JP2016533311A - Low emissivity and anti-sun glazing - Google Patents

Abstract

The present invention relates to a low emissivity and anti-sun glazing system whose properties change only very slightly when subjected to heat treatment. They consist of a stack of thin layers comprising alternating arrangements of n infrared reflective functional layers and n + 1 dielectric coatings, and a barrier layer directly over the last functional layer furthest from the substrate. (I) the first dielectric coating closest to the substrate comprises a layer made of oxide in direct contact with the substrate, and (ii) is surrounded by two functional layers 1 The silicon nitride or silicon oxide having a thickness of more than 5 nm is surrounded by a layer made of an oxide other than silicon oxide having a thickness of more than 5 nm on both sides. (Iii) the barrier layer consists of indium oxide based on zinc oxide or optionally doped with tin, and (iv) a group comprising The last dielectric coating farthest from is nitrided, starting from the substrate, with a layer made from an oxide other than silicon oxide having a thickness greater than 3 nm and a thickness greater than 10 nm in the following order: Characterized in that it comprises a layer made of silicon or silicon oxide. [Selection figure] None

Description

  The present invention relates to a glazing system which has low emissivity and anti-sunlight properties at the same time and can be incorporated into a building window or used in the field of automotive glazing.

  Such glazing systems generally comprise at least two functional layers based on an infrared reflective material and at least three dielectric coatings, each of which is a thin layer surrounded by a dielectric coating. It is formed from a transparent substrate of the glass sheet type coated with the system. The functional layer is typically a silver layer with a thickness of a few nanometers. With respect to the dielectric layers, they are transparent and are conventionally made from metal oxides and / or nitrides. These different layers are deposited by vacuum deposition techniques such as, for example, magnetically assisted cathode sputtering, more commonly referred to as “magnetoresistive sputtering”.

  These glazing systems have anti-sunlight properties and can reduce the risk of excessive overheating, for example in enclosed spaces with large glass surfaces, thereby reducing the power load to be considered in summer air conditioning . In this case, the glazing must allow the lowest possible amount of low total solar radiant energy to pass, i.e. have the lowest possible solar transmission (SF or g). . However, it is highly desirable to ensure a certain level of light transmission in order to provide sufficient illumination within the building. These somewhat conflicting requirements represent a desire to obtain a glazing unit with a high selectivity (S) defined by the ratio of light transmission to solar transmittance. These glazing systems also have a low emissivity, which allows a reduction in heat loss through high wavelength infrared radiation. They therefore improve the insulation of large glass surfaces and reduce winter energy losses and heating costs.

  These glazing systems are generally assembled as multiple glazing units, such as double or triple glazing units or laminated glazing units, and a glass sheet with a coating laminate has a coating or has a coating. Not combined with one or more other glass sheets, low emissivity multilayer lamination is in case of multiple glazing units, in contact with the internal space between the glass sheets, or in the case of laminated glazing units Present in contact with the unit's interlayer adhesive.

  In some cases, work to mechanically strengthen glazing, such as thermal strengthening of one or more glass sheets, is required to improve resistance to mechanical stress. For certain applications, it may also be necessary to give the glass sheet a slightly more complex curvature by bending at high temperatures. In the process of manufacturing and shaping glazing systems, there are certain advantages in performing a heat treatment operation on an already coated substrate rather than coating an already processed substrate. These operations are carried out at a relatively high temperature, which is due to degradation of functional layers based on infrared reflecting materials, for example silver based layers, related to their optical properties and infrared. A temperature that tends to lose characteristics. These heat treatments, in particular depending on the type of heat treatment and the thickness of the sheet, can cause the glass sheet in air to have a temperature above 560 ° C., for example from 560 ° C. to 700 ° C., in particular from about 640 ° C. to 670 ° C. Heat for 4, 6, 8, 10, 12 or 15 minutes. In the case of a bending process, the glass sheet may then be bent into a desired shape. The tempering process then consists of quenching the surface of the flat or bent glass sheet with an air jet or coolant to obtain a mechanical reinforcement of the sheet.

  Thus, if the coated glass sheet requires heat treatment, it can withstand thermal strengthening and / or bending processes without losing optical and / or energy properties (hereinafter described as “temperable”). In some cases, extreme care is required to form the coating structure. In particular, the dielectric material used to form the dielectric coating must withstand the high temperatures of the heat treatment without exhibiting any inconvenient structural changes. Examples of materials particularly suitable for this use are zinc tin mixed oxide, silicon nitride and aluminum nitride. For example, by capturing free oxygen during heat treatment or by preventing free oxygen from moving towards silver, there is an oxidizable barrier layer instead of silver at the time of processing. By ensuring, it is also necessary to ensure that the functional layer, for example a silver based layer, does not oxidize during processing.

  In addition, the formation of these layer assemblies must also provide a satisfactory color in both reflection and transmission, with the demand to tend to be as neutral as possible. The difficulty is at the same time combining color requirements with "basic" conditions: high light transmission, very low emissivity, ability to withstand heat treatment.

