Heatable low-E insulated glass comprising two titanium nitride-based layers

Abstract

A glass article having solar control properties, comprising at least one glass substrate having a stack of layers, wherein said stack sequentially comprises, from the surface of the substrate, a first module M1 made of one or more layers of a dielectric material, a first layer TiN1 containing titanium nitride, a second module M2 made of one or more layers of a dielectric material, a second layer TiN2 containing titanium nitride, a third module M3 made of one or more layers of a dielectric material, wherein the cumulative sum of the thicknesses of the TiN1 and TiN2 layers containing titanium nitride is from 25 to 60 nm, wherein the third module M3 comprises a layer containing silicon oxide or silicon oxynitride having a thickness greater than 10 nm, and wherein an intermediate layer IL of titanium, aluminum, silicon, an alloy of at least two of these elements or nickel-chromium alloy is deposited between said second layer TiN2 and said third module M3, the intermediate layer IL having a thickness of from 0.5 nm to 7 nm.

Description

TECHNICAL FIELD

[0001] The present invention relates to low-emissivity insulating laminated glass equipped with a stack comprising a thin "functional" layer (currently based on titanium nitride), i.e., acting on solar radiation and / or thermal radiation by substantially reflecting and / or absorbing near-infrared (solar) or far-infrared (thermal) radiation. The application that the present invention more specifically addresses is first of all laminated glass for vehicle glazing, such as side windows, skylights or rear windows. Without departing from the context of the present invention, this laminated glass can also be used in the field of the construction industry as solar control laminated glass. BACKGROUND ART

[0002] The "functional" or "active" layer should be understood in the meaning of the present patent application as representing a stack of layers that confers on the stack most of its thermal insulation properties. Generally, a stack made of thin layers assembled on laminated glass very basically confers on the laminated glass significantly improved insulation properties by the inherent properties of the active layer. Compared with the other layers, this layer acts on the flow of thermal infrared radiation passing through the laminated glass, and the other layers are generally made of dielectric materials and generally mainly have the chemical or mechanical protection function of the functional layer. Dielectric materials are understood to mean materials that exhibit a high resistivity in the form without a large amount of impurities, such as a resistivity greater than 10 10 ohm·meters (Ω·m) at 25 °C.

[0003] This laminated glass equipped with a stack of thin layers acts on the incident solar radiation by substantially absorbing the incident radiation by one or more functional layers or substantially reflecting by these same layers.

[0004] They are grouped together under the name of solar control laminated glass. They are commercially available and are basically used for:

[0005] - providing basic protection for the passenger compartment (motor vehicle) or a dwelling against solar radiation and preventing it from overheating, and this laminated glass is described in the industry as solar protection glazing,

[0006] - or basically providing thermal insulation for a dwelling and preventing heat loss, and these glasses are described as insulating glass.

[0007] Thermally insulating laminated glass should be understood as representing a laminated glass equipped with at least one functional layer conferring on it reduced energy losses, said layer exhibiting the property of reflecting IR radiation with a thickness of 5 to 50 micrometers. The functional layer for this function exhibits a high IR radiation reflection coefficient and is referred to as low-emissivity (or low-e). In applications, for example in the motor vehicle industry, it is often desirable to limit the heat entering the passenger compartment of a vehicle, that is to say to limit the energy transfer of solar radiation through the laminated glass. The conventional parameter used in the art to evaluate this ability is the normal emissivity ε of the laminated glass n , calculated as in Standard ISO 10292 (1994), Annex A

[0008] Generally, all the optical and thermal properties given in this specification are obtained according to the principles and methods described in International Standards ISO 9050 (2003) and ISO 10292 (1994), relating respectively to the determination of the optical and energy properties of laminated glass used in glass for the building industry

[0009] At present, there is a particular search for laminated glass which additionally provides improved visual comfort, especially in the field of motor vehicles (as side windows, rear windows or also as sunroofs). To meet this need, one of the objects of the present invention is to provide suitable laminated glass which allows the passengers of a vehicle or the occupants of a building to be not or hardly visible from the outside in daylight, but to be able to see the external environment on the side where they are located without any trouble. Such laminated glass comprises from the outside a first glass substrate, preferably tinted in its bulk, bonded to a second substrate by an intermediate thermoplastic sheet, said intermediate thermoplastic sheet being made in particular of PVB, which may also be tinted, said second substrate being preferably made of clear glass and equipped with a stack of said layers, said stack of layers preferably being located on the face thereof exposed towards the interior of the passenger compartment. In accordance with this requirement, there is currently a need for a light transmittance of the structural article made of clear glass coated with this stack of layers to be between 20 and 40%, in order to obtain a final laminated glass with a light transmittance of less than 10%. In addition, there is also a need for a low light reflectance of the structural article made of clear glass coated with this stack of layers, especially when measured on the side of the article on which the stack is deposited, to be less than 10%, preferably about or less than 5%

