PL219129B1

Heat treatable low-e coated articles and methods of making same

Abstract

A heat treatable coated article (e.g., vehicle windshield, IG unit, etc.) is provided with a dual-silver low-E coating. Before and/or after heat treatment (HT), the coating and/or coated article has a visible transmittance of at least 70%, more preferably at least 75%. Moreover, the coating and/or coated article is designed so as to have approximately the same color when viewed over a wide range of viewing angles. In certain embodiments, at least one contact layer (e.g., of or including NiCrOx) that contacts an infrared (IR) reflecting layer (e.g., Ag) is oxidation graded so that it progressively becomes less oxidized through its thickness as it nears the IR reflecting layer. In still other embodiments, a Si-rich silicon nitride layer(s) may be utilized to reduce haze.

PL219129B1, drawing sheet 1 — Sheet 1 of 7

Term

Term ended

Expired 3 July 2021, 5.2 years ago.

13 claims: 1 independent, 12 dependent

1
Patent claims Zastrzeżenia patentowe 1. Coated article having a coating applied to a glass substrate (1), characterized in that the coating comprises:an infrared (IR) reflecting layer (9 or 19) contacting and interposed between the first and second layers (7, 17, 11, or 21) where the second layer comprises NiCrO x;and wherein at least a second layer comprising NiCrOx has been sputtering in a continuous process and is gradually oxidized such that the first portion of the second layer close to said infrared (IR) reflecting layer is less oxidized than the second portion of the second layer further away from the infrared (IR) reflecting layer, where the layer the infrared reflecting (IR) includes metallic silver (Ag) and where the first part of the second layer containing NiCrOx is oxidized in the range of 0 to 40%, and the second part of the second layer after deposition is oxidized to the extent of at least 50%. 1. Wyrób powlekany obejmujący powłokę naniesioną na podłoże szklane (1), znamienny tym, że powłoka zawiera: warstwę odbijającą podczerwień (IR) (9 lub 19) stykającą się i umieszczoną jako przekładka między pierwszą i drugą warstwą (7, 17, 11 lub 21), gdzie druga warstwa zawiera NiCrOx;i gdzie co najmniej druga warstwa zawierająca NiCrOx została naniesiona przez napylanie katodowe w procesie ciągłym i jest stopniowo utleniona, tak, że pierwsza część drugiej warstwy bliska wymienionej warstwy odbijającej podczerwień (IR) jest mniej utleniona niż druga część drugiej warstwy, znajdującej się dalej od warstwy odbijającej podczerwień (IR), gdzie warstwa odbijająca podczerwień (IR) zawiera metaliczne srebro (Ag) i gdzie pierwsza część drugiej warstwy zawierającej NiCrOx jest utleniona w zakresie od 0 do 40%, a druga część drugiej warstwy po osadzeniu jest utleniona w zakresie co najmniej 50%.

429 paragraphs in 8 sections, as filed

Description of the invention

The invention relates to a coated article including a coating applied to a glass substrate. The invention encompasses heat treated low E coated articles and discloses methods of making them. Such coated articles can be used as vehicle windshields, insulating glass (IG) units, and other suitable applications.

State of Technology

Multiple coatings intended to alter the characteristics of sunlight are known in the art. Such coatings should most often reflect infrared (IR) radiation with good visible light transmittance. In the automotive industry, for example, car windshields often should have a visible transmittance of at least 70% in the United States and at least 75% in Europe, even when laminated with a polyvinyl butyral (PVB) layer sandwiched between adjacent glass layers. The need for good visible light transmittance is often incompatible with the need for good IR reflection, and it is difficult to achieve both at the same time. The production of low E coated articles is hampered by the need for a mechanically strong and / or chemically resistant coating, as well as the possibility of using a coating with a low visible light reflectance (glass side) that would not substantially change the color of the article when viewed from different angles. The ability to heat treat such coatings is also advantageous so that they can be used in the manufacture of vehicle windshields where heat bending is required, toughened IG units, and the like.

Common US Patent Application No. 5,584,902 discloses a low E coating system having a stack composed of, from the glass substrate outwardly: Si3N4 / NiCr / Ag / NiCr / Si3N4. Although this coating is heat treatable and although it is inherently a low E coating, it unfortunately has a fairly high emission factor and / or layer resistance, resulting in low Rsolar (Total Solar Reflectance) values of about 22% to about 24 %. For example, the coating disclosed in the '902 patent has a layer resistance (Rs) of 14.4 ohms / square and a normal emission factor (En) of 0.15 before heat treatment; and has an Rs of 10.5 ohms / square and a normal emission factor (En) of 0.11 after heat treatment.

Common US Patent Application No. 5,557,462 discloses a low E silver double layer coating comprising, from the glass substrate outwards, a stack: Si3N4 / NiCr // Ag / NiCr / Si3N4 / NiCr / Ag / NiCr / Si3N4. The coating system disclosed in the '462 patent has good emissivity values and good Rsolar values. Unfortunately, the coating systems disclosed in the '462 patent cannot be heat treated (for example, during heat treatment, Rs increases from about 3-5 to well above 10 and the haze begins to increase). Since the coatings disclosed in the '462 patent are not heat treatable, they cannot in practice be used in the manufacture of vehicle windshields (where hot bending is required) or for other heat treatment (HT) applications such as toughening, heat strengthening or bending. .

Certain other silver double layered coatings are described in the prior art section of said provisional application. See also U.S. Patent No. 6,060,178. A disadvantage of these coating systems is, unfortunately, the low durability before and / or after heat treatment.

Summary of the invention

It is an object of certain example embodiments disclosed herein to provide a low E heat treatable coating (or layered system) that is mechanically and / or chemically stable both before and after heat treatment, wherein the visible transmittance of the coating system is at least about 70. %.

Another object of certain example embodiments described herein is to provide a heat treatable low E coating with a double silver layer that is mechanically and chemically stable.

Another object of certain example embodiments described herein is to provide a double-layer low E silver coating that includes at least one contact layer with a gradually varying oxidation state that contacts the IR reflecting layer, wherein the degree of oxidation in the contact layer is varied or changes gradually along the thickness of this layer. One or more stepwise oxidation contact layers facilitates the production of a coating with high visible light transmittance in combination with heat treatment.

PL 219 129 B1

Another object of certain example embodiments described herein is to provide a coating comprising one or more Ni or NiCr contact layers (e.g., a NiCrO x layer) with a gradual change in the degree of oxidation along the thickness of the layer, one part of the layer being more oxidized than another part of the layer. Again, it is believed that the gradually oxidized contact layer or layers can facilitate the production of high visible light transmittance coatings in combination with heat treatment capability.

Another purpose of certain example embodiments disclosed herein is to use silicon nitride in a layered stack to reduce the haze that occurs during heat treatment. In certain embodiments disclosed herein, the silicon nitride layer may be a Si-rich layer.

Another objective of certain example embodiments disclosed herein is to provide a heat treatable double layer silver layer system designed to a) be mechanically stable, b) have a visible transmittance of at least about 70%, preferably about 75%, and c) have an Rsolar value. at least 26%, preferably at least 28%, and most preferably at least about 29%.

Another object of certain example embodiments presented herein is to provide a coating in accordance with one or more of the above-mentioned purposes that may be used in IG insulating glass units and / or for vehicle windshields.

Another object of certain example embodiments disclosed herein is to provide a low E heat treatable coating having visible transmittance combined with a normal emission factor (En) value of no greater than 0.08 (preferably no greater than 0.06) prior to heat treatment; and / or an En value of no more than 0.07 (preferably no more than 0.05) after heat treatment (HT).