  Another requirement that must be further considered is when unheated products and other heat treated products have to be combined with each other for the same application, for example within the same building facade It comes from the fact that. Thus, in the past, the development and parallel development of two low-emissivity layers, one for an unreinforced glazing unit and the other for a glazing unit intended to be reinforced or bent, and It was necessary to manufacture. This is complex both for research and development, and especially in production stock management. Since then, so-called “self-compatible” coating stacks have been developed in which their properties, in particular their optical and energy properties, change little when the substrates are subjected to a strengthening or bending type heat treatment.

  Furthermore, although the principles governing the optical properties of the material forming the layer are well known, there are additional difficulties in the production methods of these glazing units. The deposition conditions, in particular the deposition rate, depend on the nature of the material considered. The deposition rate must be sufficient for economically acceptable industrial production. It depends on several factors that guarantee functional stability over the entire surface of the sheet and without defects in the layers over time.

  Several solutions have been proposed to meet these various requirements, but no solution provides an actually satisfactory glazing unit capable of meeting these new requirements.

  EP 1140721 describes a coating lamination of a glass / dielectric I / Ag I / AZO / dielectric II / Ag II / AZO / dielectric III type silver-based layer, in particular The dielectric includes a zinc tin mixed oxide underlayer and a zinc oxide overlayer. From EP 1140721 it is understood that the coating stacks described are heat-treatable and that after heat treatment their optical properties show only slight changes. However, after heat treatment, it was shown that haze and unacceptable spots appeared on this type of layer and that the electrical resistance per square was increased, resulting in higher and therefore less favorable emissivity. (See Comparative Example 1 described below).

  Document WO 03/010105 describes a coating lamination with a double silver layer, characterized in that it comprises a Ti layer under the silver layer. All proposed stacks start with a nitride layer on the glass. They are presented as heat treatable while minimizing their optical alteration, minimizing the appearance of optical defects, and maintaining the thermal performance level of the coating stack. However, the proposed laminate has considerable drawbacks and the chemical stability of these products before heat treatment is not sufficient (see also Comparative Example 2 described below). Therefore, these layers need to be used without subsequent heat treatment or stored and optionally transported for a long time before undergoing heat treatment, and their aging resistance before heat treatment should be appropriate There is.

  Accordingly, the object of the present invention is a new low-performance which is effective with respect to optical and energy properties and which retains these performance levels with or without undergoing a strengthening or bending type heat treatment. It is to develop a laminate of emissivity and anti-solar thin layers.

In the present invention, the following information is used.
Light transmission (LT) is the percentage of the incident luminous flux of illuminant D65 / 2 ° that is transmitted by glazing.
-Light Reflection (LR) is the percentage of incident luminous flux of illuminant D65 / 2 ° reflected by glazing. This may be measured from the layer side (LRc) or the substrate side (LRg).
Energy transmission (ET) is the percentage of incident energy radiation transmitted by glazing, calculated according to standard EN410.
Energy reflection (ER) is the percentage of incident energy radiation reflected by the glazing, calculated by the standard EN410. This may be measured on the exterior side (ERext) of the building or vehicle or the interior side (ERint) of the building or vehicle.
Solar radiation transmittance (SF or g) is the percentage of incident energy radiation that is directly transmitted by glazing on the one hand, absorbed by glazing, and then emitted in the opposite direction of the energy source with respect to glazing. This is calculated according to the standard EN410 in this specification.
The U value (coefficient k) and emissivity (ε) are calculated according to standards EN673 and ISO 10292.
CIELAB 1976 value (L ^* a ^* b ^* ) is used to define the hue. This is measured by the illuminant D65 / 10 °.
・
Represents a change in hue during the heat treatment, that is, a color difference between before and after the heat treatment.
The resistance per square (R ² ) (sheet resistance) expressed in ohms per square (Ω / □) measures the electrical resistance of the thin film.
• Where values are described as “range ab” they may be equal to a or b.
The arrangement of the layer stack in multiple glazing structures is given according to the typical sequence number of the faces of the glazing unit, face 1 is on the exterior of the building or vehicle and face 4 (double gray The surface (in the case of a ging unit) or face 6 (in the case of a triple glazing unit) is on the inside.
In this specification, when a silicon nitride or silicon oxide layer is mentioned, it should be understood that a small amount of aluminum may be incorporated into the layer, as is well known in the art of magnetoelectric sputtering coatings. is there. Such aluminum is generally included as a doping agent in an amount of at most 10% by weight.
• For the sake of clarity, in this specification, when using terms such as “lower”, “upper”, “lower”, “upper”, “first” or “last”, always from the lower glass Related to a continuous layer starting and going further away from the glass. Such an arrangement may comprise additional intermediate layers between the defined layers, unless direct contact is specified.

  The invention relates to a glazing unit according to claim 1, and the dependent claims provide preferred embodiments.

