. For example, the solar control coating of US Patent No. 5,688,585 was provided on face 2 of the IG unit, while the small E coating of US Patent No. 5,376,455 was provided on face 3 of the IG unit. The need for these two separate and different coatings in an IG unit is undesirable due to cost, processing and / or properties.

It is known that there is a need to match the properties (before heat treatment to the value after heat treatment). Glass substrates are often produced in large quantities and cut to size to meet the needs of a given situation, such as a new multiple window and door of an office building, the need for windshields in vehicles, and so on. It is often desirable in such applications that some windows and / or doors are heated (i.e. heat strengthened or bent) while others do not require it. Office buildings often use IG units and / or laminates for safety and / or thermal control. It is desirable that the assemblies and / or laminates that are annealed substantially approximate their unannealed counterparts (e.g., in terms of color, reflectance, and the like, at least on the glass side) for architectural and / or aesthetic reasons. Moreover, it is sometimes desirable that some windows, doors, windshields and so on have a substantially neutral color, preferably similar to the bluish-green side of the spectrum.

It has been possible to obtain suitable properties for systems other than in the cited US Patent No. 5,688,585, but only between two different layer systems, one of which is annealed and the other is not annealed. The need to develop and use two different sandwich systems to obtain the desired properties creates additional manufacturing costs and equipment costs, which is undesirable.

U.S. Patent Nos. 6,014,872 and 5,800,933 (see Example B) disclose a low E annealed system including: glass / TiO2 / Si3N4 / NiCr / Ag / NiCr / Si3N4. But disadvantageously, an annealing of this low E layer system does not provide an equivalent in color to the unbaked (glass side) counterpart. This is because this low E sandwich system has a ΔΕ * (glass side) greater than 4.1 (i.e., for example B, Δa *_G. is 1.49, Δό *₆ is 3.81 and ∆L * (glass side) is not measured; using equation (1) below, the glass side ΔE * must be greater than 4.1, and is likely to be much greater.

PL 205 864 B1

For the above reason, it is clear to the skilled person that there is a need to develop a coating or layering system that can meet both solar control requirements and low E requirements (e.g., so that a separate low E coating does not have to be applied together on different surfaces of this IG team itself). In addition, there is also a need for a low E coating or layered system that substantially matches in color and / or reflection (when viewed with the naked eye from the glass side) of its unheated counterpart. In other words, there is a need for a suitable coating or layering system.

It is an object of the present invention to provide a low E-coating or layered system that has good color stability after annealing.

Another object of the present invention is to provide a low E coating or layered system.

Another object of the present invention is to provide a coating or layered system with improved IR reflectance properties compared to the coating systems described in US Patent No. 5,688,585.

Another object of the present invention is to provide better control of solar properties (e.g., low shading coefficient and / or visible transmittance) compared to those disclosed in US Patent 5,376,455.

Yet another object of the present invention is to provide a coating or layered system that, after heat treatment, is substantially equal to its untreated counterpart.

It has surprisingly been found that silver of substantial thicknesses can be used while producing a color stable during heat treatment (e.g., annealing, bending, or strengthening by annealing). The layered systems of the invention may be used, for example, with IG units, vehicle windows, and windshields.

A coated article comprising a layer system applied to the glass substrate (1), the layer system comprising, facing outward from the glass substrate in question:

a) a first dielectric layer (3) containing silicon nitride with a thickness of (300-380) -10^-10 m;

b) a first layer (5) containing Ni or NiCr with a thickness (20-150) -10^-10 m;

c) an infrared reflecting layer (7) comprising silver with a thickness of (40-120) -10^- m;

d) a second layer (9) comprising Ni or NiCr; and

e) a second dielectric layer (11) containing silicon nitride with a thickness of (400-500) -10^- m; according to the invention is characterized in that

(f) the coated glass substrate has a ΔE *, glass side of no more than 2.5 after heat treatment or by heat treatment; and

g) the second layer (9), comprising Ni or NiCr, has a thickness (20-150) -10^- m;

Preferably, the layer system applied to the glass substrate has a glass side ΔE * value of no greater than 2.0 after heat treatment or heat treatment, said coated article having negative both a * G and b * G color coordinates for both before heat treatment and after heat treatment of the coated product.

Preferably, the coated glass substrate has a Δa * value_G., representing an absolute value on the glass side of not more than 1.0 after heat treatment or by heat treatment.

Preferably, the coated glass substrate has a Δa * value_G., which is the absolute value on the glass side, of not more than 0.8 after heat treatment or by heat treatment.

Preferably, said coated article has a hemispherical emissivity Eh of not more than 0.25 both before and after heat treatment.

Preferably, said coated article has a hemispherical emissivity Eh of no greater than 0.20 both before and after heat treatment.

Preferably, said coated article has a sheet resistance value Rs of no more than 20 ohms / square before heat treatment.

Preferably, said coated article has a sheet resistance Rs of no more than 15 ohms / square both before and after heat treatment.

Preferably, said coated article has a sheet resistance Rs not greater than 12 ohms / square both before and after heat treatment.

Preferably, said layer system comprises the following layers with the following thicknesses:

the first layer (3) comprising silicon nitride with a thickness of (320-360) -10^-10 m;

The first layer (5) containing Ni or NiCr, with a thickness of (20 - 90) -10^-10 m; a layer (7) of silver, with a thickness of (60-80) -10^-10 m; a second layer (9) containing Ni or NiCr, with a thickness (20 - 90) -10^-10 m; a second layer (11) containing silicon nitride with a thickness of (420-480) -10^-10 m;

Preferably, said coated article has a semicircular emissivity Eh of no more than 0.25 before heat treatment and a sheet resistance Rs of no more than 20 ohms / square before heat treatment.

The use of a coated article as defined above according to the invention is characterized in that the article is used as the glazing of an IG window unit.

An IG insulating glass assembly comprising first substrates (1, 21) and a second glass substrate (23) joined by respective closest peripheral edges to form an insulating area (30) therebetween, a layered arrangement applied to one of said glass substrates in the vicinity of said insulating area, wherein said monolithic assembly arrangement comprises, facing outward from said glass substrate:

a) a first dielectric layer (3) containing silicon nitride with a thickness of (300-380) -10^-10 m;

b) a first layer (5) containing Ni or NiCr with a thickness (20-150) -10^-10 m;

c) an infrared reflecting layer (7) comprising silver with a thickness of (40-120) -10^-10 m;

d) a second layer (9) comprising Ni or NiCr; and

e) a second dielectric layer (11) containing silicon nitride with a thickness of (400-500) -10^-10 m; according to the invention is characterized in that

(f) a monolithic assembly exhibits an external or external ΔE * value of not more than 2.5 after or after heat treatment, and

g) the second layer (9), comprising Ni or NiCr, has a thickness (20-150) -10^-10 m;

Preferably, said monolithic unit has an outer or outer ∆E * value of no greater than 2.0 after annealing or annealing, said IG unit having both a * G and b * G negative values.

Preferably, said monolithic assembly has an outer or outer ∆E * value of no more than 1.5 after annealing or annealing.

An embodiment of the invention relates to a coated article comprising a substrate; a layered system applied to a substrate, said layering comprising, on the glass side towards the outside, a first layer comprising silicon nitride, a first layer comprising Ni or NiCr, an IR reflecting metal layer, a second layer comprising Ni or NiCr, and a second layer comprising nitride silicon; each of said first and second Ni or NiCr inclusive layers having a thickness of at least 20-10^-10 m; and wherein said coated article has prior to heat treatment a hemispherical emissivity (Eh) of no greater than 0.25, a sheet resistance Rs to heat treatment of no greater than 20 ohms / square, and has a value of ΔE * after heat treatment or heat treatment (reflectance coefficient) from the glass side) not more than 2.5.

The coated article of the present invention is prepared by a method that comprises applying a layer system to a glass substrate, the layer system including an infrared (IR) reflecting metal layer interposed between a first and a second dielectric layer, the glass substrate having an array deposited thereon prior to heat treatment. the layered sheet has a sheet resistance Rs of no greater than 20 ohms / square; and heat treating the substrate with the layered system applied thereto, wherein as a result of said heat treatment, the substrate with the layered system thereon has a ∆E * (glass side reflectance) value of not more than 2.5.

The invention is described below with respect to some variants thereof, which are illustrated in the following drawings, wherein:

Figure 1 is a partial sectional side view of a variant of the sandwich system according to the invention.