Another object of certain example embodiments disclosed herein is to provide a low E heat treatable coating having visible transmittance combined with a layer resistance (Rs) value of no greater than 10.0 ohms / square (more preferably no greater than 8.0 ohms / square). and most preferably no greater than about 5.0 ohm / square) prior to heat treatment; and / or an Rs value of no more than 8.0 ohm / square (more preferably no greater than 6.0 ohm / square, and most preferably no greater than about 4.0 ohm / square) after heat treatment.

Another object of certain example embodiments disclosed herein is to provide a low E heat treatable coating that has substantial reflective color stability when viewed from different viewing angles (VA) ("VA"). For example, in certain embodiments of this invention, coated articles may have a glass side reflectance a * shift (i.e., Aa *) of no greater than 4.0, more preferably no greater than 3.0, and most preferably no greater than 2.0, for VA shift of approximately 60 °.

Another object of certain example embodiments disclosed herein is to provide a low E heat-treated coating with a double silver layer having an a * shift of the glass side reflectance color ranging from -2.0 to 2.0 before and / or after a VA shift of 60 ° from the normal value, in order to reduce or limit the color change detectable by a human with the naked eye.

Another object of certain example embodiments disclosed herein is to provide a heat treatable low E coating with a double silver layer having a heat treated haze value of no greater than 0.40, preferably no greater than 0.30 (as a monolithic system and / or laminate). such as windshields of cars).

Another object of certain example embodiments of this invention is to provide a heat treatable laminate with a low E silver double layer coating having a glass side visible reflectance (RgY) (III. C, 2 degrees) of no greater than 11%, more preferably no greater than about 9.0%, most preferably no greater than 8.5%.

Another object of the present invention is to fulfill one or more of the above objectives.

Generally, certain example embodiments disclosed in the present invention meet one or more of the objectives set out above by providing a coated article that includes a coating applied to a glass substrate, the coating comprising: an infrared (IR) reflecting layer contacting and disposed between the covers of the first and second layers. wherein said second layer comprises NiCrO x; and wherein at least said second layer comprising NiCrO x is gradually oxidized such that a first portion of the second layer proximate to said infrared (IR) reflecting layer is less oxidized than a second portion of the second layer which is further away from said infrared (IR) reflecting layer .

PL 219 129 B1

Certain other exemplary embodiments disclosed herein meet one or more of the purposes or needs set out above by providing a coated article having a coating applied to a substrate, the coating comprising an infrared (IR) reflective metallic layer contacting and disposed between the first and second contact layers; the second contact layer is oxidized gradually and is oxidized gradually more and more along its thickness farther from said infrared (IR) reflecting layer.

Certain other example embodiments of this invention fulfill one or more of the above objectives or needs by providing a coated article comprising: a coating applied to a glass substrate, said coating comprising, from the glass substrate outwardly: a) at least one dielectric layer; b) a first contact layer that is at least partially oxidized; c) a first infrared (IR) reflecting layer comprising Ag; d) a second contact layer that is at least partially oxidized, the first infrared (IR) reflecting layer in contact with each of said first and second contact layers; e) at least one additional dielectric layer; f) a third contact layer that is at least partially oxidized; g) a second infrared (IR) reflecting layer comprising Ag; h) a fourth contact layer that is at least partially oxidized, said second infrared (IR) reflecting layer in contact with each of said third and fourth contact layers; i) at least one additional dielectric layer; wherein, after heat treatment (HT) and lamination, said coated article has a visible transmittance of at least about 70%, a Tsolar of no more than about 50%, an Rsolar of at least 26%, and a layer resistance (Rs) of no greater than 8.0 ohms. /square; and wherein at least two layers of said first, second, third and fourth contact layers comprise at least Ni or an alloy of Ni.

Certain other example embodiments of this invention meet one or more of the above purposes or needs by providing a coated article comprising: a coating applied to a glass substrate, said coating comprising, from the glass substrate outwardly: a) at least one dielectric layer comprising silicon nitride ; b) a first contact layer comprising Ni or a Ni alloy that is at least partially oxidized; c) a first infrared (IR) reflecting layer comprising Ag; d) a second contact layer comprising Ni or a Ni alloy that is at least partially oxidized; e) at least one additional dielectric layer; f) a third contact layer comprising Ni or a Ni alloy that is at least partially oxidized; g) a second infrared (IR) reflecting layer comprising Ag; h) a fourth contact layer comprising Ni or a Ni alloy that is at least partially oxidized; i) at least one additional dielectric layer; wherein after heat treatment (HT), said coated article has a visible transmittance of at least about 70%, a Tsolar of no greater than about 50%, an Rsolar of at least 26%, and a layer resistance (Rs) value of no greater than 8.0 ohms / square ; and

Certain other exemplary embodiments meet one or more of the above objectives or needs by providing a method of cathodically sputtering a gradually oxidized layer, the method comprising: providing a substrate; providing a sputtering device including at least one target; directing the first portion of gas close to the first side of the target and the second portion of gas close to the second side of the target such that the first portion of gas contains more oxygen than the second portion of gas, whereby as the substrate passes below the target, an infrared (IR) reflecting layer is formed gradually oxidized layer, wherein the gradually oxidized layer is oxidized more strongly in one part than in the other part.

Certain other embodiments of this invention meet one or more of the objectives set out above by providing a coated article comprising: a layer system applied to a glass substrate, the layer system comprising, from the glass substrate outwardly: Si-rich SixNy silicon nitride layer, wherein x / y is from 0.76 to 1.5 in at least part of the layer; first contact layer; and an infrared (IR) reflecting layer. In various embodiments disclosed herein, a portion of all Si rich silicon nitride layers may be Si rich.

The invention relates to a coated article having a coating applied to a glass substrate (1), characterized in that the coating comprises: an infrared (IR) reflecting layer (9 or

19) touching and interposed between the first and second layers (7, 17, 11 or 21), where the second layer comprises NiCrOx; and wherein at least a second layer comprising NiCrOx has been sputtering in a continuous process and is gradually oxidized such that the first portion of the second layer close to said infrared (IR) reflecting layer is less oxidized than the second portion of the second layer further away from the infrared (IR) reflecting layer, where

The infrared (IR) reflecting layer comprises metallic silver (Ag) and wherein the first portion of the second layer comprising NiCrO x is oxidized to between 0 and 40% and the second portion of the second layer is oxidized to at least 50% after deposition.

The coated article is preferably characterized in that a first portion of the second layer comprising NiCrO x is oxidized in the range of 0 to 20%.

Preferably, in the coated article, the first portion of the second NiCrOx inclusive layer is oxidized to from 0 to 20% and the second portion of the second NiCrOx inclusive layer is oxidized to at least up to 60%.

In the coated article, preferably the second layer containing NiCrO x becomes progressively less oxidized along its thickness as it approaches the infrared (IR) reflecting layer.

Preferably, in the coated article, the first portion of the second NiCrOx inclusive layer is conductive or semiconductive and the second portion of the second NiCrOx inclusive layer is dielectric or non-conductive.

Preferably, in the coated article, the first portion of the second layer, including NiCrOx, is less transmissive to visible light than the second portion of the second layer, including NiCrOx.

In the coated article, preferably both of the first and second layers contain NiCrOx and are gradually oxidized such that each of the first and second layers includes a first portion close to the infrared (IR) reflecting layer which is less oxidized than the second downstream portion. from the infrared (IR) reflecting layer than the first part.

The coated article is preferably characterized in that the coating comprises the following layers from the glass substrate outward: at least one dielectric layer; a first layer comprising NiCrO x; infrared (IR) reflecting layer; a second layer comprising NiCrOx; at least one additional dielectric layer; a third layer comprising NiCrO x; a second infrared (IR) reflecting layer; a fourth layer comprising NiCrO x; and at least one additional dielectric layer.