The present invention relates to an n-layer infrared reflection functional layer and an n + 1 layer dielectric coating, wherein n> 1, and an alternate arrangement of the n-layer infrared reflection functional layer and the n + 1 layer dielectric coating for each function. It relates to a glazing unit comprising a transparent substrate provided with a stack of thin layers comprising a layer surrounded by a dielectric coating. Indeed, the present invention relates only to a coating stack comprising at least two infrared reflective functional layers. The glazing according to the invention comprises a barrier layer directly over the last functional layer furthest from the substrate and is characterized by the following:
(I) the first dielectric coating closest to the substrate comprises a layer made of oxide in direct contact with the substrate;
(Ii) One or more inner dielectric coatings surrounded by two functional layers are surrounded by layers made of oxides other than silicon oxide having a thickness of more than 5 nm on both sides Comprising a layer made of silicon nitride or silicon oxide having a thickness of more than 5 nm,
(Iii) the barrier layer consists of zinc oxide based or optionally tin-doped indium oxide, and (iv) the last dielectric coating furthest from the substrate starts with Characterized in that it comprises a layer made of an oxide other than silicon oxide having a thickness of more than 3 nm and a layer made of silicon nitride or silicon oxide having a thickness of more than 10 nm. .

For the specific selection of the layers of the coating stack, as well as the presence of a layer produced primarily from an oxide in direct contact with the substrate, the layer of silicon nitride or silicon oxide in the inner dielectric coating surrounded by the oxide layer, Due to the combination of the appropriate layers of silicon nitride or silicon oxide of the final dielectric coating, such a glazing unit may provide the following advantages (another standard 4 mm thick transparent soda lime float Along with the glass sheet, the coating on a standard 6 mm thick transparent soda lime float glass sheet incorporated in a double glazing unit is spaced between layers of 15 mm glass sheet filled to 90% with argon. Is at position 2).
High light transmission (LT ≧ 68%) simultaneously with low emissivity (ε ≦ 0.038, preferably ε ≦ 0.025) limits heat loss.
• Low solar transmittance (SF <41%) can reduce the risk of excessive overheating due to sunlight.
• High selectivity (LT / SF ≧ 1.75).
A heat insulating property capable of achieving a value of U ≦ 1.1 W / (m ² K), preferably U ≦ 1.0 W / (m ² K).
-Neutrality of color in transmission and reflection, whether single glazing or multiple glazings. Preferred values for single glazing:
Transmission: 88 ≦ L ^* ≦ 94 −6 ≦ a ^* ≦ + 4 −4 ≦ b ^* ≦ + 4
Reflective substrate side surface: 25 ≦ L ^* ≦ 40 −4 ≦ a ^* ≦ + 3 −16 ≦ b ^* ≦ 0
・ Possibility of heat treatment. The coating is resistant to high temperatures or is used without heat treatment.
-Aesthetic appearance without defects. Before or after heat treatment, haze is very limited or absent and there are no unacceptable spots after heat treatment.
-After heat treatment, retention of substantially unchanged optical and energy properties allows heat treated or unheat treated products to be used in the vicinity of each other ("self-compatibility"). Single glazing with little or no change in color in transmission and reflection (ΔE ^* ≦ 8, preferably ≦ 5, more preferably ≦ 2) and / or light transmission and reflection and energy values change Or hardly changed (Δ = | (value before heat treatment) − (value after heat treatment) | ≦ 5, preferably ≦ 3, more preferably ≦ 1).
• Sufficient chemical resistance for use without heat treatment or for time intervals before heat treatment. In particular, in the results of the climate chamber test or the salt spray test according to standard EN 1036-2012, there are no defects or any discoloration seen with the naked eye after 1 day, preferably after 3 days.

  In practice, the inventors have determined that the oxides that are in direct contact with the substrate (as in many known coating stacks, such as aluminum nitride or Not only is it essential to have a layer made from a non-nitride such as silicon nitride), but also to limit the appearance of haze after heat treatment and the deterioration of resistance per square, in particular one or more layers It was also essential to have a silicon nitride or silicon oxide layer surrounded by an oxide layer in the inner dielectric coating, and ultimately because of the chemical stability of the unheated product And indium oxide based on zinc oxide or optionally tin-doped, due to self-compatibility and absence of defects after heat treatment In addition to comprising a barrier layer, it has found it was essential to have a layer of the last dielectric silicon nitride above the oxide layer in the coating or silicon oxide.