Figure 2 is a partial sectional side view of an IG unit according to the present invention in which the sandwich system according to Figure 1 may be used.

Certain embodiments of this invention provide a coating or layering system that can be used for applications such as vehicle window IGs, vehicle windshields, and other suitable applications. Certain embodiments of the invention provide a sandwich system that has excellent color fastness (i.e., a low ΔE * value and / or a low Δa * value; the letter Δ denotes a change due to heat treatment) (e.g., annealing, bending or heat strengthening) both monolithically. and for dual-glazing environments such as IG units or windshields. Such heat treatments often require heating the coated substrate to temperature

Above 593 ° C (1100 ° F) and up to 788 ° C (1450 ° F) [more preferably from about 593 ° C (1100 ° F) to about 649 ° C (1200 ° F)] for the time required to obtain the final result (e.g. annealing, bending and / or strengthening by annealing). Some embodiments of the present invention combine both (i) color stability during annealing and (ii) the use of a silver layer for IR selective reflection. Certain embodiments of the present invention combine (i) and (ii) with a color (iii) in the blue-green quadrant (i.e., third quadrant) of the color spectrum when applied to a transparent and / or green glass substrate. Certain embodiments of the present invention combine features (i), (ii) and (iii) with low emissivity properties (iv).

Figure 1 is a side sectional view of a coated article according to an embodiment of this invention. Coated article comprises a substrate 1 (e.g., a transparent, green, brown, gray, blue, or cyan glass substrate from about 1.0 to 12.0 mm thick), a first dielectric layer 3 [e.g., a nitride layer silicon (Si3N4) or containing silicon nitride (e.g., Si3N4), titanium dioxide, titanium nitride, zirconium oxide, zirconium nitride, tin oxide, silicon oxide, silicon dioxide, silicon oxinitride, or zirconium oxide], nickel (Ni) or nickel (NiCr) including layer 5 (other oxidation resistant materials can be used in place of Ni or NiCr in alternative embodiments of the invention), an infrared reflecting silver (Ag) layer containing layer 7, nickel (Ni) or nickel-chromium (NiCr) layer 9 (other oxidation resistant materials may be used instead of Ni or NiCr in alternative embodiments of this invention) and a second dielectric layer 11 (e.g. silicon nitride or containing silicon nitride (e.g. Si3N4); titanium dioxide, titanium nitride, zirconium nitride, zirconium oxide, tin oxide, silicon oxide, silicon dioxide, silicon oxinitride or zirconium oxide). Different or different layers below or above the above-described coating system may also be used. Thus, when the layer system is "on or" based on substrate 1 (directly or indirectly), other layers may be used therebetween. Thus, for example, the layer system of Fig. 1 can be considered a "on substrate 1" system even when other layers are present in between.

The IR reflecting IR layer 7 is preferably metallic Ag, although slight oxidation may occur thereon. The same applies to the 5 or 9 Ni or NiCr layers. Thus, in certain preferred embodiments of this invention, layers 5, 7, and 9 are oxidized to no more than about 25%, more preferably to no more than about 10%, and most preferably to no more than 1%. In certain preferred embodiments of this invention, layers 5 and / or 9 are non-nitrided layers and layers of unoxidized nickel or nickel alloy (for example, nickelochrome containing 80/20 wt% nickelochrome). An exemplary apparatus that may be used to form a layer of the coating systems of the present invention is a conventional sputter coating system such as the G49 Flat Glass Large Area Sputter Coater from Airco, Inc.

In embodiments of this invention where layers 3 and 11 include Si3N4, the Si-containing target used to form these layers may be doped in the range of 6-20% by weight of aluminum or stainless steel (e.g. SS # 316) with about that amount. then located in the layers thus formed. In addition, while layers 5 and 9, which may be metal nickel, nickelchrome, preferably consisting essentially of about 80-90 wt% Ni and 10-20 wt% Cr, may be used in certain preferred embodiments of this invention. Other metals or alloys may also be used in alternatives, for example, an alloy or alloys containing 10% by weight or more of Ni. Furthermore, while some other IR reflecting IR metals may be used as layer 7, such as gold or platinum in certain embodiments of this invention, layer 7 comprises substantially metallic silver in certain embodiments of this invention. For example, layers 5 and 9 contain not only SS-316, which contains substantially 10% Ni and 90% other components, mainly Fe and Cr, but also Haynes alloy 214, which gives essentially the following nominal composition:

<td>element</td><td>% by weight</td>

<td> 1</td><td> 2</td>

<td>Ni</td><td> 75,45</td>

<td>Fe</td><td> 4,00</td>

PL 205 864 B1 cont. table

<td> 1</td><td> 2</td>

<td>Cr</td><td> 16,00</td>

<td>C.</td><td> 0,04</td>

<td>Al</td><td> 4,50</td>

<td>Y</td><td> 0,01</td>

In other embodiments of this invention, coated articles may be the following: glass / silicon nitride / silver / nichrome / silver / nichrome / silicon nitride. In such embodiments of the present invention, the respective layers of silicon nitride, nichrome and / or silver may have thicknesses that approximate the thicknesses of the same materials given in the other embodiments of this invention. Alternatively, certain layers may be thinner, for example glass / silicon nitride (40-10^-10 m) / nichrome (35-10^-10 m) / silver (50-10^-10 m) / nichrome (30-10^-10 m) / silver (50-10^-10 m)

-10 -10 / nichrome (35-10^-10 m) / silicon nitride (261-10^-10 m). It is believed that these dual silver embodiments of the present invention may provide improved color fastness and / or chemical resistance as compared to the embodiment of Fig. 1 described herein. This variant may in some cases be even more durable than the variant according to Fig. 1.

Figure 2 shows a coating or layer system 22 according to Figure 1 (i.e. according to the double silver embodiment mentioned) applied to face # 2 of an IG window assembly. In order to distinguish the "inner unit from" the outer unit, the sun 19 is shown schematically on the outside. The IG unit comprises an outer glass pane or sheet 21 and an inner glass pane or sheet 23. The two glass substrates (e.g., 2 to 12 mm thick float glass) are joined at the side edges with a conventional sealant 25 and contain a common desiccant strip 27. These panes are then placed in a frame supporting a simple window or door (shown in part as schematic). By sealing the side edges of the glass panes and replacing the air in the insulating area (or chamber) with a gas such as argon, a typical IG unit with good insulating properties is formed. Optionally, insulating region 30 may be under pressure less than atmospheric pressure in certain alternative embodiments, although of course this is not always necessary. The inner wall 24 or 26 (or both) may include a sandwich arrangement (see Fig. 1) of the present invention. In the embodiment shown in Fig. 2, the inner wall 24 (i.e. surface 2) of the outer pane 21 carries the sputtering arrangement of Fig. 1 thereon.

Referring to Fig. 1, it should be noted that different layer thicknesses may be used in accordance with one or more of the objects and / or tasks set forth herein, according to certain example embodiments of this invention, but the following thicknesses and materials of the respective layers on the glass substrate 1 are preferred:

TABLE 1 (thicknesses)

<td>Layer</td><td>Favorable range, 1 · 10 '¹⁰ m</td><td>A more favorable range, 1 · 10 '¹⁰</td>

<td>Si₃N₄ (layer 3)</td><td> 300-380</td><td> 320-360</td>

<td>NiCr (layer 5)</td><td> 20-150</td><td> 20-90</td>

<td>Ag (layer 7)</td><td> 40-120</td><td> 60-80</td>

<td>NiCr (layer 9)</td><td> 20-150</td><td> 20-90</td>

<td>Si3N4 (layer 11)</td><td> 400-500</td><td> 420-480</td>

As can be seen from Table 1 above, the top Ni or NiCr layer 9 has a much thicker thickness than in the variants of the aforementioned US Patent 5,376,455. Moreover, the dielectric layers 3 and / or 11 are thinner than in this patent specification. Surprisingly, it is believed that one or more of these changes results in equal or lower ∆Ε * values ​​(described below for certain embodiments of the present invention) (i.e., better durability after heat treatment). One or both of these changes can also be attributed to the improved durability exhibited by some embodiments of the present invention. It has also been found that these variations represent a clear improvement over the patent, as the inventor has found a method of (i) using an Ag layer for IR reflection to obtain a low-E layer system, and at the same time (ii) with good processing stability. heat (i.e. small values ​​of ΔΕ * and / or values ​​of Δα *. This combination of a low E-value system with good heat treatment stability is believed to be novel and inventive.