Preferably, in the coated article, the infrared (IR) reflecting layers include silver, and at least one dielectric layer between the substrate and the first NiCrO x inclusive layer comprises silicon nitride.

The coated article preferably has a visible transmittance of at least 70%, an Rsolar of at least 26%, and a heat treated sheet resistance (Rs) of no more than 8.0 ohm / square.

The coated article preferably has a visible transmittance of at least 75%, an Rsolar of at least 28%, and a heat treated sheet resistance (Rs) of no more than 6.0 ohm / square.

In a coated article, preferably the second layer is between the infrared (IR) reflecting layer and the substrate.

Preferably, in the coated article, an infrared (IR) reflecting layer is located between the second layer and the substrate.

The invention will now be described with reference to several exemplary embodiments thereof shown in the following drawings.

Description of Drawings

Fig. 1 is a side sectional view of a coated article according to one embodiment of this invention.

Fig. 2 is a schematic view of a portion of a cross section of a laminated vehicle windshield according to an embodiment where coatings according to any embodiment of this invention may be used.

Fig. 3 (a) is a sectional view of a portion of a coating according to an embodiment showing a pair of progressively oxidized contact layers (e.g., NiCrOx layers) surrounding an infrared (IR) reflecting layer (e.g., Ag layer).

Fig. 3 (b) is a sectional view of a portion of a coating according to an embodiment of the present invention showing an infrared (IR) reflecting layer (e.g., Ag layer) surrounded by a pair of contact layers (e.g., NiCrOx layers)) of which only one layer is gradually oxidized.

Fig. 4 is a schematic sectional view showing how a gradually oxidized contact layer (e.g., a NiCrOx layer) is applied by sputtering according to one embodiment of the present invention.

PL 219 129 B1

Fig. 5 is a cross-sectional view of the layer assembly of the coatings of Examples 1-3.

Fig. 6 is a sectional view of a coated article according to another embodiment of this invention.

Detailed Description of Certain Exemplary Embodiments of the Invention

A detailed description is now provided with reference to the accompanying drawings where, for several views, like reference numerals indicate similar parts or layers.

Certain embodiments disclosed herein relate to a low E coating or sandwich system that can be used in applications such as vehicle windshields, other vehicle windows, skylights, glass doors, IG units, and the like. The coatings of certain embodiments disclosed herein have preferably low E and good visible transmittance and are heat treatable. Preferably, the coatings of certain embodiments disclosed herein are mechanically stable before and / or after heat treatment (HT) and HT does not significantly alter sheet resistance (Rs) and / or haze. It is known in the art that in order to achieve the desired results (e.g., quenching, bending, and / or heat strengthening), the conduct of HT often requires heating the coated substrate to a temperature of between 593 ° C (1,100 ° F) and 788 ° C (1,450 ° F). .

Fig. 1 is a side sectional view of a coated article according to one embodiment of this invention. The coated article comprises a substrate 1 (e.g., a clear, green, brown, or cyan glass substrate from about 1.0 to about 10.0 mm thick, preferably from about 1.8 mm to about 4 mm thick), a first dielectric antireflection layer 3, a second dielectric layer 5 to reduce haze, a first lower contact layer 7 (which is in contact with layer 9), a first conductive metallic layer 9 reflecting infrared (IR), first upper contact layer 11 (which contacts layer 9), third dielectric layer 13 (which may be applied in one or more steps in various embodiments of the present invention), fourth dielectric layer 15, second lower contact layer 17 (which contacts layer 19), a second conductive metallic infrared (IR) reflecting layer 19, a second upper contact layer 21 (which is in contact with layer 19), a fifth dielectric layer 23 and finally a sixth dielectric protective layer 25. Each "contact" layer contacts at least one infrared (IR) reflecting layer. Said layers 3 - 25 together constitute a heat treated low E coating 27 (ie, a low emissivity coating) which has been applied to a glass substrate 1 or a plastic substrate 1.

In certain embodiments of this invention, first dielectric layer 3 may be formed of or include titanium dioxide (TiOx) where x is from 1.7 to 2.3, preferably is 2.0), silicon nitride [SixNy where x / y is about 0.75 (i.e. it is Si3N4), or, alternatively , x / y is from about 0.76 to about 1.5 in Si-rich embodiments], silicon dioxide (SiOx, where x is from 1.7 to 2.3, most preferably about 2.0) niobium oxide (e.g. Nb2O5), SiZrN, tin oxide, zinc oxide, silicon oxynitride or any other suitable dielectric material. The first dielectric layer 3 serves as an antireflection layer in some embodiments of this invention.

The second dielectric layer 5 may reduce haze in some embodiments of this invention, and is preferably silicon nitride or includes silicon nitride (e.g., Si3N4or, alternatively, a silicon-rich SixNy nitride where x / y is from 0.76 to 1.5, preferably from 0.85 to 1.2). When sputtering a layer or layers of silicon nitride, an Si target or, alternatively, a Si containing target may be used with up to 3-20% by weight of aluminum and / or stainless steel (e.g. SS # 316) with about the same amount of aluminum and / or or steel in a layer or in several layers so formed. Other materials, including SiZrN, among others, may also be used to reduce the haze of layer 5.

Although Si3N4 may be used in certain embodiments to form layer 5 (and / or layer 15), it has been found that in some embodiments of this invention the silicon-rich type of silicon nitride is better at reducing haze as layer 5 and / or improving mechanical durability. In the absence of layer 5 (and / or layer 15), the haze is typically at least 0.45, while as discussed herein, with this layer or layers the haze is reduced to less than 0.4. In embodiments of the invention comprising Si-rich silicon nitride, layer 5 (and / or layer 15) is preferably composed of or includes silicon nitride Si.xNywhere x / y is from 0.76 to 1.5, more preferably from 0.85 to 1.2. For Si3N4, the refractive index "n" is about 2.04 and the extinction coefficient "k" is about 0. However, the Si rich silicon nitride, in accordance with some embodiments of this invention, may have a refractive index of at least about 2.05, preferably at least about 2. , 07, and in exemplary embodiments 2.08 (at 632 nm).

PL 219 129 B1

Also, the Si rich silicon nitride in accordance with some embodiments of the present invention may have an extinction coefficient "k" of at least about 0.001, more preferably at least about 0.003.

In the first example, in the monolithic and post-HT layer 5 of the nitride (and / or layer 15) "n" = 2.099 and "k" = 0.0034, while in the second example in the monolithic system after HT "n" = 2.168 a "K" = 0.014. Not only did Si rich silicon nitride reduce haze better than Si3N4, it was also found that in the exemplary embodiments it adhered better to the titanium oxide in layer 3. Surprisingly, it was found that Si rich silicon nitride also under the NiCrO layersx and Ag in Figs. 1, 5, and 6 reduced the sheet drag (Rs).

The infrared (IR) reflecting layers 9 and 19 are preferably metallic and conductive layers and may be made of or may include silver (Ag), gold, or any other suitable infrared (IR) reflecting material. Metallic Ag, however, is a material selected for producing the infrared (IR) reflecting layers 9 and 19 in certain example embodiments of this invention. These infrared (IR) reflecting layers facilitate the preparation of the low E coating 27.