The first dielectric according to the invention comprises a layer made of oxide as a single layer or as the lowest layer. Advantageously, this layer produced from an oxide in direct contact with the substrate is an oxide layer of at least one element selected from Zn, Sn, Ti and Zr. It is preferably a layer of zinc tin mixed oxide, more preferably zinc tin mixed oxide with a zinc tin ratio close to 50-50 wt.% (Zn ₂ SnO ₄ ), for example 52-48 wt.% Zinc tin mixed oxide. Layer. Zinc-tin mixed oxide is, for example, better stable compared to SiO ₂ or Al ₂ O ₃ because it has a better deposition rate and / or compared to eg pure ZnO or bismuth oxide. This may be advantageous because it shows sex. Still further, for example, it may be advantageous because it has less tendency to fog after heat treatment of the stack compared to Ti or Zr oxides. The layer produced from the oxide in direct contact with the substrate advantageously has a thickness of at least 15 nm, preferably at least 20 nm. These minimum thickness values can in particular ensure the chemical stability of the unheat-treated product and also ensure the resistance to heat treatment.

  The first dielectric coating preferably has a thickness of at least 15 nm, more preferably at least 20 nm. Its thickness is preferably at most 55 nm, more preferably at most 50 nm.

The inventors have given the term “inner dielectric coating” to a dielectric coating surrounded by two functional layers. In the case of a coating stack with two functional layers, there is a single inner dielectric coating. In the case of coating lamination with three functional layers, there are two inner dielectric coatings. In the following description, where an internal dielectric coating is generally referred to, the same considerations apply, even if not specifically stated, when having several internal dielectric coatings. The inner dielectric coating according to the invention is produced from silicon nitride or silicon oxide having a thickness of more than 5 nm surrounded by a layer made of an oxide other than silicon oxide having a thickness of more than 5 nm on both sides. Comprising a layer to be made. Thus, the inner dielectric coating according to the present invention comprises the following arrangements starting from the substrate in the following order, but not necessarily in direct contact:
Oxides other than SiO ₂ // Si ₃ N ₄ or oxides other than SiO ₂ // SiO ₂ .

The layer of the inner dielectric coating made from an oxide other than silicon oxide having a thickness of more than 5 nm is preferably an oxide layer of at least one element selected from Zn, Sn, Ti and Zr . These are preferably zinc tin mixed oxide layers, more preferably zinc tin mixed oxidation with a zinc tin ratio close to 50-50 wt.% (Zn ₂ SnO ₄ ), for example 52-48 wt.%. It is a layer of things. Alternatively, these may be, for example, layers of titanium zirconium mixed oxide with a weight ratio of about 65/35 Ti / Zr. The layer of inner dielectric coating made from oxides other than silicon oxide may be formed from one or more layers. They preferably have a thickness of at least 5 nm, at least 8 nm or at least 10 nm, more preferably at least 12 nm or at least 15 nm. Their thickness is preferably at most 50 nm or at most 40 nm, more preferably at most 30 nm. Advantageously, the inner dielectric coating layer made from an oxide other than silicon oxide located below the inner dielectric coating layer made from silicon nitride or silicon oxide is made from silicon nitride or silicon oxide. Thicker than those overlying the inner dielectric coating layer. This can improve the “self-compatibility” of the product.

The layer of inner dielectric coating made from silicon nitride or silicon oxide having a thickness greater than 5 nm preferably has a thickness of at least 8 nm or at least 10 nm, more preferably at least 12 nm. Its thickness is preferably at most 55 nm or at most 50 nm, more preferably 45 nm. Silicon nitride is better because it is easier to industrially deposit by magnetoelectric sputtering and with a slightly higher refractive index (n _SiN = 2.0, n _SiO2 = 1.5) than silicon oxide Is generally preferred over silicon oxide because it allows even light energy properties to be obtained. Alternatively, this layer may rather be a layer of aluminum oxide or aluminum nitride, but this solution was not preferred mainly for coating durability reasons.

  The inner dielectric coating preferably has a thickness of at least 24 nm or at least 30 nm, more preferably at least 35 nm or at least 40 nm. Its thickness is preferably at most 150 nm or at most 120 nm, more preferably at most 100 nm.

  At least one of the dielectric coatings directly over and in contact with the functional layer with the functional layer superimposed thereon (ie, the first dielectric coating or the inner dielectric coating), or preferably Each dielectric coating on which functional layers are superimposed may advantageously also comprise a layer based on zinc oxide. This is sometimes referred to as a “nucleation” or “wet” layer, which helps to promote silver growth thereon and increase resistance per square in the product. This zinc oxide based layer may consist of zinc oxide and may optionally be doped with another metal, for example aluminum, generally in a proportion of about 2% by weight and at most 10% by weight. This preferably has a thickness in the range of at most 15 nm, preferably 1.5 to 10 nm, more preferably 3 to 10 nm.