In certain example embodiments of this invention, heat treatment stability substantially matches the properties of the heat treated or untreated coating or layer system. In other words, in monolithic and / or IG applications, in certain embodiments of this invention, two glass substrates having the same coating system thereon (one heat treated and the other unheat treated when applied) have substantially the same appearance to the naked eye when viewed by the naked eye. the glass side of the article (that is, looking through at least one glass substrate prior to viewing the coating).

In certain embodiments of this invention, it has been found that the match performance (achieved in monolithic applications) may be even better in IG and / or laminate applications.

Thus, in some embodiments of the present invention, matching is achieved in monolithic systems. However, in other embodiments of the present invention, the matching is only achieved when the substrate structure comprises two or more layers of glass, for example an IG unit. The match performance improvement in the IG unit is due to the moderating effect of the inner glass pane 26 (FIG. 2). The light reflected from the inner pane 26 is approximately summed up with the light reflected from the outer pane 21. Thus, the IGU color reflected is the weight average of the colors reflected from the individual panes 21 and 26. Thus, the effect of each pane on the color obtained is proportional to the percentage. the amount of light reflected from each pane and reaching the observer in the viewer. Taking the outside observer's eye into account, the light reflected from the outer pane 21 reaches the observer's eye without disturbance. However, the light reflected from the inner pane 26 must pass through the front pane twice (once before being reflected from the inner pane and once after being reflected) before reaching the same observer's eye. As a result, the amount of light reflected from the inner pane is reduced by the square factor of the transmittance of the outer pane. For this reason, the moderating effect of the inner pane quickly decreases as the visible transmittance of the windshield 21 increases. This decreasing effect may even be increased by the fact that the reflectance of the coated pane 21 tends to increase as transmittance decreases and thus further increases the percentage the light reflected from the windscreen in the light reflected from the IG unit. For example, the coated article described in said Patent Application No. 09 / 455,026 after heat treatment had a visible transmittance of about 70% and a glass side reflectance of about 10%. The transmittance increased to about 75%, while the glass side reflectance of the heat treated article decreased to about 8%. The total external reflectance of the heat treated IG unit was 8% from the windshield, and 8% (reflectance for uncoated glass) * 0.75² = 4.5%. Thus, the light reflected from the inner pane 26 corresponded to 36% of the total external reflectance of the heat treated IG unit. This means that the AE * IGU value of the IG complex will decrease by about 36% compared to the monolithic AE * mono complex. It was found (Patent Application 09 / 455,026, pages 39 and 40) that due to an increase in transmittance of about 5% during heat treatment, the actual moderating effect was even greater (about 55%), ΔE * was measured_mabout_no = 3.95, ΔE *_IGU = 1.76). In contrast, the moderating effect is almost absent for lower transmittance coated products such as in example 2 of the present application. For the heat treated IG unit, the external reflectance from the windshield 21 was 16.51%. The transmittance of the heat treated windshield was 44.91. The total external reflectance for the IG unit shown in Fig. 2 can be calculated to be equal to 16.51% from the windshield 21 and 8% * 0.45² = 1.62% of the inner pane 26. In this case, the light from the inner pane 26 will be only about 9% of the total reflectance of the IG unit and the expected moderating effect on ∆E * will be about 9%. The additional moderating effect related to the increase in transmittance during the heat treatment due to the heat treatment in this case increases very little because the increase in transmittance is very small (T = 0.72%). It follows that achieving comparability of lower transmittance coatings with an IG unit can in practice be achieved with coated windshield 21 in a monolithic state. Thus, in some variants, usually these are variants with a transmittance greater than 60%, the value of ΔE for a monolithic (individual) substrate can be significantly higher than 2.5 and the

Possible results are still obtained in double or multiple glazed products according to the present invention. However, in certain other embodiments of this invention, typically variants with less than 60% transmittance, the ΔE value of the monolithic (individual) substrate may not be significantly greater than 2.5, preferably less than 2.5, to match properties in double or multiple glazing articles according to the present invention. In examples # 1-4, the ΔΕ * values ​​are reduced by 0.5-0.8 points for the higher transmittance samples (samples # 1 and # 3) and by 0.2-0.3 points for the lower transmittance samples (samples # 2 and # 4).

The values ​​of ∆E * and ∆a * are important in determining whether there is complete or substantial matchmaking according to the present invention. Color is described herein by reference to common a *, b * values, which in certain embodiments of this invention are both negative to provide color in the substantially preferred neutral color range narrowing to the cyan quadrant. The term Δa * simply indicates how much the color value of a * changes as a result of the heat treatment.

The term ∆E * (and ∆E) is known in the art and is reported, together with various assay techniques, in ASTM 2244-93 as well as in Hunter et al. al., The Measurement of Appearance, Issue 2, Chapter 9, page 162 et seq. (John Wiley &amp; Sons, 1987). The value of ∆E * (and ∆E) used in the art is a way of correctly expressing the change (or lack thereof) in reflectance and / or transmittance (and thus color) in an article after or due to heat treatment. The ΔE value can be calculated by the "ab method or by the Hunter method (indicated by the index" H). ΔE corresponds to the Hunter Lab L scale, the a, b scale (i.e. L_h, a_h, b_h). Similarly, ΔE * corresponds to the CIE LAB Scale L *, a *, b *. Both scales are useful and equivalent according to the present invention. For example, as reported by Hunter et al in the reference above, a rectangular coordinate scale technique (CIE LAB 1976) known as the L *, a *, b * scale may be used where:

L * stands for the brightness units (CIE 1976) a * stands for the red-green units (CIE 1976) b * stands for the yellow-green units (CIE 1976) and the distance ΔE * between L *₀and*₀ b *₀ and L *₁and*₁b *₁ equals ΔΕ * = [^ L *)² + (Δθ *)² + ^ b *)²]^1/2 (1) in which:

Δυ * = L * 1 - L *_about (2)

Δa * = a *₁ - a *₀ (3)

Δ ^ = b * 1 - b *₀ (4) wherein the subscript "0" is the coating (coated article) before heat treatment and the subscript "1 is the coating (coated article) after heat treatment; and the numbers used (for example, the numbers a *, b *, L *) are numbers calculated by the above-mentioned technique (CIE LAB 1976) of the L *, a *, b * coordinates. Similarly, ΔΕ can be calculated from Equation 1 by replacing a *, b *, L * with Hunter Lab values ​​ah, bh, Lh. Also within the scope of the present invention and quantification of ∆Ε * are the equivalent numbers after converting them by any other technique using the same concept of ∆Ε * given above.

In certain embodiments of this invention, their layered systems on transparent monolithic glass substrates have the following color prior to heat treatment when viewing the coated article (RG%) from the glass side:

Table 2

Color (RG) before heat treatment

<td></td><td>Generally</td><td>Favorable</td>

<td>and*</td><td>0.0 to 5.0</td><td>0.0 to 3.0</td>

<td>b *</td><td>-1.0 to -10.0</td><td>-3.0 to -9.0</td>

After heat treatment, in certain embodiments of this invention, sandwich systems deposited on transparent monolithic glass substrates have the following color characteristics ΔΕ * and Δa * when viewed from the glass (G) side (as opposed to the layer side) of the coated article.

PL 205 864 B1

Table 3

Color properties (AE * g &amp; Aa * G) after heat treatment

<td></td><td>Generally</td><td>Favorable</td>

<td>AE * g =</td><td> &lt;= 3,0</td><td>&lt;= 2.5 (or &lt;= 2.0)</td>

<td>сa * G =</td><td> &lt;= 1,0</td><td> &lt;= 0,8</td>

As set forth in Table 3 above, coated articles according to certain embodiments of this invention have a ∆E * (glass side) of no greater than 3.0, preferably no greater than 2.5, and more preferably no greater than 2.0; and have a ∆a * (glass side) of no greater than about 1.0, more preferably no greater than 0.8. Matching properties can be obtained when either or both of these values ​​are obtained. It has been found that the b * values ​​are not as important as the a * values ​​because changes in a * are more noticeable to the naked eye than changes in b * in some cases.