In preferred embodiments of the present invention, the contact layers 7, 11, 17 and 21 are formed of or may include a nickel oxide or a nickel alloy, such as nickel chromium oxide (NiCrOx). NiCrO x layers may be fully oxidized (ie, fully stoichiometric), or may be at least about 75% oxidized in other embodiments of this invention. Although NiCrOx is a preferred material for the production of layers 7, 11, 17 and / or 21, those skilled in the art also know other materials that can be used interchangeably (e.g. Ni oxides, Ni alloy oxides, Cr oxides, Cr alloy oxides, NiCrOxNy or any other suitable material) for producing one or more such layers. It is known that the contact layers 7, 11, 17 and / or 21 may optionally be continuous layers in various embodiments of the present invention.

When layers 7, 11, 17 and / or 21 contain NiCrOx in some embodiments of the present invention, Ni and Cr may be incorporated in varying amounts, for example, in the form of nichrome containing about 80-90% Ni and about 10-20% Cr. An exemplary sputtering target for applying these layers contains not only SS-316, which essentially contains 10% Ni and 90% other components, mainly Fe and Cr, but also Haynes alloy 214, which contains (as a nominal composition) mainly the following ingredients, by weight:

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

One or more contact layers 7, 11, 17 and / or 21 (e.g. with or including NiCrOx) is (are) preferably gradually oxidized (oxidized) in certain embodiments of this invention, with the degree of oxidation in the layer (s) varying throughout the thickness of the layer (s). For example, one or more contact layers (7, 11, 17, and / or 21) may be gradually oxidized to be less oxidized at the interface in the immediate vicinity of the infrared (IR) reflecting layer (9 or 19) therefrom. the portion of the contact layer or layers that is further away from the immediately adjacent infrared (IR) reflection layer. It is believed that the gradual oxidation of one or more contact layers 7, 11, 17 and / or 21 allows the coating 27 with a low E to both obtain heat treatment and good visible light transmittance (this has not been achieved so far with NiCrOx contact layers). in a low E double silver layer coating system; see, for example, the cited '462 patent). This is explained in more detail below with reference to Figs. 3 (a) and 3 (b).

Returning to Fig. 1, the third dielectric layer 13 functions as the interface between the two halves of the coating 27 and is of or includes tin oxide in certain embodiments of this invention. However, other dielectric materials, such as silicon nitride, titanium dioxide, niobium oxide, silicon oxinitride, zinc oxide, or the like, among others, may be used instead. The fourth dielectric layer 15 functions as a haze reducing layer in some embodiments of this invention and is preferably silicon nitride or includes silicon nitride (e.g., Si3N4, or, alternatively, includes the silicon-rich silicon nitride discussed above). But

In alternative embodiments of the present invention, other materials (e.g., SiZrN) may be interchanged to form the dielectric layer 15.

The fifth dielectric layer 23 may be tin oxide or may include tin oxide in certain embodiments of this invention. However, other dielectric materials, such as silicon nitride, titanium dioxide, niobium oxide, silicon oxinitride, zinc oxide, or the like, among others, may be used instead. A protective dielectric top layer is provided at least for improved durability, and may be silicon nitride or may include silicon nitride (e.g., Si3N4) in certain embodiments of this invention. However, other dielectric materials may be used in the layer 25 instead, such as, but not limited to, titanium dioxide, silicon oxinitride, tin oxide, zinc oxide, niobium oxide, SiZrN, or the like.

Different or different layers can also be introduced underneath or above said coating 27. Thus, while the layer system or coating 27 is "on" or "applied" (directly or indirectly) to substrate 1, another layer or layers may be interposed therebetween. Thus, for example, the coating 27 of Fig. 1 may be considered to be "on" and "applied" to the substrate 1, even when different or different layers are present between the layer 3 and the substrate 1. Moreover, some embodiments of the present invention may not include certain coating layers 27, while in other embodiments other layers may also be included without departing from the spirit of certain embodiments of the present invention.

Fig. 2 shows a laminate (e.g., vehicle windshield) according to one embodiment of the present invention including the coating 27 of Fig. 1. As shown in Fig. 2, a laminate (e.g., vehicle windshield) includes a first glass substrate 1 on which it is provided. there is a coating 27 and a second glass substrate 31. Between these substrates is a layer of PVB arranged in a known manner to make contact with one side of the coating 27. In the form shown in Fig. 2 the coating 27 is on the second face (i.e. face 2) 37 of the laminate. The first surface 35 is on the outer side of the laminate exposed to the outside of the car, the second surface 37 is on the inside or inside of the outer substrate 1, the third surface 39 is inside the inner substrate 31 and the fourth surface 41 inside the car. The coatings 27 are preferably on both second 37 or each of the two thirds 39 of the surfaces of such laminates (the same also applies to the IG units).

Returning to Fig. 1, while different thicknesses may be used in accordance with one or more of the discussed purposes, the following exemplary thicknesses and the following exemplary materials for the respective layers for the glass substrate 1 for the embodiment shown in Fig. 1 are preferred:

Table 1. (exemplary materials and their thicknesses: embodiments of the invention according to Fig. 1); 1 A = 1 x 10-8 cm

<td>layer</td><td>preferred range, A.</td><td>a more preferred range, A.</td><td>for example, A.</td>

<td>T1O2 (layer 3)</td><td>0-400 A.</td><td>50-250 A.</td><td>100 A.</td>

<td>SixNy (layer 5)</td><td>0-400 A.</td><td>50-250 A.</td><td>170 A.</td>

<td>NiCrOx (layer 7)</td><td>5-100 A.</td><td>10-50 A.</td><td>18 A.</td>

<td>Ag (layer 9)</td><td>50-250 A.</td><td>80-120 A.</td><td>105 A.</td>

<td>NiCrOx (layer 11)</td><td>5-100 A.</td><td>10-50 A.</td><td>16 A.</td>

<td>SnO2 (layer 13)</td><td>0-800 A.</td><td>500-850 A.</td><td>650 A.</td>

<td>SixNy (layer 15)</td><td>0-800 A.</td><td>50-250 A.</td><td>170 A.</td>

<td>NiCrOx (layer 17)</td><td>5-100 A.</td><td>10-50 A.</td><td>18 A.</td>

<td>Ag (layer 19)</td><td>50-250 A.</td><td>80-120 A.</td><td>105 A.</td>

<td>NiCrOx (layer 21)</td><td>5-100 A.</td><td>10-50 A.</td><td>16 A.</td>

<td>SnO2 (layer 23)</td><td>0-500 A.</td><td>100-300 A.</td><td>150 A.</td>

<td>Si3N4 (layer 25)</td><td>0-500 A.</td><td>100-300 A.</td><td>250 A.</td>

PL 219 129 B1

Fig. 6 illustrates a low E heat treatable coating 27 according to another embodiment of the present invention. The coating 27 of Fig. 6 is the same as the coating of Fig. 1 described above, except that (i) either the dielectric layer 3 is removed or (ii) layers 3 and 5 are replaced with a single layer 40 of silicon nitride. In other embodiments of the present invention, silicon nitride layer 40 may be formed of or include Si3N4. In other embodiments, silicon nitride layer 40 may be formed of or include SixNywherein x / y may be from about 0.65 to about 0.80, or, alternatively, from about 0.76 to about 1.5 in silicon-rich embodiments. In another particular embodiment of Fig. 6, layer 40 may be made of or include SiZrN. The nitride layer 40 is advantageous because it reduces haze and is preferably from about 10 to about 500 x 10 in thickness-8 cm (500 Å), more preferably from about 200 to about 400 x 10-8 cm (400 A). In this embodiment, the thickness of the upper infrared reflecting layer 19 may also be increased from about 0 to about 10 x 10-8 cm (10 Å), and / or the thickness of the upper dielectric layer 25 can be increased by from about 0 to about 10%. In another aspect of the Fig. 6 embodiment, silicon nitride may be used to form layer 40, but such that the bottom of the layer is Si.3N4 or included Si3N4while the top portion is the silicon-rich type of silicon nitride discussed above. As with all embodiments of this invention, the silicon-rich silicon nitride exhibits improved haze reducing properties as compared to Si3N4. The Figure 6 embodiment has reduced visible transmittance (but still at least 70%) compared to the Figure 6 embodiment. 1, but may be more stable under certain conditions and the Rsolar value may be greater than that of the Fig. 1 embodiment, which of course is preferred.