  According to the present invention, the stack comprises a barrier layer directly overlaid on the last functional layer furthest away from the substrate, i.e. above the last functional layer and in direct contact therewith. This barrier layer is based on zinc oxide (ie, at least 50 atomic percent, preferably at least 60 atomic percent, more preferably at least 70 atomic percent, even more preferably at least 80 atomic percent of the metallic portion of the oxide). Or indium oxide optionally doped with tin. More preferably, the barrier comprises zinc oxide optionally doped with aluminum or indium oxide optionally doped with tin. Even more preferably, the barrier layer is a layer of pure ZnO (denoted iZnO) or a layer of zinc oxide (AZO) doped with aluminum in a proportion of at most 10% by weight, preferably about 2% by weight. Is indicated). These types of barriers have the advantage of improving product “self-compatibility” and resistance per square. The barrier layer preferably has a thickness in the range of at most 20 nm or at most 18 nm, more preferably at most 16 nm, preferably from 1 to 18 nm, or from 2 to 18 nm, more preferably from 3 to 16 nm.

  The last dielectric coating according to the invention, furthest from the substrate, is a layer made of an oxide other than silicon oxide having a thickness of more than 3 nm and a thickness of more than 10 nm starting from the substrate in the following order: And a layer made of silicon nitride or silicon oxide having a thickness.

The last dielectric coating layer produced from an oxide having a thickness of more than 3 nm is preferably an oxide layer of at least one element selected from Zn, Sn, Ti and Zr. It is preferably a layer of zinc tin mixed oxide, more preferably a layer of (Zn ₂ SnO ₄ ) zinc tin mixed oxide with a zinc tin ratio close to 50-50% by weight. This preferably has a thickness of at least 4 nm, more preferably at least 5 nm or at least 6 nm. Its thickness is preferably at most 25 nm or at most 20 nm, more preferably at most 18 nm or at most 15 nm.

  Above this oxide layer of the final dielectric coating is a layer made of silicon nitride or silicon oxide that has a thickness of greater than 10 nm, although not necessarily in direct contact therewith. It preferably has a thickness of at least 12 nm or at least 14 nm, more preferably at least 15 nm or at least 16 nm. Its thickness is preferably at most 40 nm or at most 35 nm, more preferably at most 30 nm or at most 25 nm. Silicon nitride is easier to deposit industrially by magnetotube sputtering, and it can provide better mechanical stability and better heat treatment resistance than silicon oxide in the final dielectric Therefore, it is generally preferred over silicon oxide. This silicon nitride layer may be the last layer of the coating stack. Alternatively, this layer may rather be a layer of aluminum oxide or aluminum nitride, but this solution was not preferred mainly for coating durability reasons.

  Advantageously, the last dielectric coating may comprise a protective topcoat that forms the last layer of the coating stack. This preferably consists of an oxide or substoichiometric oxide of at least one element selected from Ti and Zr, more preferably, for example with a weight ratio of Ti / Zr close to about 65/35. It consists of titanium-zirconium mixed oxide. Such a layer may improve the chemical and / or mechanical stability of the glazing. This protective topcoat preferably has a thickness of at least 3 nm, preferably at least 5 nm. Its thickness is preferably at most 15 nm or at most 12 nm, more preferably at most 10 nm or at most 8 nm.

  The final dielectric coating preferably has a thickness of at least 10 nm or at least 15 nm, more preferably at least 20 nm or at least 22 nm. Its thickness is preferably at most 80 nm or at most 60 nm, more preferably at most 50 nm or at most 48 nm.

The dielectric coating is essentially one or more other dielectric layers, eg metal oxide, nitride or oxynitride, preferably ZnO, TiO ₂ , SnO, as long as direct contact between the above layers is preserved It may additionally comprise one or more layers of dielectric material made from ₂ , Si ₃ N ₄ , ZrO ₂ , zinc tin mixed oxide, or titanium zirconium mixed oxide. In the case of zinc-tin mixed oxides, it may have a proportion of zinc tin close to 50-50% by weight, or a proportion of zinc tin close to 90-10% by weight.

  Advantageously, the inner dielectric coating may comprise a dielectric material having a refractive index greater than 2.2. This type of material may actually allow further increases in glazing selectivity. This is preferably an oxide comprising one element selected from Ti, Nb and Zr, more preferably a titanium-zirconium mixed oxide with a weight ratio of Ti / Zr close to about 65/35, for example. is there.

  The infrared reflective functional layer is preferably a silver-based layer. It may consist of silver or optionally be doped with palladium or gold, for example in a proportion of at most 5% by weight, preferably about 1% by weight. Incorporation of a small amount of dopant in the silver-based layer can improve the chemical stability of the stack. The functional layer advantageously has a thickness of at least 6 nm or at least 8 nm, preferably at least 9 nm. Their thickness is preferably at most 22 nm or at most 20 nm, more preferably 18 nm. These thickness ranges may allow the desired low emissivity and anti-sun radiation functions to be achieved while maintaining good light transmission. In a coating stack having two functional layers, it may be preferred that the thickness of the second functional layer furthest away from the substrate is slightly larger than the first to obtain better selectivity. . In the case of coating lamination with two functional layers, the first functional layer can have a thickness of, for example, 8 to 18 nm, and the second functional layer can have a thickness of 10 to 20 nm.