Examples 1-4

The following 4 examples of coated articles (each article was annealed and then heat treated) were made in accordance with certain embodiments of this invention. For each of these four examples, the following layer system was used: glass / Si3N4 / NiCr / Ag / NiCr / Si3N4 (see, for example, Fig. 1). For each of these examples, the substrate was a substantially clear soda lime glass 5.6-6.0 mm thick. In these 4 examples the coater / method kits for the 4 examples were as follows:

Examples 1-2 were made using a G-49 Flat Glass Large Area Sputter Coating Machine from Airco, Inc. at a line speed of 170 IPM (pulses per minute) using the following 3-5 zones; "* Means Al content about 10% and gas flow (e.g. Ar, N2) was measured in cm³. All of Examples 1-2 were C-Mag wheels, with the exception of the wheels used to apply the Ag and NiCr layers (targets 19-21) were flat. Moreover, in Examples 1-2, a first layer of silicon nitride was applied in coating zone 3 using alternating current, NiCr and Ag layers were applied in coating zone 4 using direct current, and a surface layer of silicon nitride was applied in coating zone 5 by means of an alternating current. The sputter coating was performed by the sputtering method of Examples 1-2.

Table 4

Coater and conditions of the coating methods for Examples 1-2

Example # 1.

<td>Cathode</td><td>Shield</td><td>Power, kW</td><td>Voltage, V</td><td>Pressure, (• 0.13 Pa)</td><td>Ar flow</td><td>N2 flow</td>

<td> #13</td><td>Si / Al *</td><td> 27,7</td><td> 444</td><td> 2,5</td><td> 551</td><td> 1489</td>

<td> #14</td><td>Si / Al *</td><td> 22,7</td><td> 451</td><td> 2,5</td><td> 551</td><td> 1489</td>

<td> #15</td><td>Si / Al *</td><td> 27,7</td><td> 459</td><td> 2,5</td><td> 551</td><td> 1489</td>

<td> #16</td><td>Si / Al *</td><td> 27,7</td><td> 481</td><td> 2,5</td><td> 551</td><td> 1489</td>

<td> #17</td><td>Si / Al *</td><td> 27,7</td><td> 453</td><td> 2,5</td><td> 551</td><td> 1489</td>

<td> #18</td><td>Si / Al *</td><td> 27,7</td><td> 480</td><td> 2,5</td><td> 551</td><td> 1489</td>

<td> #19</td><td>NiCr</td><td> 10,5</td><td>on</td><td> 2,7</td><td> 1110</td><td> 0</td>

<td> #20</td><td>Ag</td><td> 4,15</td><td>on</td><td> 2,7</td><td> 1110</td><td> 0</td>

<td> #21</td><td>NiCr</td><td> 10,5</td><td>on</td><td> 2,7</td><td> 1110</td><td> 0</td>

<td> #22</td><td>Si / Al *</td><td> 33,6</td><td> 465</td><td> 2,5</td><td> 541</td><td> 1336</td>

<td> #23</td><td>Si / Al *</td><td> 33,6</td><td> 462</td><td> 2,5</td><td> 541</td><td> 1336</td>

<td> #24</td><td>Si / Al *</td><td> 33,6</td><td> 452</td><td> 2,5</td><td> 541</td><td> 1336</td>

<td> #25</td><td>Si / Al *</td><td> 33,6</td><td> 456</td><td> 2,5</td><td> 541</td><td> 1336</td>

<td> #26</td><td>Si / Al *</td><td> 33,6</td><td> 478</td><td> 2,5</td><td> 541</td><td> 1336</td>

<td> #27</td><td>Si / Al *</td><td> 33,6</td><td> 463</td><td> 2,5</td><td> 541</td><td> 1336</td>

PL 205 864 B1

Example # 2.

<td>Cathode</td><td>Shield</td><td>Power, kW</td><td>Voltage, V</td><td>Pressure, (• 0.13 Pa)</td><td>Ar flow</td><td>N2 flow</td>

<td> #13</td><td>Si / Al *</td><td> 27,7</td><td> 444</td><td> 2,5</td><td> 551</td><td> 1489</td>

<td> #14</td><td>Si / Al *</td><td> 22,7</td><td> 451</td><td> 2,5</td><td> 551</td><td> 1489</td>

<td> #15</td><td>Si / Al *</td><td> 27,7</td><td> 459</td><td> 2,5</td><td> 551</td><td> 1489</td>

<td> #16</td><td>Si / Al *</td><td> 27,7</td><td> 481</td><td> 2,5</td><td> 551</td><td> 1489</td>

<td> #17</td><td>Si / Al *</td><td> 27,7</td><td> 453</td><td> 2,5</td><td> 551</td><td> 1489</td>

<td> #18</td><td>Si / Al *</td><td> 27,7</td><td> 480</td><td> 2,5</td><td> 551</td><td> 1489</td>

<td> #19</td><td>NiCr</td><td> 17,0</td><td>on</td><td> 2,7</td><td> 1110</td><td> 0</td>

<td> #20</td><td>Ag</td><td> 4,15</td><td>on</td><td> 2,7</td><td> 1110</td><td> 0</td>

<td> #21</td><td>NiCr</td><td> 10,5</td><td>on</td><td> 2,7</td><td> 1110</td><td> 0</td>

<td> #22</td><td>Si / Al *</td><td> 33,6</td><td> 465</td><td> 2,5</td><td> 541</td><td> 1336</td>

<td> #23</td><td>Si / Al *</td><td> 33,6</td><td> 462</td><td> 2,5</td><td> 541</td><td> 1336</td>

<td> #24</td><td>Si / Al *</td><td> 33,6</td><td> 452</td><td> 2,5</td><td> 541</td><td> 1336</td>

<td> #25</td><td>Si / Al *</td><td> 33,6</td><td> 456</td><td> 2,5</td><td> 541</td><td> 1336</td>

<td> #26</td><td>Si / Al *</td><td> 33,6</td><td> 478</td><td> 2,5</td><td> 541</td><td> 1336</td>

<td> #27</td><td>Si / Al *</td><td> 33,6</td><td> 463</td><td> 2, 5</td><td> 541</td><td> 1336</td>

Examples 3-4 were prepared on a Leybold TG-1 sputter coater at a line speed of 4 m / min; where again "* is the content of the aluminum target (Al) about 10% and the gas flow (e.g. Ar, N2) is measured in cm³. Wheels 34, 42, 55, and 61 were 2 x C-Mag, dials 44, 51, and 53 were flat, and dial 65 was a Twin-Mag. The pressure was converted to Pa. The coater was set up and operated as in the sputtering examples 3-4.

Table 5

Coater and conditions of the coating methods for Examples 3-4

Example # 3.

<td>Cathode</td><td>Shield</td><td>Power, kW</td><td>Voltage, V</td><td>Pressure, (• 0.13 Pa)</td><td>Flow Ar</td><td>Flow N2</td><td>Frequency (kHz)</td>

<td> #34</td><td>Si / Al *</td><td> 64,5</td><td> 395</td><td> 3,6</td><td> 203</td><td> 452</td><td> 28,1</td>

<td> #42</td><td>Si / Al *</td><td> 64,5</td><td> 341</td><td> 3,1</td><td> 200</td><td> 452</td><td> 28,7</td>

<td> #44</td><td>NiCr</td><td> 12,5</td><td> 385</td><td> 2,5</td><td> 220</td><td> 0</td><td>DC</td>

<td> #51</td><td>Ag</td><td> 4,55</td><td> 466</td><td> 2,3</td><td> 3,15</td><td> 0</td><td>DC</td>

<td> #53</td><td>NiCr</td><td> 12,5</td><td> 421</td><td> 2,4</td><td> 220</td><td> 0</td><td>DC</td>

<td> #55</td><td>Si / Al *</td><td> 62</td><td> 473</td><td> 3,5</td><td> 200</td><td> 447</td><td> 27,8</td>

<td> #61</td><td>Si / Al *</td><td> 64</td><td> 374</td><td> 4,5</td><td> 200</td><td> 447</td><td> 28,1</td>

<td> #65</td><td>Si / Al *</td><td> 62</td><td> 326</td><td> 3,5</td><td> 200</td><td> 377</td><td> 27,8</td>

Example # 4

<td>Cathode</td><td>Shield</td><td>Power, kW</td><td>Voltage, V</td><td>Pressure, (• 0.13 Pa)</td><td>Flow Ar</td><td>Flow N2</td><td>Frequency (kHz)</td>

<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td>

<td> #34</td><td>Si / Al *</td><td> 64,5</td><td> 395</td><td> 3,6</td><td> 203</td><td> 452</td><td> 28,1</td>