In certain example embodiments of this invention, the coating (layer) 27 systems of all embodiments of this invention before / after monolithic heat treatment (HT) have the low E shown in Table 2.

Table 2. Monolithic system before / after heat treatment (HT)

<td>properties</td><td>generally</td><td>advantageously</td><td>more preferably</td>

<td>Rs (ohm / square, before HT)</td><td> < 10,0</td><td> < 8,0</td><td> < 5,0</td>

<td>Rs (ohm / square, post HT)</td><td> < 8,0</td><td> < 6,0</td><td> < 4,0</td>

<td>En (before HT)</td><td> < 0,08</td><td> < 0,06</td><td>not given</td>

<td>En (after HT)</td><td> < 0,07</td><td> < 0,05</td><td>not given</td>

<td>haze (after HT)</td><td> < 0,40</td><td> < 0,30</td><td> < 0,28</td>

Coatings 27, according to certain example embodiments of this invention (for example, according to Fig. 1-6) have the following properties of color, transmittance, reflectance, haze (for example below is a preferred grayish color) on a clear soda lime glass substrate (for example 2.1 mm thick glass) laminated to another similar clear substrate soda-lime glass (e.g. in the form of PVB (polyvinyl butyral) automotive windshields or with indicator oil between two substrates) as shown in Fig. 2 (i.e., surface 2 of the laminate) as given in Table 3. In Table 3 below, R.gY is the reflection of visible light from outside the vehicle as shown in Figs. 2 and R.fY is the reflection of visible light from the other side of the laminate, i.e. from inside the vehicle in Fig. 2, and the a *, b * values under these respective reflection parameters also correspond to the glass side (g) (e.g. outside the vehicle in Fig. 2) and film (f) (e.g. inside the car in Fig. 2), respectively.

Table 3. Color and transmittance after HT: laminated form

<td>property</td><td>generally</td><td>advantageously</td>

<td>Tvis (III. A, 2 degrees)</td><td> > 70%</td><td>> 75% (Fig. 1 only)</td>

<td>Tvis (III. C, 2 degrees)</td><td> > 70%</td><td>> 75% (Fig. 1 only)</td>

PL 219 129 B1 cont. table 3

<td>Rsolar</td><td> > 26%</td><td> > 28%</td>

<td>T.solar</td><td> < 50%</td><td> < 48%</td>

It has been surprisingly found that stacks of layers according to certain embodiments of this invention exhibit slight shifts in the color of visible light caused by a change in viewing angle (VA) when viewed from the glass side of the article (e.g.

Fig. 2). Table 4 below shows, for example, small Aa * valuesg obtained with coated laminated articles of certain embodiments of this invention when viewed from a normal viewing angle (i.e., right angles) from a viewing angle altered by 60 °. In other words, Table 4 below shows that, according to some embodiments of the present invention, low values for Δa * can be kept.g even assuming a 60 ° change in viewing angle (VA), so that coated articles do not change color when viewed from different angles when viewed with the naked eye. The Ab * values are considered to be less important than the Δa * values because changes in a * are usually more noticeable to the naked eye than corresponding changes in b *. In certain example embodiments of this invention, a * g ranges from -2.0 to +2.0 both before and after a 60 ° (VA) viewing angle change such that a * g stays close to the b * axis (i.e. The b * axis is the vertical axis in the blue (-) / yellow (+) range while the a * axis is the horizontal axis in the green (-) / red (+) range even though the viewing angle index changes, thus minimizing exposure. color changes.

Table 4. Color change when the viewing angle (VA) changes by 60 °

<td>property</td><td>generally</td><td>more preferably</td><td>most preferably</td>

<td>RgY (VA normal)</td><td> < 11%</td><td> < 9%</td><td> < 8%</td>

<td>a * g (VA normal)</td><td>-2.0 to +2.0</td><td>-1.0 to +1.0</td><td>-1.0 to 0.0</td>

<td>Aa * (VA 60 ° change)</td><td> < 3,0</td><td> < 2,0</td><td>not given</td>

It has been mentioned above that the low E silver double layer coating system of US Pat. No. 5,557,462 (i.e., the glass / Si3N4 / NiCr / Ag / NiCr / Si3N4 / NiCr / Ag / NiCr / Si3N4 system) cannot be heat treated at least because that during the heat treatment, the Rs value increases from about 3-5 to well above 10 and the haze begins to increase. It is now believed that if the thickness of the NiCr layers were significantly increased in the '462 patent in an attempt to achieve heat treatment, it would unfortunately reduce the visible light transmittance to a value well below 70%, which would of course make coated articles unsuitable for use on windshields. vehicles.

However, it has surprisingly been found that by gradually oxidizing one or more non-crystalline contact layers 7, 11, 17 and / or 21, the resultant coated article can maintain good visible light transmittance, with low E, including a low R value.s and good durability in heat treatment (for example, in quenching, hot bending and so on). This is explained in more detail with reference to Figs. 3 (a) and 3 (b).

As shown in Fig. 3 (A), both contact layers 7 and 11 (and / or 17 and 21) on both sides of the applied infrared (IR) reflecting layer 9 (and / or 19) are gradually oxidized so as to be

Are less oxidized (including completely unoxidized layers in certain optional embodiments of this invention) on an interfacial infrared (IR) reflecting layer (for example, on an interface Ag layer). In other words, the two contact layers on either side of the Ag layer 9 are oxidized less along their respective thicknesses as they approach the Ag layer 9. Accordingly, in some embodiments of this invention, parts (e.g., 5x10-8 cm (5A)) of layers 7 and 11 (or 17 and 21) the nearest layers 9 (or 19) are oxidized ranging from about 0 to about 40%, preferably from about 0 to about 20%, more preferably from about 0 to about 10%. Meanwhile, parts (for example, parts 5x10-8 cm (5A)) of layers 7 and 11 (or 17 and 21) furthest from layer 9 (or 19 are at least about 50% oxidized, preferably at least about 60% oxidized, more preferably at least about 60% oxidized 75%, and most preferably they are oxidized to at least about 85%.

Thus, the contact layers are progressively less oxidized along their respective thicknesses as it approaches the infrared (IR) reflecting layer 9, 19. In certain embodiments of the present invention, this causes contact layers 7 and 11 (or 17 and 21) to become conductive layers, or at least semiconducting layers at the interface with an infrared (IR) reflecting layer 9 (or 19), and are substantially non-conductive layers. in other parts of layers 7 and 11 (or 17 and 21), i.e. in the part 5 Å farthest from layer 9 (or 19). Thus, when contact layers with or containing partially oxidized NiCrOx, the value of x decreases progressively along the thickness of the layer towards the infrared (IR) reflecting layer 9, 19. This value of x may even in some cases approach zero or be equal to zero close to the immediately adjacent infrared (IR) reflecting layer.