  In some embodiments of the invention, the stack is at least one other than the last functional layer, or preferably a barrier layer that is directly overlaid (ie, over and in direct contact with) each functional layer. May be included. The barrier layer is based on zinc oxide (ie, at least 50 atomic percent, preferably at least 60 atomic percent, more preferably at least 70 atomic percent, and even more preferably at least 80 atomic percent of the metallic portion of the oxide). Indium oxide), or indium oxide optionally doped with tin. More preferably, the barrier consists of zinc oxide optionally doped with aluminum, or indium oxide optionally doped with tin. Even more preferably, the barrier layer is a layer of pure ZnO (denoted iZnO) or a layer of zinc oxide (AZO) doped with aluminum in a proportion of at most 10% by weight, preferably about 2% by weight. Is indicated). These types of barriers have the advantage of improving product “self-compatibility” and resistance per square. The barrier layer preferably has a thickness in the range of at most 20 nm or at most 18 nm, more preferably at most 16 nm, preferably from 1 to 18 nm, or from 2 to 18 nm, more preferably from 3 to 16 nm.

In some embodiments of the invention, the lamination of the thin layers starts from the substrate and in the following order:
(I) a layer of zinc tin mixed oxide having a thickness in the range of 20-40 nm;
(Ii) an optionally doped layer of zinc oxide having a thickness in the range of 3-10 nm;
(Iii) a first silver-based functional layer having a thickness in the range of 9-17 nm;
(Iv) a barrier layer of zinc oxide, optionally doped with aluminum, having a thickness in the range of 2-16 nm;
(V) optionally a layer of zinc oxide having a thickness in the range of 4-10 nm, or another metal in a Zn / metal weight ratio of at least 80/20, preferably at least 90/10 (eg A layer based on zinc oxide comprising Al);
(Vi) a layer of zinc tin mixed oxide having a thickness in the range of 10-50 nm;
(Vii) a layer of silicon nitride having a thickness in the range of 10-50 nm;
(Viii) a layer of zinc tin mixed oxide having a thickness in the range of 5-50 nm;
(Ix) an optionally doped layer of zinc oxide having a thickness in the range of 3-10 nm;
(X) a second silver-based functional layer having a thickness in the range of 10-20 nm;
(Xi) a zinc oxide barrier layer, optionally doped with aluminum, having a thickness in the range of 2-16 nm;
(Xii) optionally a layer of zinc oxide having a thickness in the range of 4 to 10 nm, or another metal with a Zn / metal weight ratio of at least 80/20, preferably at least 90/10 (eg A layer based on zinc oxide comprising Al);
(Xiii) a layer of zinc-tin mixed oxide having a thickness in the range of 3-20 nm;
(Xiv) a layer of silicon nitride having a thickness in the range of 10-35 nm;
(Xv) optionally comprising or consisting of at least a layer of titanium-zirconium mixed oxide having a thickness in the range of 3 to 10 nm.

  In these embodiments of the invention, the thickness of layer (vi), or where applicable, the sum of the thicknesses of layers (v) and (vi) is advantageously the layers (viii) and (ix ) Greater than the total thickness.

In another embodiment of the invention, the inner dielectric coating starts from the substrate and is in the following order:
(I) optionally a layer of zinc oxide having a thickness in the range of 4-10 nm, or another metal with a Zn / metal weight ratio of at least 80/20, preferably at least 90/10 (eg A layer based on zinc oxide comprising Al);
(Ii) a layer of zinc-tin mixed oxide having a thickness in the range of 10-30 nm;
(Iii) a layer of silicon nitride having a thickness in the range of 10 to 45 nm;
(Iv) a layer of zinc-tin mixed oxide having a thickness in the range of 5-30 nm;
(V) an optionally doped layer of zinc oxide having a thickness in the range of 3-10 nm, and between layer (ii) and layer (iii) or between layer (iii) and layer (iv) A layer of titanium-zirconium mixed oxide having a thickness in the range between 2 and 30 nm, or one between layer (ii) and layer (iii) and the other between layer (iii) and layer (iv) At least two layers of titanium-zirconium mixed oxide having a thickness in the range of 2 to 30 nm.

  In these embodiments of the invention, there may be grounds for adding the layer thickness of the titanium-zirconium mixed oxide, the thickness of layer (ii) or where applicable, of layers (i) and (ii) The sum of the thicknesses is advantageously greater than the sum of the thicknesses of layers (iv) and (v), where there can be a basis for adding the thickness of the titanium-zirconium mixed oxide layer.

  The glazing unit according to the invention is preferably used in a plurality of glazing units, for example double or triple glazing units. They may have the following properties:

  Certain embodiments of the present invention are described by way of example with respect to Examples 1-10, as well as Comparative Examples 1-4.

  All thicknesses in the examples and comparative examples are given in angstroms. All layers were deposited using magnetically assisted cathode sputtering under vacuum. When heat treatment was performed, it was performed under the following conditions: 9 minutes 30 seconds curing in a static oven at 670 ° C.