<td> #42</td><td>Si / Al *</td><td> 64,5</td><td> 341</td><td> 3,1</td><td> 200</td><td> 452</td><td> 28,7</td>

PL 205 864 B1 cont. example 4

<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td>

<td> #44</td><td>NiCr</td><td> 19</td><td> 385</td><td> 2,5</td><td> 220</td><td> 0</td><td>DC</td>

<td> #51</td><td>Ag</td><td> 4,55</td><td> 466</td><td> 2,3</td><td> 3,15</td><td> 0</td><td>DC</td>

<td> #53</td><td>NiCr</td><td> 12,5</td><td> 421</td><td> 2,4</td><td> 220</td><td> 0</td><td>DC</td>

<td> #55</td><td>Si / Al *</td><td> 62</td><td> 473</td><td> 3,5</td><td> 200</td><td> 447</td><td> 27,8</td>

<td> #61</td><td>Si / Al *</td><td> 64</td><td> 374</td><td> 4,5</td><td> 200</td><td> 447</td><td> 28,1</td>

<td> #65</td><td>Si / Al *</td><td> 62</td><td> 326</td><td> 3,5</td><td> 200</td><td> 377</td><td> 27,8</td>

After spraying onto a glass substrate as above, it was tested in Examples 1-4 and found to have the following monolithic properties (not IG unit) when the monolithic product was heat treated in a conventional soaking oven at about 685 ° C (1265 ° C). F) in three-minute cycles and cooled to room temperature (note: a * and b * color coordinates are in accordance with the CIE LAB 1976, 111. CIE-C 2 ° observer technique).

Table 6

Properties for examples 1-4 (monolithic)

Example # 1

<td>Value / measurement</td><td>Before heat treatment</td><td>After heat treatment</td>

<td>Transmission (YOU)%</td><td> 56,36</td><td> 59,21</td>

<td>L * t</td><td> 79,82</td><td> 81,41</td>

<td>a * T</td><td> -3,14</td><td> -3,27</td>

<td>b * T</td><td> -3,93</td><td> -4,68</td>

<td>glass side reflectance (G): RgY (%)</td><td> 12,68</td><td> 11,52</td>

<td>1 * LG</td><td> 42,27</td><td> 40,44</td>

<td>a * G</td><td> -1,95</td><td> -1,53</td>

<td>b * G</td><td> -6,72</td><td> -7,06</td>

<td>ΔΕ * (this is from the glass side (G))</td><td></td><td> 1,9</td>

<td>on*_G. (the absolute value)</td><td></td><td> 0,42</td>

<td>film / coating side reflectance (F): RfY (%)</td><td> 2,71</td><td> 2,78</td>

<td>L * f</td><td> 18,86</td><td> 19,12</td>

<td>a * F</td><td> 11,58</td><td> 12,73</td>

<td>b * F</td><td> 0,28</td><td> -1,59</td>

<td>R_s (sheet resistance, ohm / square]</td><td> 12,0</td><td> 10,8</td>

<td>total solar coordinate T,%</td><td> 38</td><td></td>

<td>solar coordinate Rout</td><td> 16</td><td></td>

<td>U value</td><td> 21,46*10·^-5 kWh (0.74 BTU)</td><td></td>

<td>S value of U</td><td> 20,01*10'^-5 kWh (0.69 BTU)</td><td></td>

<td>shading coefficient (SC)</td><td> 0,54</td><td></td>

<td>SHGC</td><td> 0,463</td><td></td>

<td>heat gain</td><td> 117</td><td></td>

<td>Eh (hemispherical emissivity)</td><td> 0,176</td><td></td>

PL 205 864 B1

Example # 2

<td>Value / measurement</td><td>Before heat treatment</td><td>After heat treatment</td>

<td>T ransmission (YOU)%</td><td> 44,19</td><td> 44,91</td>

<td>L * t</td><td> 72,39</td><td> 72,83</td>

<td>a * T</td><td> -3,68</td><td> -3,2</td>

<td>b * T</td><td> -5,82</td><td> -6,3</td>

<td>glass side reflectance (G): RgY (%)</td><td> 17,05</td><td> 16,51</td>

<td>1 * LG</td><td> 48, 33</td><td> 47,64</td>

<td>a * G</td><td> -1,26</td><td> -1,37</td>

<td>b * G</td><td> -3,09</td><td> -3,37</td>

<td>ΔE * (this is from the glass side (G))</td><td></td><td> 0,8</td>

<td>Δa *_G. (the absolute value)</td><td></td><td> 0,11</td>

<td>film / coating side reflectance (F): RfY (%)</td><td> 4,6</td><td> 4,63</td>

<td>L * f</td><td> 25,55</td><td> 25,66</td>

<td>a * F</td><td> 15,09</td><td> 13,7</td>

<td>b * F</td><td> 11,73</td><td> 14,62</td>

<td>Rs (sheet resistance, ohm / square)</td><td> 11,3</td><td> 10,6</td>

<td>total solar coordinate T,%</td><td> 29</td><td></td>

<td>solar coordinate Rout</td><td> 20</td><td></td>

<td>U value</td><td> 21,46*10'^-5 kWh (0.74 BTU)</td><td></td>

<td>S value of U</td><td> 20,3*10 ⁵ kWh (0.70 BTU)</td><td></td>

<td>shading coefficient (SC)</td><td> 0,45</td><td></td>

<td>SHGC</td><td> 0, 385</td><td></td>

<td>heat gain</td><td> 99</td><td></td>

<td>E._h (hemispherical emissivity)</td><td> 0,169</td><td></td>

Example # 3

<td>Value / measurement</td><td>Before heat treatment</td><td>After heat treatment</td>

<td> 1</td><td> 2</td><td> 3</td>

<td>T ransmission (YOU)%</td><td> 56,98</td><td> 58,71</td>

<td>L * t</td><td> 80,17</td><td> 81,13</td>

<td>a * T</td><td> -2,82</td><td> -2,82</td>

<td>b * T</td><td> -2,23</td><td> -2,73</td>

<td>glass side reflectance (G): RgY (%)</td><td> 15,27</td><td> 14,21</td>

<td>1 * LG</td><td> 46</td><td> 44,53</td>

<td>a * G</td><td> -2,17</td><td> -1,81</td>

<td>b * G</td><td> -8,63</td><td> -8,95</td>

<td>ΔΕ * (glass side (G))</td><td></td><td> 1,5</td>

PL 205 864 B1 cont. example 3

<td> 1</td><td> 2</td><td> 3</td>

<td>сa * G (absolute value)</td><td></td><td> 0,36</td>

<td>film / coating side reflectance (F): RfY (%)</td><td> 2,19</td><td> 2,32</td>

<td>L * f</td><td> 16,47</td><td> 17,1</td>

<td>a * F</td><td> 13,68</td><td> 13,76</td>

<td>b * F</td><td> -14,48</td><td> -13,25</td>

<td>Rs (sheet resistance, ohm / square)</td><td> 11,5</td><td> 10,5</td>

<td>total solar coordinate T,%</td><td> 39</td><td></td>

<td>solar coordinate R._ouvol</td><td> 19</td><td></td>

<td>U value</td><td> 21,46*10^-5 kWh (0.74 BTU)</td><td></td>

<td>S value of U</td><td>19.72d0 '⁵ kWh (0.68 BTU)</td><td></td>

<td>shading coefficient (SC)</td><td> 0,55</td><td></td>

<td>SHGC</td><td> 0,47</td><td></td>

<td>heat gain</td><td> 119</td><td></td>

<td>Eh (hemispherical emissivity)</td><td> 0,170</td><td></td>

Example # 4

<td>Value / measurement</td><td>Before heat treatment</td><td>After heat treatment</td>

<td> 1</td><td> 2</td><td> 3</td>

<td>T ransmission (YOU)%</td><td> 50,08</td><td> 51,08</td>

<td>L * t</td><td> 76,12</td><td> 76,73</td>

<td>a * T</td><td> -3,61</td><td> -2,88</td>

<td>b * T</td><td> -5,02</td><td> -4,66</td>

<td>glass side reflectance (G): RgY (%)</td><td> 14,62</td><td> 13,82</td>

<td>1 * LG</td><td> 45,1</td><td> 43,98</td>

<td>a * G</td><td> -0,59</td><td> -1,36</td>

<td>b * G</td><td> -4,33</td><td> -4,52</td>

<td>ΔΞ * (this is from the glass side (G))</td><td></td><td> 1,4</td>

<td>on*_G. (the absolute value)</td><td></td><td> 0,77</td>

<td>film / coating side reflectance (F): RfY (%)</td><td> 3,83</td><td> 3,67</td>