It is believed that the less oxidized portions of the contact layers 7 and 11 (and / or 17 and 21) close to the infrared (IR) reflecting interface of layer 9 (or 19) make coating 27 withstand heat treatment (HT) and provide good adhesion to layer 9, 19. However, these less oxidized (or unoxidized) portions of the contact layers are also less transparent to visible light than the more oxidized portions of the contact layers. So, in the case of gradual oxidation: (a) the highly oxidized portions of the progressively oxidized contact layers 7 and 11 (and / or 17 and 21) are more transparent to visible light and allow the coating 27 to maintain good visible transmittance, while (b) the less oxidized portions of the progressively oxidized contact layers better support the infrared (IR) reflecting layer (infrared (IR) reflecting layers) 9, 19 during heat treatment (HT), they provide good adhesion and ensure the adhesion of the coating.

The embodiment of the present invention in Fig. 3 (b) is similar to the embodiment shown in Fig. 3 (a), except that only one of the contact layers in contact with the infrared (IR) reflecting layer is gradually oxidized. In this particular embodiment, the upper contact layer is gradually oxidized (upper contact layers 11, 12 are gradually oxidized) as discussed above, while the lower layer is not gradually oxidized and is substantially oxidized or is oxidized to at least about 50%. In certain embodiments of the present invention, all four non-crystalline contact layers 7, 11, 17 and 21 may thus be gradually oxidized, while in other embodiments only the upper contact layers 11 and 21 may be gradually oxidized. In still other embodiments of the present invention, the three contact layers may be oxidized gradually, or alternatively only one of the contact layers may be oxidized gradually. While NiCrOx is the preferred material for making progressively oxidized contact layers, those skilled in the art are also familiar with other materials that can be used interchangeably (e.g. that the silver double layer coating system can maintain good transmittance and good low E properties, even when using HT.

Fig. 4 shows how a gradually oxidized contact layer 7, 17 can be applied to a substrate as part of a coating according to an exemplary embodiment of the present invention by asymmetrically introducing oxygen gas into the area of the target. The substrate 1 with part of the layer system thereon passes in the D direction through the sputter coater. Sputtering target 51 in sheath 53 may include a NiCr target or any Ni-containing target discussed above when the contact layer (e.g., layer 7) is to be manufactured with or includes NiCrO.x. Other metallic or ceramic targets can be used when other materials are to be used as the contact layer (s). As the substrate 1 moves in the direction D below the disc 51, gas is introduced around the disc on both sides 57 and 59 thereof.

PL 219 129 B1

At one side 57 of target 51 is introduced at least gaseous oxygen (e.g., O2) (i.e. an oxygen flux of about 30 ml / min to about 60 ml / min at 4.1 kW) and optionally a mixture of oxygen and an inert gas such as argon (Ar) to the coating zone below and / or near the target. However, less oxygen gas is used on the other side 59 of target 51 and more other gas, such as argon, is introduced into the coating zone below and / or near the target. For example, the gas flowing from the side 57 of the target may include any of the following mixtures: (a) 100% oxygen, (b) a 70/30 oxygen / argon mixture, (c) a 50/50 oxygen / argon mixture, (d) a mixture 30 / 70 oxygen / argon, or (e) a 50/25/25 oxygen / argon / nitrogen mixture; while the gas flowing from the other side 59 of the target may contain (a) 100% argon or any other inert gas, (b) a 50/50 argon / nitrogen mixture or (c) a 90/10 argon / oxygen mixture. Thus, the flow of oxygen gas is greater on the side 57 of the target than that on the other side 59. Thus, when the substrate 1 passes under the target 51, the first part of the applied layer 7 due to the presence of oxygen gas is more oxidized on the side 57 of the target, while when a further part of the applied layer 7 is significantly less oxidized due to the lack of gaseous oxygen at the exit side of the target. Thus, near target 51, the substrate first passes through the sputter coating area enriched with oxygen gas and then passes through the sputter coating area depleted in oxygen gas. After the layer 7 of Fig. 1 has been applied, the substrate advances and target 60 may be used to sputter the coating layer 9 onto the substrate from the previously applied layers.

The amounts of oxygen and / or other gases can of course be adjusted in any desired manner to the degree of oxidation of the contact layers. When a gradual oxidation of the contact layer (s) 11, 21 on the upper side of the infrared (IR) reflecting layer 9, 19 is desired, the gas stream shown in Fig. 4 and described above, the more oxygen containing stream is on the target side 59, the less oxygen containing or oxygen free stream is on the target side 57.

Examples 1-3

The following three examples of coated articles were made in accordance with certain aspects of the present invention. For each of the three examples, the coating / layer 27 system shown in Fig. 5 was cathodically sputtered onto a large 2.1 mm thick clear soda lime glass substrate 1, and a specimen of at least 76.2 mm x 76.2 mm was cut. mm (3 in x 3 in). A six-chamber sputter coating device from Leybold Tetra-G was used to sputter the coatings 27 on substrates 1. Each chamber contained 5 cathodes, i.e. the sputter coating device had a total of 30 cathode targets. In cathode numbering, the first digit is used to identify the chamber of the cathodic coating apparatus and the second digit is used to identify the position of the cathode in that chamber. For example, cathode number 32 is the second cathode (second digit) in the third sputter chamber. Cathode numbers C13, C14, C23, C62, C31, C32, C62, C64 and C65 were Twin Mag II cathodes; the C42 cathode was a C-Mag type double cathode; and cathodes C44, C51 and cathodes C44, C51 and C53 were planar cathodes. It is known to those skilled in the art that the first half of the coating 27 can be applied in the cathodic coater and then the article can be reintroduced into the device to apply the second half of the coating to the substrate. In the cathodic coater, layers 7-11 and 17-21 were cathodically sputtered onto the substrate using direct current, while other layers were cathodically sputtered onto the substrate using a medium frequency alternating current type system. The following "*" indicates an Al content of about 10%. The transmission speed for each example was 2.6 m / min. The apparatus systems and process conditions for the three examples are given in Table 5. All gas flow rates (e.g., oxygen, argon, nitrogen) are given in ml / min. In the following examples, although not specified in the cards, the oxygen flow was blocked on the sides of the above-mentioned NiCr targets to gradually oxidize the contact layers 11 and 21 as shown in Fig. 3 (B) (that is, in these examples only two contact layers 11 and 21 above the respective silver layers were gradually oxidized). Volts are for cathode voltage and amps (A) are for cathode current. "Tr" means trimmer, console trimmer (Tr) trimmer (Tr) Mid and pump trimmer (Tr) are measured in ml / min. Pressures were measured in mbar x 10-3. The gas trimmer deals with individually adjustable gas jets along the cathode length to make corrections for layer thickness uniformity. The NiCr targets were approximately 80/20 NiCr targets. The method for each example was split into three separate tabs (ie, parts 1-3) because too much information was provided; only the cathode and target data are given for all three cards in each example for ease of reference. Both silicon nitride layers 5 and 15 were Si-rich across all thicknesses (all thicknesses); as can be seen, much more inert argon (Ar) gas than nitrogen gas was used for sputtering these silicon nitride layers.

TABLE 5. Coating apparatus and methods for Examples 1-3.

Example 1.