[0010] Another essential property of laminated glass is its ability to withstand heat treatment and more particularly bending, especially in the field of vehicle laminated glass

[0011] This ability is generally first measured by the appearance (more precisely the absence) of physical damage after such treatment, said physical damage being cracks which appear for example in the coating and are highly visible to vehicle passengers

[0012] Another criterion is also the ability of the assembled glass that has undergone said heat treatment to maintain (or even improve) its thermal insulation properties, as measured by the aforementioned normal emissivity.

[0013] The most effective stacks currently on the market for solving the aforementioned complex problems are generally deposited by magnetron sputtering techniques and incorporate silver-type metal layers that operate substantially in a mode of reflecting most of the incident IR (infrared) radiation. Thus, these stacks are mainly used as low-emissivity (or low-e) types of assembled glass for thermal insulation in buildings as well as in vehicles. However, these layers are very sensitive to moisture, which means that they can hardly be used on single assembled glass and are therefore mainly used on double or laminated assembled glass on their face 2 or 3 in order to prevent moisture. The stacks according to the invention do not include such silver-type layers, or indeed do not include gold- or platinum-type layers or indeed do not include copper-type layers. More generally, the stacks according to the invention do not contain such noble metals, or contain them in very negligible amounts, especially in the form of inevitable impurities.

[0014] Other insulating assembled glasses based on stacks have been proposed, where titanium nitride or titanium oxynitride are used as one or more functional layers, with silicon nitride used as the aforementioned dielectric layer above and between said functional layers, for example in publications WO2019 / 002737 or US10294147B2. However, as reported below, experiments conducted by the applicant have shown that when the coatings of such assembled glass are subjected to heat treatment such as bending (as currently practiced in the technical field of the present application), they exhibit cracks.

[0015] Thus, in view of certain specific applications or arrangements, it has become necessary to develop novel and suitable stacks.

[0016] Based on the results obtained by the applicant's company, the above problems have been solved by the glass articles and assembled glasses now described. Summary of the Invention

[0017] According to a first aspect, the present invention relates to a glass article having solar control properties, more particularly useful for manufacturing vehicle assembled glass such as a car roof or for manufacturing architectural assembled glass for buildings, which comprises at least one glass substrate equipped with a stack of layers, wherein said stack successively comprises, starting from the surface of the substrate:

[0018] - A first module M1, consisting of one or more layers comprising a dielectric material and preferably based on a dielectric material,

[0019] - A first layer TiN1 containing titanium nitride,

[0020] - A second module M2, consisting of one or more layers comprising a dielectric material and preferably based on a dielectric material,

[0021] - A second TiN2 layer containing titanium nitride,

[0022] - A third module M3, consisting of one or more layers containing a dielectric material and preferably based on a dielectric material,

[0023] wherein the cumulative sum of the thicknesses of the TiN1 and TiN2 layers containing titanium nitride is 25 to 60 nm, wherein the third module M3 includes a layer containing silicon oxide or silicon oxynitride with a thickness greater than 10 nm, and wherein an intermediate layer IL of titanium, aluminum, silicon, an alloy of at least two of these elements, or a nickel-chromium alloy is deposited between the second TiN2 layer and the third module M3, and the thickness of the intermediate layer IL is 0.5 nm to 7 nm.

