JP6433489B2 - Solar radiation adjustment glazing - Google Patents

Description

  The present invention relates to solar glazing glazings that can be incorporated into glazings for architectural or automotive applications that also exhibit low emissivity properties and optionally anti-sunlight properties.

  Such glazing is generally n functional layers and n + 1 dielectric layers based on a material that reflects infrared, where n ≧ 1, each functional layer being surrounded by a dielectric layer , Comprising a transparent substrate, for example a glass sheet, coated with a stack of thin layers comprising n functional layers and n + 1 dielectric layers. The functional layer is generally a layer of silver with a thickness of a few nanometers, while the dielectric layer is transparent and is conventionally made from metal oxides and / or nitrides. These different layers are generally coated by a magnetron sputtering type vacuum coating technique.

  Low emissivity glazing, for example, has the property of reflecting infrared radiation emitted from the interior of a building, thereby suppressing heat loss. Often, it is simultaneously required to have as high a luminous transmission (LT) as possible. These two requirements, low emissivity and high transmission, generally lead to conflicting solutions with respect to structure. It is therefore necessary to make difficult compromises. Glazing with solar protection properties, for example, reduces the risk of excessive overheating due to sunlight in an enclosed space with a large glass surface, thereby reducing summer air conditioning requirements. In that case, the glazing must transmit the lowest possible total solar radiant energy, ie 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 ensure sufficient illumination within the building. These somewhat conflicting requirements are reflected in the desire to obtain a glazing with a high selectivity (S) defined by the ratio LT / SF. By having even lower emissivity properties, such glazing improves thermal insulation of large glass surfaces and reduces winter energy losses and heating costs.

  Such glazings are typically assembled with multiple glazing units, such as double or triple glazing or laminated glazing, where a coated glass sheet is coated with one or more coated or uncoated sheets. Associated with other glass sheets. The coating stack is placed in contact with the space between the two glass sheets in the case of multiple glazings or in contact with the bonding layer in the case of stacked glazings.

  In some cases it is necessary to mechanically strengthen the glazing by heat treatment of the glass sheet in order to improve its resistance to mechanical constraints. For certain applications, it may be necessary to bend the glass sheet at high temperatures. In the entire process of producing glazing, it may be advantageous to heat treat the already coated glass sheet rather than coating the already heat treated glass sheet. These operations are performed at relatively high temperatures, and under such conditions, functional layers that reflect infrared light, such as silver-based layers, degrade and their optical properties and their properties against infrared light are degraded. There is a tendency to lose. Depending on the type of heat treatment and the thickness of the glass sheet, these heat treatments can be carried out at a temperature of at least 560 ° C., for example, 560 ° C. to 700 ° C., especially about 640 ° C. to 670 ° C. , 6, 8, 10, 12 or 15 minutes. This treatment comprises a rapid cooling step to introduce a stress difference between the glass surface and the central part so that the so-called tempered glass sheet safely breaks up into small pieces upon impact after the heating step. May be. If the cooling step is not very strong, then the glass is simply heat strengthened, which in any case provides better mechanical resistance.

  If the coated glass sheet requires heat treatment, to ensure that the coating stack can withstand tempering or bending types of heat treatment without losing optical and / or energy properties during manufacture It is necessary to pay attention to. Such a stack is sometimes referred to as “heat treatable” or “temperable”. Dielectric materials that resist high temperatures without detrimental structural changes have to be selected: for example, zinc-tin mixed oxide, silicon nitride and aluminum nitride. In addition, ensuring that there is a barrier layer that itself oxidizes during processing, for example by scavenging free oxygen or preventing such oxygen from moving towards silver. This should prevent the functional layer based on silver from oxidizing during the heat treatment.

  The coating stack must simultaneously satisfy other conditions such as chemical and mechanical resistance, and aesthetics (especially colors in reflection and transmission, the market generally demands neutral colors as much as possible). The difficulty is to combine all these conditions with the “basic” conditions of high light transmission, low emissivity, and low solar transmittance, along with the ability to optionally undergo heat treatment. One additional difficulty stems from the manufacturing process used to manufacture such glazing. The coating conditions, in particular the deposition rate, depend on the assumed material properties. The speed must be sufficient for economically acceptable industrial production. It depends on several factors that ensure process stability over the entire surface of the glass sheet and without coating defects throughout the manufacturing time.