Example 1 (part 1)

<td>cathode</td><td>shield</td><td>tension, V</td><td>power, kW</td><td>flow Ar, ml / min</td><td>O2 flow, ml / min</td><td>N2 flow, ml / min</td>

Example 1 (part 2, continued from part 1 above (common cathode and target)

<td>cathode</td><td>shield</td><td>ampere, AND</td><td>tension tank V</td><td>frequency, kHz</td><td>gas trimmer</td>

<td> 42</td><td>Si *</td><td>not given</td><td> 230</td><td> 26,18</td><td>N2</td>

PL 219 129 B1 cont. Example 1

<td> 42</td><td>Si *</td><td>not given</td><td> 220</td><td> 26,18</td><td>N2</td>

Example 1 (part 3, continued from part 1-2 above [common cathode and target])

<td>cathode</td><td>shield</td><td>console Tr</td><td>median Tr</td><td>pump Tr</td><td>pressure</td><td>lambda</td><td>active lambda</td>

Example 2 (part 1)

<td>cathode</td><td>shield</td><td>tension, V</td><td>power, kW</td><td>stream Ar, ml / min</td><td>stream O2, ml / min</td><td>stream of N2 ml / min</td>

PL 219 129 B1 cont. example 2

Example 2 (part 2 continued from part 1 above (common cathode and target)

<td>cathode</td><td>shield</td><td>ampere, AND</td><td>tank voltage V</td><td>frequency, kHz</td><td>gas try mera</td>

<td> 42</td><td>Si *</td><td>not given</td><td> 230</td><td> 26,18</td><td>N2</td>

<td> 42</td><td>Si *</td><td>not given</td><td> 230</td><td> 26,18</td><td>N2</td>

PL 219 129 B1

Example 2 (part 3, continued from part 1-2 above (common cathode and target)

<td>cathode</td><td>shield</td><td>console Tr</td><td>median Tr</td><td>pump Tr</td><td>pressure</td><td>lambda</td><td>active lambda</td>

Example 3 (part 1)

<td>cathode</td><td>shield</td><td>tension, V</td><td>power, kW</td><td>stream Ar, ml / min</td><td>stream O2, ml / min</td><td>stream N2, ml / min</td>

PL 219 129 B1 cont. example 3

Example 3 (part 2, continued from part 1 above (common cathode and target)

<td>cathode</td><td>shield</td><td>ampere, AND</td><td>tension tank V</td><td>frequency, kHz</td><td>gas trimmer</td>

<td> 42</td><td>Si *</td><td>not given</td><td> 230</td><td> 26,18</td><td>N2</td>

<td> 42</td><td>Si *</td><td>not given</td><td> 230</td><td> 26,18</td><td>N2</td>

Example 3 (part 3, continued from part 1-2 above (common cathode and target)

<td>cathode</td><td>shield</td><td>console Tr</td><td>median Tr</td><td>pump Tr</td><td>pressure</td><td>lambda</td><td>active lambda</td>

PL 219 129 B1 cont. example 3

After sputtering the coatings 27 of Examples 1-3 onto the respective substrates 1 as above, they were tested and measured as shown in Table 6 (i.e. in monolithic form). The heat treatment was performed by placing the coated articles in an oven heated to a temperature of about 625 ° C for about 5 minutes.

TABLE 6. Examples 1-3. Monolithic system before and after heat treatment (HT)

<td>properties</td><td>example 1</td><td>example 2</td><td>example 3</td>

<td>Tvis, III. A, 2 degrees (before HT)</td><td> > 70%</td><td> > 70%</td><td> > 70%</td>

<td>Tvis, III. A, 2 degrees (after HT)</td><td> > 78%</td><td> > 78%</td><td> > 78%</td>

<td>Rs (ohm / square, before HT)</td><td> 4,43</td><td> 4,37</td><td> 4,27</td>

<td>Rs (ohm / square, post HT)</td><td> 3,46</td><td> 3,33</td><td> 3,44</td>

<td>En (before HT)</td><td> < 0,06</td><td> < 0,06</td><td> < 0,06</td>

<td>En (after HT)</td><td> < 0,05</td><td> < 0,05</td><td> < 0,05</td>

<td>haze (after HT)</td><td> 0,15</td><td> 0,28</td><td> 0,22</td>

Thereafter, all the heat treated monolithic coated articles of Examples 1-3 were laminated to another suitable 2.1 mm thick clear soda lime glass substrate 1, with a PVB layer of about 0.8 mm placed between the substrates in a known manner. wherein a coating 27 has been placed on the surface 2 as shown in Fig. 2. Thereafter, coated laminated articles obtained (see Fig. 2) was tested and measured and found to have the following properties given in Table 7. In Table 7, the side of the glass (G) is the same as the exterior of the vehicle in Fig. 2, while the side of the film (F) is the same as inside the vehicle in Fig. 2.

Table 7. Color for Examples 1-3 in post-HT laminated form (i.e., as in Fig. 2)

<td>value and measurement</td><td>example 1</td><td>example 2</td><td>example 3</td>

<td>III. C. 2 degrees</td><td></td><td></td><td></td>

<td>transmission (TY or Tvis),%</td><td> 75,37</td><td> 75,32</td><td> 74,68</td>

PL 219 129 B1 cont. table 7

<td>glass side reflectance (G) RgY,%</td><td> 7,93</td><td> 8,02</td><td> 8,22</td>

<td>layer / coating side reflectance (F), RfY,%</td><td> 7,83</td><td> 7,85</td><td> 8,11</td>

<td>III. D65. 2 degrees</td><td></td><td></td><td></td>

<td>transmission (TY or Tvis),%</td><td> 75,69</td><td> 75,34</td><td> 74,71</td>

<td>glass side reflectance (G) RgY,%</td><td> 7,93</td><td> 8,03</td><td> 8,22</td>

<td>layer / coating side reflectance (F), RfY,%</td><td> 7,84</td><td> 7,85</td><td> 8,12</td>

<td>III. A. 2 degrees</td><td></td><td></td><td></td>

<td>transmission (TY or Tvis),%</td><td> 75,27</td><td> 75,23</td><td> 74,78</td>

<td>III. C. 10 degrees</td><td></td><td></td><td></td>

<td>transmission (TY or Tvis),%</td><td> 75,16</td><td> 75,08</td><td> 74,91</td>

<td>glass side reflectance (G) RgY,%</td><td> 8,01</td><td> 8,14</td><td> 8,31</td>

<td>layer / coating side reflectance (F), RfY,%</td><td> 7,87</td><td> 7,90</td><td> 8,16</td>

<td>III. D65. 10 degrees</td><td></td><td></td><td></td>

<td>transmission (TY or Tvis),%</td><td> 75,19</td><td> 75,12</td><td> 74,92</td>

PL 219 129 B1 cont. table 7

<td>glass side reflectance (G) RgY,%</td><td> 8,01</td><td> 8,14</td><td> 8,31</td>

<td>layer / coating side reflectance (F), RfY,%</td><td> 7,88</td><td> 7,91</td><td> 8,16</td>

<td>III. A. 10 degrees</td><td></td><td></td><td></td>

<td>transmission (TY or Tvis),%</td><td> 75,20</td><td> 75,15</td><td> 74,85</td>

Moreover, it was found that in each of Examples 1-3, chemically and mechanically stable articles were obtained as defined below, both before HT and after HT.

As can be seen from the above, more Ar gas than N gas was used during the sputtering of each silicon nitride layer. In the examples, the Ar / N ratio was about 225/165 (i.e. 1.36) as stated above. In preferred embodiments of the present invention, the Ar / N ratio is from about 1.15 to about 3.0, more preferably from about 1.20 to about 2.0, and most preferably from about 1.2 to about 1.5. This ratio, in which more inert gas (e.g., Ar) than nitrogen was used for sputtering the silicon nitride layers, made it possible to obtain Si-rich silicon nitride layers as discussed above.

Table 8 below compares the viewing characteristics of the HT laminate of Example 1 at normal angle (VA) with viewing after changing the viewing angle by 60 degrees (that is, when the VA is 60 degrees different from the normal VA by 60 degrees). As can be seen, Example 1 gives very good color fastness over a wide range of viewing angles such that an observer looking at the laminate of Example 1 both at the normal angle VA (i.e. in a straight line such that the line or location is perpendicular to the plane of the article) and also at a VA angle of 60 degrees, he would hardly notice any color change at all. This is due to the small value of Aa * glass side refractive index (G) (i.e., Aa * is the difference between a * under normal VA and after changing the viewing angle by 60 degrees). Note: a color at 60 degrees represents a standard observer according to III. D65, 10 degrees.