[0024] More particularly, the present invention relates to a glass article, especially vehicle or building glazing having solar control properties, which includes at least one glass substrate equipped with a stack of layers, wherein the stack sequentially includes from the surface of the substrate:

[0025] - A first module M1, which includes a layer based on a dielectric material with a thickness t1 or a set of layers based on a dielectric material with a cumulative thickness t1, - A first TiN1 layer, which contains titanium nitride and has a thickness of 10 nanometers to 30 nanometers,

[0026] - A second module M2, which includes a layer based on a dielectric material with a thickness t2 or a set of layers based on a dielectric material with a cumulative thickness t2, - A second TiN2 layer, which contains titanium nitride and has a thickness of 10 nanometers to 30 nanometers,

[0027] - A third module M3, which includes a layer based on a dielectric material with a thickness t3 or a set of layers based on a dielectric material with a cumulative thickness t3, wherein the cumulative sum of the thicknesses of the TiN1 and TiN2 layers containing titanium nitride is 25 to 60 nm,

[0028] wherein the third module M3 includes a layer containing silicon oxide or silicon oxynitride, with a thickness greater than 10 nm, preferably greater than 20 nm, and

[0029] wherein an intermediate layer IL of titanium, aluminum, silicon, an alloy of at least two of these elements, or a nickel-chromium alloy is deposited between the second TiN2 layer and the third module M3, and the thickness of the intermediate layer IL is 0.5 nm to 7 nm, preferably 1 nm to 6 nm.

[0030] It has been found that such an article can effectively solve the above technical problems.

[0031] The preferred embodiments of the present invention are reported in the appended claims, which, of course and if appropriate, can be combined with each other.

[0032] According to other preferred embodiments, but not all reported in the claims:

[0033] - The cumulative thickness TiN1 + TiN2 of the first titanium nitride-based layer and the second titanium nitride-based layer is less than 50 nm, preferably less than 45 nm.

[0034] - The ratio of the thickness t1 / t3 is less than 0.55.

[0035] - The thickness TiN1 of the first titanium nitride-based layer is from 15 nm to 25 nm, inclusive.

[0036] - The thickness TiN2 of the second titanium nitride-based layer is from 15 nm to 25 nm, inclusive.

[0037] - The thickness t1 of the first module M1 is from 1 nm to 50 nm, inclusive,

[0038] - The thickness t1 of the first module M1 is less than 25 nm, particularly from 1 nm to 25 nm, inclusive, preferably from 4 nm to 20 nm, inclusive.

[0039] The thickness t2 of the second module M2 is from 20 nm to 100 nm, inclusive,

[0040] - The thickness t2 of the second module M2 is from 20 nm to 100 nm, inclusive, preferably from 25 nm to 80 nm, inclusive.

[0041] - The thickness t3 of the third module M3 is from 20 nm to 65 nm, inclusive, preferably from 25 nm to 60 nm, inclusive, and very preferably from 30 nm to 50 nm, inclusive.

[0042] - The coating does not contain a silver-based or gold-based layer.

[0043] - The coating does not contain a layer based on a transparent conductive layer (TCO) such as ITO or SnO2:F.

[0044] - M1 consists of a single layer based on a dielectric material.

[0045] - M1 comprises and more preferably consists of a single layer containing or based on silicon nitride or silicon oxide, preferably a single layer containing or based on silicon nitride.

[0046] - M2 is a single layer containing or based on a single dielectric material, the single dielectric material preferably being selected from silicon oxide or silicon oxynitride, preferably containing or based on silicon dioxide.

[0047] - M2 is a group of layers made of a dielectric material, preferably including layers containing or based on a material selected from silicon oxide or silicon oxynitride.

[0048] - M2 includes at least one layer containing silicon nitride and one layer containing silicon oxide, and one or more intermediate layers IL are deposited between the titanium nitride layer and the layer containing silicon oxide.

[0049] - M2 is a set of layers made of a dielectric material, and the set is composed of one or more layers containing or based on a material selected from silicon oxide or silicon oxynitride and one or more layers containing or based on silicon nitride.

[0050] - M2 is a set of layers made of a dielectric material, and the set is composed of a first layer containing or based on silicon nitride, a layer containing or based on a material selected from silicon oxide or silicon oxynitride, and a second layer containing or based on silicon nitride.

[0051] - The silicon oxynitride-based layer is characterized by a refractive index between an unnitrided oxide layer and an unoxidized nitride layer at 550 nm. The silicon oxynitride-based layer preferably has a refractive index greater than 1.55, 1.60 or 1.70 or a refractive index between 1.55 and 1.99 at 550 nm; a refractive index between 1.60 and 1.97; a refractive index between 1.70 and 1.95 or a refractive index between 1.70 and 1.90.

[0052] - The above-mentioned silicon oxynitride material exhibits a molar ratio of O / (O + N) of 0.94 to 0.25, preferably a molar ratio of O / (O + N) of 0.87 to 0.36.