  A number of solutions have been proposed to meet these various requirements, but there is currently no solution that provides a glazing that actually best meets all these requirements.

  EP 803481 describes GL / D1 / Ag / Ti / D2 and GL / D1 / Ag / Ti / D2 / Ag / Ti / D3 (GL means glass, D means dielectric) Disclosed are heat treatable low emissivity single silver and double silver coating stacks, where the materials used for the dielectric include zinc tin mixed oxide, zinc oxide and titanium oxide It becomes. Alternatively, EP 1140721 describes a heat treatable low emissivity coating stack of the type GL / D1 / Ag / AZO / D2 (AZO means zinc oxide doped with aluminum). Again, the material used for the dielectric comprises zinc tin mixed oxide, zinc oxide and titanium oxide.

  However, the inventors have found that the lamination according to EP 803481 results in some defects regarding mechanical durability and that the lamination according to EP 1140721 is cloudy and unacceptable after heat treatment It was noticed that it showed spots (see Comparative Example 1 below).

  For the purpose of the present invention, in the course of improving such conventional prior art coating laminations, the inventors have already noticed the same disadvantages of the lamination of EP 1140721, from glass substrates, A first dielectric comprising at least three layers in the order of aluminum (oxy) nitride / tin oxide or zinc tin mixed oxide / zinc oxide, and at least two layers: a main zinc tin mixed oxide layer and 10 nm We have found WO 2007/080428 which has attempted to solve this with a second dielectric comprising an outermost protective thin layer of less than thickness. However, the present inventors have also shown a non-negligible drawback in coating lamination according to WO 2007/080428, i.e. their chemical resistance before any heat treatment is not sufficient (the following comparative examples) (See 2 and 3). However, the coating according to the invention must be useful without subsequent heat treatment or must be sufficiently resistant to aging before heat treatment since it must be stored before undergoing heat treatment.

  Furthermore, the simple addition of a thin protective topcoat known to improve mechanical durability to such conventional prior art coating laminates is in order to achieve the level of performance that the present invention is aimed at. Proven not enough.

EP 506507 and WO 2012/127162 both disclose single silver infrared reflective films that terminate in SiO ₂ layers of about 25 nm and 40-120 nm, respectively. Although the lamination of EP 506507 is described as being heat-treatable, such features are not described in WO2012 / 127162. Both documents describe a barrier layer which is a metallic SiO ₂ layer deposited by magnetoelectric sputtering on and in contact with the silver layer.

On the other hand, depositing a SiO coating by plasma enhanced chemical vapor deposition (“PECVD”), for example from WO 2012/160145, to increase the efficiency of SiO ₂ deposition compared to SiO ₂ by sputtering. It has been known. However, the inventors have discovered that in such types of coating stacks, simply replacing sputtered SiO ₂ with PECVD-SiO ₂ presents many difficulties. In particular, the inventors have not been able to simultaneously achieve low haze values and good resistance to wear (see Comparative Examples 4-9 below).

  The object of the present invention is therefore efficient in terms of optical and energy properties, maintains these properties after possible heat treatment, is chemically and mechanically resistant, and is aesthetically pleasing (neutral) Color and low haze) and to develop a new type of coating laminate with solar control properties that are practical and efficient to manufacture.

は、熱処理の間の色合いの変化、すなわち、熱処理前後間の色の差異を表す。
− オームパースクエア（Ω／□）で表されるシート抵抗（Ｒ^２またはＲｓ）は、薄フィルムの電気抵抗を測定する。
− 値が「ａ〜ｂに含まれる」と記載される場合、それらはａまたはｂと等しくてもよい。
− 複数のグレイジングにおけるコーティング積層の配置は、グレイジング面の標準連続番号に従って与えられ、面１は、建築物または車両の外側であり、および面４（二重グレイジング）または面６（三重グレイジング）は内側である。 In the present invention, the following convention is used.
-Light transmission (LT) is the percentage of incident luminous flux of the illuminant D65 / 2 ° transmitted by glazing.
-Light reflection (LR) is the percentage of incident luminous flux of illuminant D65 / 2 ° reflected by glazing. This can be measured on the coating 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 glazing, calculated according to standard EN410. This can be measured on the coating side (ERc) or the substrate side (ERg).
The solar transmittance (SF or g) is the fraction of incident energy radiation that is partly directly transmitted by glazing and partly absorbed by glazing and then emitted in the opposite direction of the energy source with respect to glazing. Percent. This is calculated according to the standard EN410 in this specification.
-U values and emissivity (ε or E) are calculated according to the standards EN673 and ISO 10292.
CIELAB 1976 value (L ^* a ^* b ^* ) is used to define the color. 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.
- sheet resistance represented in ohms per square (Ω / □) (R ² or Rs) measures the electrical resistance of the thin film.
-Where values are described as “included in ab”, they may be equal to a or b.
The arrangement of the coating stacks in the glazing is given according to the standard serial number of the glazing surface, surface 1 is outside the building or vehicle and surface 4 (double glazing) or surface 6 (triple) Glazing) is inside.