<td>L * f</td><td> 23,09</td><td> 22,56</td>

<td>a * F</td><td> 15,93</td><td> 11,79</td>

<td>b * F</td><td> 3,51</td><td> 10,42</td>

<td>R_s (sheet resistance, ohm / square)</td><td> 11,0</td><td> 9,1</td>

<td>total solar coordinate T,%</td><td> 33</td><td></td>

<td>solar coordinate Rout</td><td> 19</td><td></td>

PL 205 864 B1 cont. example 4

<td> 1</td><td> 2</td><td> 3</td>

<td>U value</td><td> 21,17^10⁵ kWh (0.73 BTU)</td><td></td>

<td>S value of U</td><td> 20,0210⁵ kWh (0.69 BTU) 0.69</td><td></td>

<td>shading coefficient (SC)</td><td> 0,49</td><td></td>

<td>SHGC</td><td> 0,42</td><td></td>

<td>heat gain</td><td> 107</td><td></td>

<td>Eh (hemispherical emissivity)</td><td> 0,164</td><td></td>

Each of Examples 1-4 was also found to produce chemically and mechanically stable products under the conditions outlined above both before and after heat treatment.

It can be seen from the above that each of Examples 1-4 provides products with comparable properties because, when viewed from the glass side (G) of the respective products, the ΔE * value was not greater than 2.5, preferably not greater than 2.0, while when Δa *_G. (its absolute value as used herein) was not greater than 1.0, and preferably not greater than 0.8. These values ​​(i.e., ∆E * and ∆a *) are important when measuring from the glass side (G) of the coated article as opposed to the film side (F) because for most applications the articles are viewed predominantly from their glass side. As regards, for example, equivalent properties, Example 3 gave the following values ​​(glass side (G)).

<td>L * (before HT): 46</td><td>L * (after HT): 44.53</td><td>AL * = 1.47</td>

<td>a * (before HT): -2.17;</td><td>a * (after HT): -1.81</td><td>Aa * = 0.36</td>

<td>b * (before HT): - 8.63</td><td>b * (after HT): -8.95</td><td>Ab * = 0.32</td>

2 2 1/2

So, using the equation ΔE * = [(AL *) + (Aa *) + (Ab *)] (this is equation (1) above), we can denote that [(1.47)² + (0, 36)² + (0,32)²]^1/2 = (2,3929)^1/2 = 1.5 = ΔE * (glass side). This relatively low glass side reflectance value ΔE * indicates an equivalent property (before heat treatment compared to heat treated properties).

Each monolithic article of the above examples also had low emissivity properties, as seen in each of the above examples, and had a hemispherical emissivity (Eh) of no more than 0.25, more preferably no more than 0.20, before and / or after the heat treatment. (HT). Thicker Ag layers may also be used which will result in lower sheet emissivity and / or drag than the values ​​reported herein, in accordance with certain embodiments of this invention. You can compare these low emissivity values ​​of 0.48 with the values ​​up to 0.73 in US Patent 5,688,585. Each of Examples 1-4 given above also had low sheet resistance Rs values ​​of no more than 20 ohms / square, preferably no more than 15 ohms / square, and more preferably no more than about 12 ohms / square (before and / or after HT). Again, compare these low sheet resistance (Rs) values ​​with the sheet resistance values ​​of 89-269 ohms / square according to US Patent 5,688,585. Accordingly, it can be seen that the articles of Examples 1-4 present indeed have low E properties, while at the same time they may surprisingly substantially achieve properties that match the properties before or after the heat treatment.

Coated monolithic articles according to certain embodiments of this invention preferably have visible transmittance (TY,%) of no greater than about 60%, preferably from about 40-60% before HT, and most preferably from about 48 to 58% before heat treatment. Monolithic coated articles according to certain embodiments of this invention preferably have visible transmittance (TY,%) from about 10 to about 65% post HT, more preferably from about 40 to 60% post HT. Similarly, coated articles according to certain embodiments of this invention preferably have a shading factor (SC) of no greater than about 0.65 (before and / or after HT), more preferably from about 0.40 to about 0.60 before and / or after HT. . Additionally, monolithic coated articles according to certain embodiments of this invention preferably have a glass side reflectance (RG Y,%) value of at least 11%, more preferably from 12 to 20% before HT and from about 11 to about 19% after HT.

PL 205 864 B1

It will also be seen that, according to certain preferred embodiments of this invention, the monolithic coated articles have an? * G value from about 0.0 to about -5.0, more preferably from about 0.0 to 2.5, prior to heat treatment and / or after. heat treatment. Thereby, coated articles according to certain embodiments of this invention have a desirable neutral or bluish green color, particularly when b * G is also negative.

The above-mentioned properties can be measured on transparent float glass with a nominal substrate thickness of about 6 mm or on any other substrate of any other suitable thickness from 1 to 12 mm. In addition, it should be noted that the units of Examples 1-4 can also be used in an IG unit, windshields, windows, and the like.

Each of the above-mentioned examples 1-4 HT was then used in an IG unit as shown in fg.2 (for example, where a chamber or insulation area between two panes can be filled with gas (Ar)), measurements for these IG applications are given below in tables 7 and 8.

Table 7

Product properties for examples 1-4 (IG or IGU) (IG unit in Fig. 2, pane 26 - uncoated clear glass, thickness 6 mm)

Example # 1

<td>Value / measurement</td><td>Before heating up</td><td>After soaking</td>

<td>T ransmission (YOU)%</td><td> 50,17</td><td> 52,52</td>

<td>L * t</td><td> 76,17</td><td> 77,59</td>

<td>a * T</td><td> -4,54</td><td> -4,67</td>

<td>b * T</td><td> -3,54</td><td> -4,08</td>

<td>external reflectance (out): R._ouyou (%)</td><td> 15,15</td><td> 14,45</td>

<td> 1 * ^L. out</td><td> 45,84</td><td> 44,87</td>

<td>about*^and*out</td><td> -2,44</td><td> -1,76</td>

<td>b * out</td><td> -6,66</td><td> -7,15</td>

<td>AE * out (glass side (out))</td><td></td><td> 1,34</td>

<td>Aa * out (absolute value)</td><td></td><td> 0,68</td>

<td>reflection coefficient film / coating side (internal): RinY (%)</td><td> 9,81</td><td> 9,82</td>

<td>L * In</td><td> 37,51</td><td> 37,51</td>

<td>a * In</td><td> 3,01</td><td> 3,46</td>

<td>b * In</td><td> -0,48</td><td> -1,84</td>

<td>total solar coordinate T,%</td><td> 31</td><td></td>

<td>solar coordinate Rout</td><td> 18</td><td></td>

<td>U value</td><td> 9,86 • 10'⁵ kWh (0.34 BTU)</td><td></td>

<td>S value of U</td><td> 10,73 • 10'⁵ kWh (0.37 BTU)</td><td></td>

<td>shading coefficient (SC)</td><td> 0,43</td><td></td>

<td>TY /% / SC</td><td> 116,7</td><td></td>

<td>SHGC</td><td> 0,39</td><td></td>

<td>heat gain</td><td> 96</td><td></td>

PL 205 864 B1

Example # 2

<td>value / measurement</td><td>before heat treatment</td><td>after heat treatment</td>

<td>T ransmission (YOU)%</td><td> 39,47</td><td> 40,16</td>

<td>L * t</td><td> 76,09</td><td> 76,59</td>

<td>a * T</td><td> -4,95</td><td> -4,51</td>

<td>b * T</td><td> -4,97</td><td> -5,45</td>

<td>external reflectance (out): RoutY (%)</td><td> 18,86</td><td> 18,48</td>

<td>L * out</td><td> 50,53</td><td> 50,07</td>

<td>^and*out</td><td> -1,82</td><td> -1,92</td>

<td>b * out</td><td> -3,57</td><td> -3,96</td>

<td>AE * out (glass side (out))</td><td></td><td> 0,54</td>

<td>Aa * out (absolute value)</td><td></td><td> 0,1</td>

<td>reflection coefficient from film / coating side (inner): RinY (%)</td><td> 11,11</td><td> 11,04</td>