[0053] - M3 does not include a layer containing silicon nitride.

[0054] - M1 and M3 are single layers.

[0055] - The TiN1 layer has a thickness greater than that of the TiN2 layer.

[0056] - The TiN2 layer has a thickness greater than that of the TiN1 layer

[0057] - The thickness of one or more intermediate layers IL is 1 to 6 nm, more preferably 2 to 5 nm, including the limits.

[0058] - One or more intermediate layers IL are made of titanium, aluminum, silicon, an alloy of at least two of these elements, and more preferably made of titanium.

[0059] - The glass substrate on which the stack is deposited is made of transparent glass.

[0060] - The assembled glass includes two glass substrates assembled from thermoplastic sheets, and the assembled glass is equipped with the stack of layers, and the stack is preferably located on the surface of the substrate facing the outer surface of the assembled glass.

[0061] - The aforementioned assembled glass includes a first glass substrate, preferably colored in its body, bonded to a second substrate through an intermediate thermoplastic sheet, in particular an intermediate thermoplastic sheet made of PVB. The second substrate is made of transparent glass and is equipped with a stack of layers, which is preferably located on the face exposed on its outer surface facing the assembled glass. By colored in its body is meant that the substrate contains in its glass composition elements intended to impart color to it (i.e., elements different from "transparent" glass), in particular elements such as cobalt, iron, selenium, and in fact even chromium, which may also be intended to reduce its light transmittance.

[0062] - The one or more glass substrates are tempered or bent.

[0063] Preferably, the titanium nitride layer is based on titanium nitride or, more preferably, consists essentially of titanium nitride.

[0064] The titanium-based layer according to the invention contains, for example, more than 50% by weight of titanium nitride, preferably more than 80% by weight or even more than 90% by weight of titanium nitride.

[0065] The titanium nitride according to the invention does not have to be stoichiometric (Ti / N atomic ratio of 1), but can be over-stoichiometric or sub-stoichiometric. According to an advantageous embodiment, the N / Ti ratio is from 1 to 1.2. In addition, the titanium nitride according to the invention can contain a small amount of oxygen, for example from 1 mol% to 10 mol% of oxygen, in particular from 1 mol% to 5 mol% of oxygen.

[0066] According to a particularly preferred form, the titanium nitride layer according to the invention corresponds to the general formula TiN x O y , where 1.00 < x < 1.20 and where 0.01 < y < 0.10.

[0067] However, once deposited in the form of a thin layer, the dielectric material can contain additional elements used, which significantly increase its electrical conductivity, for example, to improve the cathodic sputtering efficiency of the precursor material constituting the magnetron target. Preferably, modules M1, M2, and M3 include one or more layers selected from materials based on silicon nitride, silicon oxynitride, and silicon oxide or are composed thereof. Materials based on silicon nitride, silicon oxide, or silicon oxynitride are, for example, materials mainly and preferably made essentially of such a compound, but which can nevertheless also contain other minor elements, especially as substitutes for cations, especially to facilitate deposition in the form of a thin layer by conventional techniques such as magnetron sputtering as described above. For example, layers according to the invention made of silicon nitride or silicon oxynitride, in fact even of silicon oxide, especially those deposited by magnetron, usually contain additional elements such as Al, Zr, B, etc., the proportion of which can be, for example, up to 10 atomic %, even sometimes up to 20 atomic % or even up to 30 atomic % based on the total amount of cations (i.e., atoms other than O and N within the layer).

[0068] The assembled glass according to the invention can be a single assembled glass comprising (possibly tinted in its mass) a single glass substrate, on face 2 of which the stack of thin layers is located, the faces of the substrate being numbered from the outside to the inside of the building or passenger compartment it is equipped for.

[0069] According to another embodiment, especially for the field of motor vehicles, the assembled glass according to the invention can be a laminated assembled glass, which includes two glass substrates assembled by a thermoplastic sheet, and the assembled glass is equipped with a stack of layers as described above. Preferably, the stack is deposited on the face of the substrate facing the inside of the building or passenger compartment it is equipped for.

[0070] The above glass articles can be very significantly tempered and / or bent.