Examples 1-8
The layer stack according to the invention recorded in Table I was deposited on a glass sheet and then heat treated. The values of resistance per square before and after heat treatment are shown in the table, indicating that this treatment hardly changes the value (Δ <0.4). These glazing units have proven to be “temperable” and “self-compatible”. The heat-treated product does not show haze or spots and before heat treatment, the product has good chemical stability.

  The following properties were measured in the samples according to Example 1a, Example 7 and Example 8 before the heat treatment, and the change in Δ was calculated between the values before and after the heat treatment.

Example 9
Examples of coating lamination with three functional layers according to the present invention are deposited on a glass sheet and shown in Table II.

This type of coating stack is resistant to heat treatment and is self-compatible (ΔE ^* <8). In double glazing (as defined above), an LT value of 50-65% and a selectivity higher than 1.9 are obtained.

Comparative Examples 1 and 2
The stack of non-inventive layers recorded in Table III was deposited on a glass sheet and then heat treated. The values of resistance per square before and after the heat treatment are shown in the table, which shows that the value was greatly deteriorated by this treatment. These glazing units can therefore not be considered “self-compatible”. Further, in these comparative examples, after the heat treatment, intense haze that can be recognized with the naked eye occurred.

A comparison between Comparative Example 1 and the example according to the invention demonstrates the following.
· Having a silicon nitride or silicon oxide layer surrounded by an oxide layer in the inner dielectric coating to limit the haze appearance and increase the resistance per square after heat treatment leading to an increase in emissivity As well as the advantages of having a layer of silicon nitride above the oxide layer in the final dielectric coating, especially for self-compatibility.

  Comparative Example 2 shows a coating stack in which the layer in contact with the glass is made from nitride and not from oxide as in the present invention. The samples according to this comparative example were subjected to a climate chamber test and a salt spray (“neutral salt spray”) test according to standard EN 1096-2012 before any heat treatment. One day after the climatic chamber, the sample according to Comparative Example 2 deteriorated more than the sample according to Example 1, which was the same after 3 days. One day after the salt spray, the sample according to Comparative Example 2 deteriorated more than the sample according to Example 1, which was the same after 2 days. These degradations were evident by the appearance of spots and / or defects visible to the naked eye. This demonstrates the advantage of having a layer made from an oxide in direct contact with the substrate, especially for better chemical stability of the unheat treated product.

In the table below,
ZSO ₅ represents a (Zn ₂ Sn ₂ O ₄ ) zinc tin mixed oxide with a zinc tin ratio close to 50-50% by weight.
AZO represents zinc oxide doped with aluminum in a proportion of about 2% by weight.
SiN represents silicon nitride.
TZO represents a titanium-zirconium mixed oxide with a weight ratio of about 65/35 Ti / Zr.

Example 10 and Comparative Examples 3 and 4
Examples of coating lamination according to the present invention and two comparative examples not according to the present invention were deposited on a glass sheet as follows.

  The following characteristics were observed:

  The results of the neutral salt spray test are given on a scale from 1 to 5 in the table, 5 means no degradation and 1 means very degraded.

  The comparison between Example 10 and Comparative Examples 3 and 4 shows the beneficial effect of the presence of a layer made from an oxide other than silicon oxide in the upper dielectric coating between the barrier layer and the silicon nitride layer. : Much better resistance to neutral salt spray by heat treatment, and much less change in light and energy transmission.

Claims (17)