<td>L * in</td><td> 33, 97</td><td> 39,65</td>

<td>a * in</td><td> 5,77</td><td> 5,32</td>

<td>b *^{b *}in</td><td> 3,03</td><td> 3,50</td>

<td>total solar coordinate T,%</td><td> 24</td><td></td>

<td>solar coordinate Rout</td><td> 21</td><td></td>

<td>U value</td><td> 9,86·10^-5 kWh (0.34 BTU)</td><td></td>

<td>S value of U</td><td> 10,44·10'⁵ kWh (0.36 BTU)</td><td></td>

<td>shading coefficient (SC)</td><td> 0,36</td><td></td>

<td>YOU,% / SC</td><td> 109,6</td><td></td>

<td>SHGC</td><td> 0,31</td><td></td>

<td>heat gain</td><td> 78</td><td></td>

Example # 3

<td>Value / measurement</td><td>Before heat treatment</td><td>After heat treatment</td>

<td> 1</td><td> 2</td><td> 3</td>

<td>T ransmission (YOU)%</td><td> 50,50</td><td> 51,84</td>

<td>L * t</td><td> 76,37</td><td> 77,18</td>

<td>a * T</td><td> -4,21</td><td> -4,19</td>

<td>b * T</td><td> -1, 94</td><td> -2,34</td>

<td>external reflectance (out): RoutY (%)</td><td> 17,93</td><td> 17,35</td>

<td>L * out</td><td> 49,41</td><td> 48,69</td>

<td>^and*out</td><td> -2,68</td><td> -2,58</td>

<td>^b* out</td><td> -8,14</td><td> -8,44</td>

<td>AE * out (glass side (out)</td><td></td><td> 0,70</td>

<td>Aa * out (absolute value)</td><td></td><td> 0,1</td>

PL 205 864 B1 cont. example 3

<td> 1</td><td> 2</td><td> 3</td>

<td>film / coating side reflectance</td><td> 9,47</td><td> 9,52</td>

<td>(internal): RinY (%)</td><td></td><td></td>

<td>L * in</td><td> 36,87</td><td> 36,97</td>

<td>a * in</td><td> 3,21</td><td> 3,39</td>

<td>h *^{b *}in</td><td> -5,91</td><td> -5,83</td>

<td>total solar coordinate T,%</td><td> 32</td><td></td>

<td>solar coordinate Rout</td><td> 20</td><td></td>

<td>U value</td><td>9.86d0 '⁵kWh (0.34 BTU)</td><td></td>

<td>S value of U</td><td> 10,44·10^-5 kWh (0.36 BTU)</td><td></td>

<td>shading coefficient (SC)</td><td> 0,46</td><td></td>

<td>YOU,% / SC</td><td> 109,8</td><td></td>

<td>SHGC</td><td> 0,4</td><td></td>

<td>heat gain</td><td> 97</td><td></td>

Example # 4

<td>Value / measurement</td><td>Before heat treatment</td><td>After heat treatment</td>

<td> 1</td><td> 2</td><td> 3</td>

<td>T ransmission (YOU)%</td><td> 44,41</td><td> 45,60</td>

<td>L * t</td><td> 72,50</td><td> 73,28</td>

<td>a * T</td><td> -4,91</td><td> -4,28</td>

<td>b * T</td><td> -4,37</td><td> -4,18</td>

<td>external reflectance (out): RoutY (%)</td><td> 16,84</td><td> 16,04</td>

<td> 1 * ^L. out</td><td> 48,05</td><td> 47,02</td>

<td>about*^and*out</td><td> -1,31</td><td> -1,87</td>

<td>b * out</td><td> -4,81</td><td> -4,97</td>

<td>AE *_out (glass side (out)</td><td></td><td> 1,18</td>

<td>Aa *_out (the absolute value)</td><td></td><td> 0,56</td>

<td>reflection coefficient from the side of the film / coating (inner side: RinY (%)</td><td> 10,57</td><td> 10,47</td>

<td>L * in</td><td> 38,86</td><td> 38,67</td>

<td>a * in</td><td> 5,70</td><td> 3,75</td>

<td>b *^{b *}in</td><td> -0,05</td><td> 2,59</td>

<td>total solar coordinate T,%</td><td> 27</td><td></td>

<td>solar coordinate R._ouvol</td><td> 20</td><td></td>

<td>U value</td><td> 9,86·10^-5 kWh (0.34 BTU)</td><td></td>

<td>US value</td><td> 10,44·10^-5 kWh (0.36 BTU)</td><td></td>

PL 205 864 B1 cont. example 4

<td> 1</td><td> 2</td><td> 3</td>

<td>shading coefficient (SC)</td><td> 0,4</td><td></td>

<td>YOU,% / SC</td><td> 111</td><td></td>

<td>SHGC</td><td> 0,35</td><td></td>

<td>heat gain</td><td> 86</td><td></td>

It can be seen from the above tables for each of Examples 1-4 that the value of ∆Ε * improves when applied to an IG unit (see, for example, Fig. 2). For products with higher visible transmittance (see examples 1 and 3), the improvement of ΔΕ * (the improvement of ΔΕ * can be assessed using ΔΕ ^ οπο - ΔΕ *_G.) is slightly better than the ∆Ε * improvement for the visible transmittance examples (see examples 2 and 4). As shown in Table 8 below, the ΔΕ * improvement (i.e., the improvement of ΔΕ * ™ ΔΕ * ^ values) for the products of Examples 1-4 had the following values, respectively: 0.57, 0.21, 0.85 and 0 , 19. Table 8 below lists the ΔΕ * values ​​measured on the reflective side of the glass for the IG version of Examples 1-4 with a Hunter Lab UltraScan ΧΕ Spectrophotometer twice (2), these two measurements representing the instrument inaccuracy as an example.

Table 8

ΔΕ * for examples 1-4 (mono compared to IG)

<td>Measurement</td><td>Ex. 1 monolith.</td><td>Ex. 1 IG</td><td>Ex. 2 monolith.</td><td>Ex. 2 IG</td><td>Ex. 3 monolith.</td><td>Ex. 3 IG</td><td>Ex. 4 monolith.</td><td>Ex. 4 IG</td>

<td>Tvis,%</td><td> 56,36</td><td></td><td> 44,19</td><td></td><td> 56,98</td><td></td><td> 50,08</td><td></td>

<td>ΔE * g</td><td> 1,9</td><td> 1,34</td><td> 0,8</td><td> 0,54</td><td> 1,5</td><td> 0,70</td><td> 1,4</td><td> 1,18</td>

<td>Aa * g</td><td> 0,42</td><td> 0,68</td><td> 0,11</td><td> 0,10</td><td> 0,36</td><td> 0,10</td><td> 0,77</td><td> 0,56</td>

<td>ΔE * g (2)</td><td> 1,87</td><td></td><td> 0,59</td><td></td><td> 1,33</td><td></td><td> 1,49</td><td></td>

<td>Δa * g (2)</td><td> 0,80</td><td></td><td> 0,17</td><td></td><td> 0,21</td><td></td><td> 0,67</td><td></td>

<td>AF * mono- -ΔΕ * ^ υ</td><td></td><td> 0,57</td><td></td><td> 0,21</td><td></td><td> 0,85</td><td></td><td> 0,19</td>

<td>^{ΔΕ *} (2) mono^-- ΔΕ * ^ υ</td><td></td><td> 0,53</td><td></td><td> 0,05</td><td></td><td> 0,63</td><td></td><td> 0,31</td>

<td>ΔΕ *,% improvement%</td><td></td><td> 29,8</td><td></td><td> 28,3</td><td></td><td> 54,7</td><td></td><td> 14,0</td>

(2) - repeated measurement indicating instrument inaccuracy.

As can be seen from the above tables 7 and 8, as for the IG unit, it is shown in Fig. 2, each of the coatings of Examples 1-4 is a coating with comparable properties, because when the respective products are viewed from the outside (for example, from the outside of the building where the IG unit was placed), the value of Δ wartość * was not greater than 3.0, preferably not greater than 2.5, more preferably not greater than 2.0, and most preferably not greater than about 1.5 (for Example 1, ΑΕ * (external reflectance) for the IG unit was 1.34, for Example 2 was 0.54. for example 3 it was 0.70 and for example 4 it was 1.18)]; while the value of Δa *_outsider (in this specification it is an absolute value) was not greater than 1.0, preferably not greater than 0.8. These values ​​(i.e. ΔΕ * and Δa *) are important as they are measured from the outside of the glass (G) and outside of the coated article (outside of the structure in Fig. 2) as in most applications the articles are mostly viewed from outside for example. the building where the IG team was located.