[0071] The method for manufacturing the article / assembled glass according to the invention includes, for example, at least the following stages:

[0072] - Introducing the glass substrate into a cathodic sputtering device,

[0073] - Depositing at least a bottom layer of a dielectric material in a first compartment,

[0074] - Sputtering a titanium target by a plasma generated from a nitrogen-containing gas in a subsequent compartment,

[0075] - Depositing at least an intermediate layer of a dielectric material in a subsequent compartment,

[0076] - Sputtering a titanium target by a plasma generated from a nitrogen-containing gas in a subsequent compartment,

[0077] - In a subsequent compartment, at least one covering layer of dielectric material is deposited.

[0078] Furthermore, when appropriate within the stack, in an intermediate compartment, a metal target made of titanium, aluminum, silicon, an alloy of at least two of these elements, or nickel-chromium alloy is sputtered by a plasma generated from argon gas for depositing the above-mentioned IL intermediate layer.

[0079] In this specification, the terms "underlying layer" and "covering layer" refer to the respective positions of the layer relative to one or more functional layers in the stack, which is supported by a glass substrate. In particular, when the stack contains a single underlying layer and a single covering layer, the underlying layer is the layer in contact with the glass substrate, and the covering layer is the outermost layer of the stack, facing away from the substrate.

[0080] The term "intermediate layer" denotes one or more layers located between two associated layers respectively disposed thereunder and thereon, one of the associated layers typically being a layer containing titanium nitride.

[0081] Within the meaning of the present invention, the thickness of a layer should be understood to mean the true geometric thickness of the layer, as can be specifically measured by conventional electron microscopy techniques or similar techniques.

[0082] The coatings according to the present invention are generally deposited by a deposition technique of the magnetic field-assisted vacuum sputtering type of the material or material precursor to be deposited, which deposition technique is generally known in the art as the magnetron sputtering technique. This technique is currently widely used and well-known, especially when the coating to be deposited consists of a more complex stack of continuous layers with a thickness of several nanometers or dozens of nanometers. One or more metal intermediate layers (IL) according to the present invention are deposited by sputtering a target made of the corresponding metal in a neutral atmosphere of an inert gas (usually argon). For example, an intermediate layer made of Ti is deposited by sputtering a titanium target in a 100% argon atmosphere. However, it is contended that during a heat treatment process, such as in the bending or tempering of the final assembled glass, a part of this intermediate layer may be partially oxidized or nitrided. Detailed Description

[0083] The present invention and its advantages are described in more detail below by non-limiting examples, which are according to the present invention and comparative. In all examples and the specification, unless otherwise stated, the thicknesses given are geometric thicknesses.

[0084] All substrates of the examples are made of transparent glass of type Planiclear with a thickness of 2 mm sold by Saint-Gobain Glass France. All layers are deposited in a known manner by magnetic field-assisted cathode sputtering, generally known as magnetron cathode sputtering as described above.

[0085] In a known manner, different successive layers are deposited in successive compartments of a cathodic sputtering device, each compartment being equipped, in a suitable atmosphere, with a specific metal target made of Si (doped with aluminum) or Ti, as selected for depositing a specific layer of the stack.

[0086] More specifically, a silicon nitride layer is deposited in a compartment of the device by a metal silicon target (doped with 8% by weight of aluminum) in a reactive atmosphere containing nitrogen mixed with argon. Thus, the silicon nitride layer also contains aluminum.

[0087] More specifically, a silicon oxide layer is deposited in a compartment of the device by the same metal silicon target (doped with 8% by weight of aluminum) in a reactive atmosphere containing oxygen mixed with argon. Thus, the silicon oxide layer also contains aluminum.

[0088] Thus, those skilled in the art will understand that, within the meaning of the present invention, these layers are considered to be based on silicon nitride or silicon oxide.

[0089] A titanium nitride layer is deposited in other compartments of the device by a pure metal titanium target in a reactive atmosphere containing only nitrogen and argon.

[0090] A titanium intermediate layer is deposited in a compartment of the device from the same pure metal titanium target in an atmosphere containing only argon.

[0091] The conditions for magnetron deposition of these layers are technically known in the art.