  According to one of its aspects, the present invention provides a glazing as defined by claim 1. The dependent claims define preferred and / or other aspects of the invention.

  The present invention relates to n functional layers and n + 1 dielectric layers that reflect infrared rays, where n ≧ 1, each functional layer being surrounded by a dielectric layer, and n functional layers that reflect infrared rays And a glazing having a transparent substrate coated with a stack of thin layers comprising n + 1 dielectric layers. This is due to the fact that at least one dielectric layer overlying the functional layer comprises a layer consisting essentially of silicon oxide, and that the laminate is any functional layer, directly above the dielectric layer. It is characterized by the fact that it comprises a barrier layer based on zinc oxide on and in direct contact with any functional layer having a silicon oxide layer.

  For the sake of clarity, when using terms such as lower, upper, lower, upper, first or last in this document, always start from the lower glass and continue upward further away from the glass. Regarding the layer. Such an arrangement may comprise additional intermediate layers between the defined layers, unless direct contact is specified.

Such a glazing according to the invention has proven to provide the following advantages for a specific combination of a silicon oxide layer and a zinc oxide based barrier (a thin layer stack is 4 mm thick): Deposited on normal clear soda lime float glass, incorporated into double glazing with another normal clear soda lime float glass of 4 mm thickness at 15 mm intervals, filled with 90% argon, In position 2).
High light transmission with low emissivity limits heat loss (single functional layer stack: LT ≧ 73%, ε ≦ 0.074, or ε ≦ 0.044, preferably ε ≦ 0.024; Multi-functional layer structure lamination: LT> 68%, ε ≦ 0.038, preferably ε ≦ 0.025).
Solar radiation transmittance adjustment: SF that is low but not too low allows the energy portion of solar radiation to pass and free energy to be used in winter (eg, single functional layer stack: 55% to 65 % SF). Or a lower SF can reduce the risk of excessive overheating due to sunlight (eg, dual functional layer stack: SF <41%).
U ≦ 1.3 W / (m ² K), or U ≦ 1.2 W / (m ² K), preferably U ≦ 1.1 W / (m ² K), or U ≦ 1.0 W / (m Insulation capacity capable of achieving a U value of ² K).
• Neutral color in single or multiple glazings, in transmission or reflection. It has preferred values in the following single glazing.
Transmission: −6 ≦ a ^* ≦ + 5 −6 ≦ b ^* ≦ + 6
Reflective coating side surface: −6 ≦ a ^* ≦ + 6 −25 ≦ b ^* ≦ 10
Reflective substrate side surface: −5 ≦ a ^* ≦ + 3 −20 ≦ b ^* ≦ + 4
The possibility of being heat-treated, the coating stack being subjected to high temperatures, or being used without any heat treatment.
-Aesthetic aspect without defects. Without heat treatment or after heat treatment, the haze is very limited or absent and there are no unacceptable spots after heat treatment.
-In some cases, preservation of substantially unchanged optical and energy properties after heat treatment allows the use of heat treated or unheat treated products in the vicinity of each other ("self-adapting""). Single and / or multiple glazings with little or no color change in transmission and reflection (ΔE ^* ≦ 8, preferably ≦ 5, more preferably ≦ 2) and / or light and energy transmission and There is little or no change in the reflection value (Δ = | (value before heat treatment) − (value after heat treatment) | ≦ 5, preferably ≦ 3, more preferably ≦ 2).
• Sufficient chemical resistance for use without heat treatment or for time intervals prior to any heat treatment. In particular, in the results of the Cleveland test according to ISO 6270-1: 1998 (exposure to steam arising from a tank of deionized water heated to 50 ° C.), there is no discoloration seen with the naked eye after 1 day, preferably after 3 days.
・ Sufficient mechanical resistance. In particular, for example, abrasion resistance as tested by the wet brush test (described below) yields a score of less than 3.