n layers of infrared reflective functional layers and n + 1 layers of dielectric coating, wherein n> 1, alternating arrangement of n layers of infrared reflective functional layers and n + 1 layers of dielectric coating, each functional layer being dielectric In a glazing comprising a transparent substrate provided with a stack of thin layers comprising so as to be surrounded by a coating, and a barrier layer directly overlaid on the last functional layer furthest from the substrate,
(I) the first dielectric coating closest to the substrate comprises a layer made of oxide in direct contact with the substrate;
(Ii) the one or more inner dielectric coatings surrounded by two functional layers are surrounded by layers made of oxides other than silicon oxide having a thickness of more than 5 nm on both sides; Comprising a layer made of silicon nitride or silicon oxide having a thickness greater than 5 nm,
(Iii) the barrier layer is made of indium oxide based on zinc oxide or optionally doped with tin, and (iv) the last dielectric coating furthest from the substrate starts from the substrate A layer made of an oxide other than silicon oxide having a thickness of more than 3 nm and a layer made of silicon nitride or silicon oxide having a thickness of more than 10 nm, in the following order: A characteristic, glazing.   The glazing of claim 1, wherein the layer made from an oxide in direct contact with the substrate is a layer of zinc tin mixed oxide.   The glazing of claim 1 or 2, wherein the layer made from an oxide in direct contact with the substrate has a thickness of at least 20 nm.   4. The gray according to claim 1, wherein the layer made from an oxide other than silicon oxide of the one or more inner dielectric coatings is made from a zinc-tin mixed oxide. Zing.   Each dielectric coating, each dielectric coating having a functional layer superimposed thereon, comprises a zinc oxide based layer directly under and in contact with the functional layer. Glazing as described in any one of 1-4.   6. Glazing according to claim 5, wherein each zinc oxide-based layer directly under and in contact with the functional layer has a thickness in the range of at most 15 nm, preferably 3-10 nm.   Above and in direct contact with each functional layer, the stack comprises a barrier layer made of zinc oxide optionally doped with aluminum, or indium oxide optionally doped with tin. Item 7. The glazing according to any one of Items 1 to 6.   Grazing according to any one of the preceding claims, wherein the or each barrier layer has a thickness in the range of at most 20 nm, preferably 2-18 nm.   The last dielectric coating forms the last layer of the stack and includes a protective topcoat comprising an oxide of at least one element selected from Ti and Zr, optionally a substoichiometric oxide. 9. Glazing according to any one of the preceding claims, additionally comprising.   10. Glazing according to claim 9, wherein the protective topcoat has a thickness of at most 15 nm, preferably in the range of 3 to 10 nm. The lamination of the thin layers starts from the substrate, in the following order:
(I) a layer of zinc tin mixed oxide having a thickness in the range of 20-40 nm;
(Ii) an optionally doped layer of zinc oxide having a thickness in the range of 3-10 nm;
(Iii) a first silver-based functional layer having a thickness in the range of 9-17 nm;
(Iv) a barrier layer of zinc oxide, optionally doped with aluminum, having a thickness in the range of 2-16 nm;
(V) optionally a layer of zinc oxide having a thickness in the range of 4-10 nm, or another metal in a Zn / metal weight ratio of at least 80/20, preferably at least 90/10 (eg A layer based on zinc oxide comprising Al);
(Vi) a layer of zinc tin mixed oxide having a thickness in the range of 10-50 nm;
(Vii) a layer of silicon nitride having a thickness in the range of 10-50 nm;
(Viii) a layer of zinc tin mixed oxide having a thickness in the range of 5-50 nm;
(Ix) an optionally doped layer of zinc oxide having a thickness in the range of 3-10 nm;
(X) a second silver-based functional layer having a thickness in the range of 10-20 nm;
(Xi) a zinc oxide barrier layer, optionally doped with aluminum, having a thickness in the range of 2-16 nm;
(Xii) optionally a layer of zinc oxide having a thickness in the range of 4 to 10 nm, or another metal with a Zn / metal weight ratio of at least 80/20, preferably at least 90/10 (eg A layer based on zinc oxide comprising Al);
(Xiii) a layer of zinc-tin mixed oxide having a thickness in the range of 3-20 nm;
(Xiv) a layer of silicon nitride having a thickness in the range of 10-35 nm;
(Xv) optionally comprising or consisting of at least a layer of titanium-zirconium mixed oxide having a thickness in the range of 3-10 nm. The glazing described.   11. A gray according to any one of the preceding claims, wherein the stack of thin layers comprises a layer of dielectric material having a refractive index higher than 2.2 in at least one of the dielectric coatings. Zing.   13. A glazing according to claim 12, wherein the dielectric material having a refractive index higher than 2.2 is an oxide of at least one element selected from Ti, Nb and Zr. The inner dielectric coating starts from the substrate in the following order:
(I) optionally a layer of zinc oxide having a thickness in the range of 4-10 nm, or another metal with a Zn / metal weight ratio of at least 80/20, preferably at least 90/10 (eg A layer based on zinc oxide comprising Al);
(Ii) a layer of zinc-tin mixed oxide having a thickness in the range of 10-30 nm;
(Iii) a layer of silicon nitride having a thickness in the range of 10 to 45 nm;
(Iv) a layer of zinc-tin mixed oxide having a thickness in the range of 5-30 nm;
(V) an optionally doped layer of zinc oxide having a thickness in the range of 3-10 nm, and between layer (ii) and layer (iii) or between layer (iii) and layer (iv) A layer of titanium-zirconium mixed oxide having a thickness in the range between 2 and 30 nm, or one between layer (ii) and layer (iii) and the other between layer (iii) and layer (iv) 14. A glazing according to claim 12 or 13, comprising or consisting of at least two layers of a titanium-zirconium mixed oxide having a thickness in the range of 2 to 30 nm between.   14. The layer according to claim 1, wherein the layer made from an oxide other than silicon oxide of the one or more inner dielectric coatings is made from a titanium zirconium mixed oxide. Glazing as described in. A color change in transmission and reflection between the unheated glazing and the heat-treated glazing, defined by ΔE ^* , of at most 8, preferably at most 5, in a single glazing. A glazing as claimed in any one of the preceding claims.   2. A change in light and energy transmission and reflection values between the unheated glazing and the heat-treated glazing of at most 5, preferably at most 3, in a single glazing. Glazing as described in any one of -16.