[0092] In a subsequent embodiment, the glass substrate is thus successively covered by a stack of layers including two functional layers made of titanium nitride (for the sake of convenience, subsequently denoted as TiN, even if the actual stoichiometry of the layer is not necessarily so). For all embodiments, the first module M1 placed between the glass surface and the first functional layer TiN1 is made of silicon nitride (for the sake of convenience, subsequently denoted as Si3N4, even if the actual stoichiometry of the layer is not necessarily so). Different configurations of the second module M2 and the third module M3 are experimented with using silicon nitride or silicon oxide (for the sake of convenience, subsequently denoted as SiO2, even if the actual stoichiometry of the layer is not necessarily so) to examine the ability of the resulting stack to withstand heating methods such as bending processes while providing thermal insulation properties, which varies with the materials used.

[0093] The deposition conditions are adjusted according to conventional techniques for magnetron deposition in order to obtain different stacks, the layer sequences and their thicknesses (in nanometers nm) of which are given in Table 1 below, starting from the glass surface:

[0094] [Table 1]

[0095]

[0096] *Comparison

[0097] **According to the present invention

[0098] Measurement of the characteristics of the assembled glass

[0099] The thermal and optical properties of the glass articles thus obtained are measured according to the following principles and criteria: 1°) Optical properties:

[0100] Measurements are made according to European standard ISO 9050 (2003). More specifically, according to light source D 65 , the light transmittance T Lc and light reflectance are measured on the R L side between 380 and 780 nm.

[0101] 2°) Thermal properties:

[0102] The thermal insulation property of the glass article is evaluated by determining the normal incidence emissivity ε n measured according to the conditions described in Appendix A of standard ISO 10292 (1994) on the inner face of the substrate of the stack covered with the layer before and after the thermal bending process.

[0103] Measure the light transmittance T L , light reflectance R Lc and light normal emissivity ε n values (in percentage) of the assembled glass equipped with the stack.

[0104] B - Results

[0105] The results obtained for the monolithic glass articles according to the above examples are grouped together in Table 2, as follows:

[0106] [Table 2]

[0107]

[0108] It is observed that such glass articles obtained according to the present invention exhibit a low light reflectance (less than 10%), while the light transmittance is not overly high (about 20 - 25%). This property enables such glass articles to be inserted as part of the assembled glass, such as skylights required by the market, which are suitable for allowing vehicle passengers or occupants of buildings equipped with such assembled glass to observe the outside of the vehicle unobstructed.

[0109] The articles according to Comparative Example 1 (according to the prior art cited above) could not withstand the applied heat treatment, as shown by the very large number of cracks observed. However, their energy insulation properties were acceptable, as represented by the low emissivity values. The assembled glasses according to Comparative Examples 2 and 3, in which several one or more silicon nitride layers had been replaced by one or more other silicon oxides, had better heat treatment resistance, but the thermal insulation properties were reduced.

[0110] By comparison, Examples 4 to 6 according to the invention presented the best compromise between heat treatment resistance and thermal insulation properties. In particular, Examples 5 and 6 showed emissivity values comparable to those obtained with the stacks in the prior art (see Example 1), but without cracks after bending processing.

Claims

1. A glass article having solar control properties, comprising at least one glass substrate equipped with a stack of layers, wherein said stack successively comprises, starting from the surface of said substrate: - A first module M1 made of at least one layer, said one or more layers comprising a dielectric material, - A first layer TiN1 comprising titanium nitride, - A second module M2 made of at least one layer, said one or more layers comprising a dielectric material, - A second layer TiN2 comprising titanium nitride, - A third module M3 made of at least one layer, said one or more layers comprising a dielectric material, wherein the cumulative sum of the thicknesses of the TiN1 and TiN2 layers comprising titanium nitride is 25 to 60 nm, wherein the third module M3 comprises a layer comprising silicon oxide with a thickness greater than 10 nm, and wherein an intermediate layer IL of titanium or a titanium alloy is deposited between the second layer TiN2 and the third module M3, the intermediate layer IL having a thickness of 0.5 nm to 7 nm, wherein the coating does not contain a silver-based or gold-based layer.