  We actually have this combination of a silicon oxide layer and a zinc oxide based barrier to achieve a compromise between high resistance to rubbing (rubbing) and low haze. Found that is essential.

  Therefore, the present invention provides n functional layers and n + 1 dielectric layers that reflect infrared rays, where n ≧ 1, and each functional layer is surrounded by a dielectric layer. The present invention relates to a coating stack having a functional layer and n + 1 dielectric layers. Low emissivity coatings generally include a single functional layer that reflects infrared radiation, whereas coatings with low emissivity and anti-sun radiation characteristics generally include two or three functional layers that reflect infrared radiation. Including. Preferably, the functional layer reflecting infrared radiation is a silver-based layer and is silver or silver doped at a rate of at most 5% by weight, preferably about 1% by weight, for example with palladium or gold. Consists of. Incorporation of a low amount of dopant in the silver-based layer can improve the chemical resistance of the coating stack. Advantageously, the functional layer has a thickness of at least 6 nm or at least 8 nm, preferably at least 10 nm, and the thickness is preferably at most 22 nm or at most 20 nm, preferably at most 18 nm or at most 16 nm. is there. Such a range of thicknesses makes it possible to achieve the required low emissivity and / or anti-sun characteristics while retaining the required light transmission. In the case of a coating stack having two functional layers that reflect infrared radiation, the thickness of the second functional layer, ie the functional layer furthest away from the substrate, is slightly larger than the thickness of the first functional layer Is preferred. As an example, the first functional layer has a thickness of 8 to 18 nm, and the second functional layer has a thickness of 10 to 20 nm.

According to the invention, the at least one dielectric layer above the functional layer comprises a layer consisting essentially of silicon oxide. For example, in a single functional layer configuration stack, the silicon oxide layer is present in the second upper dielectric layer, and in a dual function layer configuration stack, the silicon oxide layer is the second or third dielectric layer. Means present in each of the layers, or each of the second and third dielectric layers. Layers consisting essentially of silicon oxide may contain other materials, such as aluminum, as long as they do not affect the properties of the layer and the coating stack. In general, such additional materials are present in the layer in an amount of at most 10 atomic%, preferably at most 5 atomic%. The silicon oxide may be completely or partially oxidized within the range of transition from SiO to SiO ₂ .

  Advantageously, the layer consisting essentially of silicon oxide is obtained by plasma enhanced chemical vapor deposition (PECVD). It is an efficient method of depositing silicon oxide that provides a high deposition rate for PECVD and enables high speed deposition. However, PECVD can induce the presence of contaminants in layers such as hydrogen or carbon based contaminants, which can optionally be at least partially oxidized. Preferably they should be as low as possible. It may be advantageous for the layer consisting essentially of silicon oxide to have an extinction coefficient of less than 1E-4 at a wavelength of 632 nm, a refractive index of at least 1.466 and a carbon content of at most 3 atomic%. This can provide high thermal durability to the silicon oxide layer and ensure that the coating stack incorporating such layer best withstands further heat treatment.

  Preferably, the layer consisting essentially of silicon oxide has a thickness of more than 10 nm. This minimum thickness may ensure that the silicon oxide layer acts as a barrier to the diffusion of oxygen into the coating stack and promotes the thermal, mechanical and chemical stability of the coating. Preferably, the layer consisting essentially of silicon oxide has a thickness of at most 125 nm in order to avoid too much haze.

  The stack according to the invention is any functional layer, on top of any functional layer having a silicon oxide layer on the dielectric layer directly above it, and a barrier layer based on zinc oxide in direct contact therewith Comprising. This zinc oxide based barrier layer is in an amount of 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. Zn is included. Preferably, the barrier layer consists of zinc oxide and is optionally doped with aluminum. More preferably, the barrier layer is a layer of pure ZnO (denoted iZnO) or a layer of zinc oxide doped with aluminum (denoted AZO) at a rate of at most 10% by weight, preferably about 2% by weight. Is). It has been discovered that such a barrier is essential to provide high mechanical resistance and low haze.

  In a preferred embodiment, the stack comprises a barrier layer based on zinc oxide on and in direct contact with each functional layer, preferably consisting of zinc oxide, optionally doped with aluminum. Become. This may facilitate a further improvement in the overall stability of the coating with respect to heat treatment resistance, mechanical and chemical resistance, while providing a good visual aesthetic.