Each of the IG units listed above had the low emissivity and sheet drag properties discussed above in relation to the monolithic embodiments of the invention. The IG units according to certain embodiments of this invention preferably have visible transmittance (TY,%) of no greater than about 60%, preferably from about 30% to about 60%, before HT, most preferably from about 35% to about 55%, before HT. IG coated articles according to certain embodiments of this invention preferably have visible transmittance (TY,%) from about 10% to about 55% after HT, more preferably from about 35% to about 55% after HT. In a similar fashion, coated articles according to the IG embodiments of this present

According to the invention, they preferably have a shading coefficient (SC) of no greater than about 0.50 (before and / or after HT), preferably from about 0.25 to 0.47 (before and / or after HT). In addition, IG coated articles (see, e.g., FIG. 2) according to certain embodiments of this invention preferably have a glass side reflectance (RGY,%) value of from about 10 to about 22% before HT and / or after HT.

It can also be seen that according to certain preferred embodiments of this invention, IG products are characterized by an a * G value (equivalent to a * out value) from about 0.0 to about -5.0, more preferably from about 3.0 to about -3. 0, before and / or after heat treatment. Thereby, coated articles according to certain embodiments of this invention have a favorable neutral or blue-green color, especially when b * G is also negative.

Finally, in certain preferred embodiments of the present invention, the ratio of the visible transmission (TY,%) to the shading coefficient (SC) (i.e., TY,% / SC) is preferably not greater than 125.0, preferably in the range of about 90 to about 125, and more preferably from about 100 to about 120. In some IG embodiments, this is combined with total solar transmittance ranging from about 20 to about 34%, more preferably from about 24 to 34%.

Certain terms are used primarily in the glass coating art, particularly in determining the properties and solar performance of coated glass. Such terms are used herein in accordance with their known normal meanings. For example, the following terms are used in this specification:

The intensity of reflected visible light, that is, "reflectance, is defined as a percentage and is reported as RXY or Rx (as the Y value quoted below in ASTM E-308-85), where" X is either "G - for the glass side or" F - for the foil side. The term "from the side of the glass (or" G) means viewing from the side of the glass substrate opposite to the side where the coating is placed, while the term "from the side of the film (or" F) means viewing from the side of the glass substrate on which the coating is placed.

Color properties were measured and reported herein using the coordinates and scale: a *, b * CIE LAB (ie, CIE a * b * plot, I11. CIE-C, observer 2 °). Other similar coordinates with the subscript "h" may be equivalently used to denote normal use of the Hunter Lab Scale, ie I11. CIE-C, 10 ° observer, or CIE LUV coordinates u * v *. These scales are defined herein in accordance with ASTM D-2244-93 "Standard Test Method for Calculation of Color Differences from Instrumentally Measured Color Coordinates, 9/15/93, extended to ASTM E-308-95, Annual Book of ASTM Standards. , vol. 06.01 “Standard Method for Computing the Colors of Objects by 10 Using the CIE System and / or as stated in IES LIGHTING HANDBOOK 1981 Reference Volume.

The terms "emittance and" transmittance are well understood in the art and are used herein in accordance with their known meanings. The term "transmittance therefore means solar transmittance, which is made up of visible light transmittance (TY), infrared (IR) transmittance and UV transmittance (Tuv). Total solar energy transmittance (TS) can usually then be determined as a weighted average of these other values. Regarding these transmittances, the visible transmittance described herein can be characterized by the CIE Illuminant C standard, 2 ° observer, technique 380-720 nm; Near Infrared (IR) transmittance at 720-2500 nm; ultraviolet (UV) transmittance at 300-800 nm; and total solar transmittance at 300 - 2500 nm. However, a specific infrared (IR) range (that is, the range 2,500-40,000 nm) is used for the emittance.

Visible light transmittance can be measured using known techniques. For example, using a Perkin Elmer Lambda 900 or Hitachi U4001 spectrophotometer, a transmission spectral curve is obtained. The visible transmission is then calculated using the above-mentioned methodology according to ASTM 308 / 2244-93. If desired, less than the prescribed number of wavelength points may be used. Another technique for measuring visible transmittance uses an industrial spectrometer such as the Spectrogard spectrophotometer from Pacific Scientific Corporation. This instrument directly measures and reports visible transmittance (that is, the Y value in a trichromatic colorimetry system according to ASTM E-308-85) using an I11 observer. C, 2 °.

"Emittance (E) is a measure or property of both absorption and light reflectance at given wavelengths. When the transmittance is zero, which is approximately the case with flotation glass for wavelengths above 2500 nm, the emittance can be represented by the formula:

E = 1 - (reflectance) of the film

In construction, the emittance values ​​are particularly important in the so-called "middle range, sometimes also called" the far range of the infrared (IR) spectrum, i.e.

About 2,500 to about 40,000 nm as defined, for example, in the WINDOW 4.1 Program, LBL-35298 (1994) by Lawrence Berkeley Laboratories as set forth in the reference below. The term "emittance is used in this description to refer to the values ​​of the emittance measured in the infrared range as defined in ASTM Standard E 1585-93 for the measurement of infrared energy for the calculation of emittance, under the title" Standard Test Method for Measuring and Calculating Emittance of Architectural Fiat Glass Products Using Radiometrie Measurements. The standard and its provisions are incorporated herein by reference. In this standard, the emittance factor is given as hemispherical emittance (Eh) and as normal emittance (En).

Actual data collection for measuring such emission factor values ​​is performed in the usual manner, for example with a Beckman Model 4260 spectrophotometer with a "VW" adapter (Beckman Scientific Inst. Corp.). This spectrophotometer measures the reflectance as a function of the wavelength and on this basis calculates the emission factor using the above-mentioned ASTM Standard 1585-93.

Another term used in this specification is "sheet resistance. Sheet resistance (Rs) is a term known in the art and is used herein as used herein. It is given in ohms per square. Generally speaking, the term refers to the resistance in ohms of any square of a layer system on a glass substrate to an electric current passing through the layer system. The sheet resistance tells to what extent a layer or layer system reflects infrared (IR) energy and is therefore often used together with the emission factor as a measure of this property. "Sheet resistance may, for example, be advantageously measured with a four point test ohmmeter, alternatively a four point test ohmmeter with a Magnetron Instruments Corp. Model M-800 head, manufactured by Signatone Corp., Santa Clara, California.

The term "chemical stability or" chemically stable is used herein synonymously with the term "chemical resistance or" chemically resistant. Chemical stability is determined by boiling a 2 inch x 5 inch (50.1 mm x 12.7 mm) coated glass substrate sample at approximately 500 mL of 5%. HCl within 5 minutes [ie at about 104.4 ° C (220 ° F)]. As used herein, a sample is considered to pass this test (ie, that the layering is "chemically resistant, or that is considered" chemically stable, or that is "chemically stable) if at least half of the layering of the sample remains after 5 minutes.

"The mechanical stability is determined in this specification on the basis of the following tests. The test uses a Pacific Scientific Abrasion Tester (or equivalent) in which a nylon brush (e.g. 500 cycles using a 150 g load on a 152.4 mm x 43.18 mm (6 inch x 17 inch) specimen. If, after this test, no obvious scratches are visible to the naked eye in visible light, the product is considered to have passed the test and to be "mechanically stable or" mechanically stable. "

The term "heat treatment" as used herein means heating the article to a temperature sufficient to temper, bend, or strengthen the glass-containing article. This definition includes, for example, heating a coated article to a temperature of at least 1100 ° F (593 ° C) [e.g., from about 550 ° C to about 900 ° C] for a time sufficient for heat tempering.

The term "U-value or" U-factor (synonymous with "thermal transmittance) is an accepted term in the art and as used herein in accordance with its well-known meaning. "The U value is given in this description in kWh (and, in addition in parentheses, in BTU / hr / ft²/ ° F); it can be determined by the sheathed hot-box method given in and in accordance with ASTM-C-1199-91.

The term "shading factor" is an art-recognized term as used herein in accordance with its well-known meaning. Its value is determined according to ASHRAE Standard 142 "Standard Method for Determining and Expressing the Heat Transfer and Total Optical Properties of Fenestration Products by ASHRAE Standards Project Committee, SPC 142, September 1995.