2. The glass article according to claim 1, comprising at least one glass substrate equipped with a stack of layers, wherein said stack successively comprises, starting from the surface of said substrate: - A first module M1, which includes a dielectric material-based layer with a thickness t1 or a set of dielectric material-based layers with a cumulative thickness t1, - A first TiN1 layer, which contains titanium nitride and has a thickness of 10 nanometers to 30 nanometers, - A second module M2, which includes a dielectric material-based layer with a thickness t2 or a set of dielectric material-based layers with a cumulative thickness t2, - A second TiN2 layer, which contains titanium nitride and has a thickness of 10 nanometers to 30 nanometers, - A third module M3, which includes a dielectric material-based layer with a thickness t3 or a set of dielectric material-based layers with a cumulative thickness t3, wherein the cumulative sum of the thicknesses of the TiN1 and TiN2 layers comprising titanium nitride is 25 to 60 nm, wherein the third module M3 includes a layer comprising silicon oxide with a thickness greater than 10 nm, and wherein an intermediate layer IL of titanium or a titanium alloy is deposited between the second layer TiN2 and the third module M3, the intermediate layer IL having a thickness of 0.5 nm to 7 nm.

3. The glass article according to claim 1 or 2, wherein said intermediate layer IL is in direct contact with said layer of silica.

4. The glass article according to claim 1 or 2, comprising the following layer sequence: TiN2 / IL / SiO(N) / optional TiZrO, wherein SiO(N) represents that said layer contains silica, and TiZrO represents a layer of titanium oxide, zirconium oxide or an oxide of titanium and zirconium.

5. The glass article according to claim 1 or 2, wherein said module M1 comprises a layer containing silicon nitride.

6. The glass article according to claim 1 or 2, wherein module M2 comprises a layer containing silica or silicon oxynitride, and wherein at least one intermediate layer IL of titanium or a titanium alloy is deposited in the stack between a) the TiN1 layer and / or the TiN2 layer and b) said layer containing silica or silicon oxynitride, said intermediate layer having a thickness of 1 to 7 nm.

7. The glass article according to claim 6, wherein said stack comprises the following layer sequence: TiN1 / IL / SiO(N) / IL / TiN2, wherein SiO(N) represents a layer containing silica or silicon oxynitride.

8. The glass article according to claim 6, wherein said stack comprises the following layer sequence: TiN1 / IL / SiO(N) / SiN x / Optional IL / TiN2 wherein SiN x represents a layer containing silicon nitride, and SiO(N) represents a layer containing silicon oxide or silicon oxynitride.

9. The glass article according to claim 6, wherein said stack comprises the following layer sequence: TiN1 / IL / SiO(N) / SiN x / SiO(N) / IL / TiN2 wherein SiN x represents a layer containing silicon nitride, and SiO(N) represents a layer comprising silicon oxide or silicon oxynitride.

10. The glass article according to claim 6, wherein said stack is composed of successive layers from the substrate surface: (Glass) / SiN x / TiN1 / IL / SiO(N) / IL / TiN2 / IL / SiO(N) / Optional TiZrO, wherein SiN x represents a layer containing silicon nitride, and the SiO(N) between TiN1 and TiN2 represents a layer containing silicon oxide or silicon oxynitride, the other SiO(N) represents a layer containing silicon oxide, and TiZrO represents a layer of titanium oxide, zirconium oxide, or an oxide of titanium and zirconium.

11. The glass article according to claim 6, wherein said stack comprises the following layer sequence: (Glass) / SiN x / TiN1 / IL / SiO(N) / SiN x / Optional IL / TiN2 / IL / SiO(N) / Optional TiZrO, wherein SiN x represents a layer containing silicon nitride, and the SiO(N) between TiN1 and TiN2 represents a layer containing silicon oxide or silicon oxynitride, the other SiO(N) represents a layer containing silicon oxide, and TiZrO represents a layer of titanium oxide, zirconium oxide, or an oxide of titanium and zirconium.

12. The glass article according to claim 8, wherein the ratio between the cumulative thickness of one or more SiO(N) layers included in said M2 module and the thickness of the SiN x layer is higher than 2.

13. The glass article according to claim 1 or 2, wherein the thickness of said TiN1 layer is from 10 nm to 25 nm, and the thickness of said TiN2 layer is from 15 nm to 25 nm, including the limits.

14. The glass article according to claim 1 or 2, wherein the thickness t1 of the first module M1 is from 1 nm to 50 nm, inclusive, wherein the thickness t2 of the second module M2 is from 20 nm to 100 nm, inclusive, and wherein the thickness t3 of the third module M3 is from 20 nm to 65 nm, inclusive.

15. An assembled glass, comprising a single glass article as claimed in any one of the preceding claims.

16. An assembled glass, which from the outside comprises a first glass substrate bonded to the glass article as claimed in any one of the preceding claims by an intermediate thermoplastic sheet.

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