Table 8. Color change when the viewing angle (VA) is changed by 60 degrees (example 1)

<td>properties</td><td>example 1 (normal VA)</td><td>example 1 (after VA change by 60 °)</td>

<td>T.vis</td><td> 75,27%</td><td>not given</td>

<td>a * T</td><td> -2,2</td><td>not given</td>

<td>b * T</td><td> 4,2</td><td>not given</td>

<td>T.solar</td><td> 46,75%</td><td></td>

<td>Rsolar</td><td> 30,15</td><td> 36,11</td>

<td>Aa * g (VA change by 60 degrees)</td><td> 1,83</td><td>same</td>

<td>AL * g (VA change by 60 degrees)</td><td> 11,4</td><td>same</td>

PL 219 129 B1

As seen above, in Table 8, the change in refractive index Aa *g (for a change of VA by 60 degrees) in accordance with some aspects of the present invention is preferably no greater than 3.0, more preferably no greater than 2.0. In Table 8 it was 1.83. Further, in some embodiments of the present invention, the Tsolar value is preferably no greater than 50%, more preferably no greater than 48%, and most preferably no greater than about 47%.

Certain embodiments of the present invention after heat treatment and lamination were rated as follows for the glass side reflection color (G):

Table 9

<td>parameter</td><td>normal VA</td><td>VA change of 60 degrees</td>

Certain terms are mainly used in the glass coating art, especially to describe the properties and changes in the sunlight characteristics of coated glass. Such terms are used according to their known normal meanings. For example, the description uses:

The intensity of reflected visible light, that is, "reflectance", is defined as a percentage and is reported as RxY or Rx (that is, as the Y value given below in ASTM E-308-85), where "X" is either "G" for glass side or "F" for layer side. "Glass side" (i.e. "G") means viewed from the side of the glass substrate opposite to the side where the coating is placed, while "layer side" (i.e. "F") means viewed from the side of the glass substrate where there is a shell.

The color properties were measured and listed below using the CIE LAB 1976 a * and b * a * and b * coordinates and scale (i.e. CIE 1976 a * b * plot, observer III. CIE-C 2 degrees), with:

L * stands for brightness units (CIE 1976), and * stands for red-green units (CIE 1976), b * stands for yellow-green units (CIE 1976).

Other similar coordinates with the subscript "h" may be equivalently used to denote normal use of the Hunter method (ie units) of Ill. C, observer of 10 degrees or CIE LUV coordinates u * v *. These scales in this specification are in accordance with ASTM D-2244-93 "Standard Test Method for Calculation of Color Differences from Instrumentally Measured Color Coordinates", 9/15/93, extended by 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 "emission factor" (or "emittance") and "transmittance" are understood in the art and used herein in accordance with their well-known meanings. Thus, the term "transmittance" means, for example, solar transmittance, which consists of visible light transmittance (TY of Tvis), infrared energy (IR) transmittance (TIR) and UV light transmittance (TUV). Total solar energy transmittance (TS or Tsolar) can be defined as a weighted average of these other values. Regarding these transmittances, visible transmittance for building purposes can be characterized using the Iluminant C, 2 degree technique; while the visible light transmittance for the automotive industry can be characterized using the standard III. A 2 degree technique; (for these techniques, see, for example, ASTM E-308-95, which is hereby incorporated by reference). As for the emission factor, a specific infrared (IR) range is used (that is, the range 2,500 - 40,000 nm). Various standards for the calculation and measurement of any and / or all of the above parameters can be found in the above-mentioned provisional application, with priority being claimed in this application.

The term Rsolar refers to the total solar energy reflectance (glass side); it is the weighted average of IR reflectance, visible reflectance and UV reflectance. The value of this term can be calculated in accordance with DIN 410 and ISO 13837 (12/98) Table 1, p. 22 for vehicle applications and in accordance with the ASHRAE 142 standard for construction applications, both of which are incorporated herein as links.

"Haze" is defined as follows. Light scattered in many directions causes a loss of contrast. The term "haze" is used herein in accordance with ASTM D 1003, which defines haze as the percentage of light that deviates on average by more than 2.5 ° from the beam when passed through.

Incident light. Haze can be measured with a Byk Gardner haze meter (all dimensionless haze values in this specification were measured with such a haze meter).

The "emission factor" (or "emittance") (E) is a measure or property of both absorption and reflectance for a given wavelength. It is usually represented by the formula:

E = 1 - (reflectance) of the layer

In construction, the emission factor values are particularly important in the so-called "middle range", sometimes also called the "far range" of the infrared (IR) spectrum, i.e. in the range from about 2,500 to about 40,000 nm as defined for example in WINDOW 4.1 program, LBL35298 (1994) by Lawrence Berkeley Laboratories as set forth in the reference below. The term emission factor is used herein to refer to the values of the emission factors measured in the infrared range as defined in ASTM Standard E 1585-93 "Standard Test Method for Measuring and Calculating Emittance of Architectural Flat Glass Products Using Radiometric Measurements". The standard and its provisions are incorporated herein by reference. In this standard, the emission factor is expressed as the hemispherical emission factor (Eh) and as the normal emission factor (En).

Actual data collection for measuring such emission factor values is done in the usual way and can be done, for example, by using 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 in accordance with the meaning given. It is given in ohms per square unit. Generally speaking, the term refers to the resistance in ohms for any square of the layer system on the glass substrate to the 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. For example, "sheet resistance" may be advantageously measured with a four point test ohmmeter or alternatively a four point test ohmmeter with a Magnetron Instruments Corp. head type Model M-800 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 in 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 (i.e., that the layered system is "chemically resistant" or that it is considered "chemically stable" or that it is "chemically stable") if at least half of the layering of the sample remains after the test. 5 minutes.

"Mechanical durability" is defined herein on the basis of the following tests. The trial uses a Pacific Scientific Abrasion Tester (or equivalent) in which a nylon brush (e.g., Hand & Nail Brush, Model 1280 manufactured by Wright Bernet of Franklin Park, Illinois) is cycled over the layering of 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 durable" or to have "mechanical durability".

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

Many other properties, changes, and improvements can be determined by one of ordinary skill in the art from the above disclosure. For example, without limitation, the above-mentioned progressively oxidized contact layers and Si-rich silicon nitride layers may be used both in a stack with single silver layers and in a stack with the double silver layers disclosed herein. Such features, changes and improvements are therefore considered part of the present invention, the scope of which will be defined by the appended claims.

Contents8

201 members in 8 offices

This recordMember, by publication datePriority claim

Priority claims6

Priority claims
Document	Office	Kind	Date
21710100	United States of America	P	2000-07-10
79422401	United States of America	A	2001-02-28
09794224	–	–	–
60217101	–	–	–
US20000217101P	–	–	–
US20010794224	–	–	–

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WO0204375A3	World Intellectual Property Organization (WIPO)	A3	2002-04-25
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EP1238950A2	European Patent Office (EPO)	A2	2002-09-11
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Showing 100 of 201

Heat treatable low-e coated articles and methods of making same

Abstract

Term

PL 219 129 B1

PL 219 129 B1

PL 219 129 B1

PL 219 129 B1

PL 219 129 B1

PL 219 129 B1

PL 219 129 B1

PL 219 129 B1

Priority claims6

Members201

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Titles2

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