  The barrier layer based on zinc oxide may have a thickness of at most 35 nm or at most 30 nm, preferably at most 25 nm or at most 20 nm, more preferably 1-20 nm, 2-18 nm, or 3-18 nm. .

In a preferred embodiment of the invention, starting from the substrate, the first dielectric layer (ie the lowest dielectric layer) comprises an oxide layer in direct contact with the substrate. Advantageously, the oxide layer in direct contact with the substrate is an oxide layer of at least one material selected from Zn, Sn, Ti and Zr. Preferably, this is a layer of zinc tin mixed oxide with a zinc tin ratio close to about 50-50% by weight, for example 52-48% by weight (Zn ₂ SnO ₄ ), respectively. Zinc-tin mixed oxide can be advantageous because it exhibits good deposition rate, good durability, and does not have a tendency to fogging after heat treatment of the coating stack.

  The oxide layer in direct contact with the substrate preferably has a thickness of at least 5 nm, 8 nm or 10 nm, more preferably at least 15 nm, even more preferably at least 20 nm. Such a minimum thickness value may in particular ensure the chemical resistance of the unheated product, but may also ensure the product's resistance to heat treatment.

  Advantageously, each dielectric layer below the functional layer (ie, the first dielectric layer in a single functional layer stack, the first and second dielectric layers in a dual functional stack), etc. A layer based on zinc oxide in direct contact with the substrate. Such a layer, sometimes referred to as a “seed layer”, promotes the growth of silver thereon. Said layer based on zinc oxide consists of zinc oxide or is optionally doped with another metal, for example aluminum, generally in a proportion of at most 10% by weight, preferably about 2% by weight. Also good. This preferably has a thickness of at most 15 nm, preferably 1.5 to 10 nm, more preferably 2 to 8 nm.

The dielectric layer is one or more layers other than those described above, eg, metal oxides, nitrides or oxynitrides, preferably ZnO, so long as the direct contact described as essential herein is maintained. One or more layers of a dielectric material comprising TiO ₂ , SnO ₂ , Si ₃ N ₄ , ZrO ₂ , zinc tin mixed oxide, or titanium zirconium mixed oxide may additionally be included. In the case of zinc-tin mixed oxides, a proportion of about 50-50 wt.% Zinc tin or a proportion of about 90-10 wt.% Zinc tin can be exhibited. The presence of a high refractive index material can further facilitate an increase in glazing light transmission. This can be, for example, an oxide comprising one element selected from Ti, Nb and Zr, preferably a titanium-zirconium mixed oxide with a weight ratio Ti / Zr of about 65/35, for example. .

  The dielectric layer of a single, double or triple functional layer stack may exhibit the following optical thickness expressed in nm.

  In some embodiments, the last top dielectric layer comprises a protective topcoat that is the last layer of the stack. This preferably consists of an oxide or substoichiometric oxide comprising at least one element selected from Ti and Zr, preferably with a weight ratio Ti / Zr of, for example, about 65/35 It consists of titanium-zirconium mixed oxide. Such a layer may improve the chemical and / or mechanical durability of the glazing. This protective topcoat advantageously has a thickness of at least 2 nm, preferably at least 3 nm, preferably its thickness is at most 20 nm, at most 15 nm or at most 12 nm, more preferably at most 10 nm or At most 9 nm.

In some embodiments of the invention, the lamination of the thin layers starts from the substrate,
(I) a layer of zinc-tin mixed oxide having a thickness of 27-45 nm;
(Ii) a layer of zinc oxide, optionally doped with aluminum, having a thickness of 1-8 nm and in contact with layer (iii);
(Iii) a functional layer based on silver having a thickness of 7 to 16 nm;
(Iv) a zinc oxide barrier layer, optionally doped with aluminum, having a thickness of 1 to 32 nm, preferably 1 to 18 nm, more preferably 1 to 5 nm, in contact with layer (iii);
(V) a layer of zinc-tin mixed oxide or a layer based on zinc oxide having a thickness of 15-35 nm;
(Vi) a layer of silicon oxide having a thickness of 20-50 nm, preferably 20-30 nm, advantageously deposited by PECVD;
(Vii) optionally comprising or consisting of at least a layer of titanium-zirconium mixed oxide having a thickness of 2 to 10 nm.

In another embodiment of the invention, the lamination of the thin layers starts from the substrate,
(I) a layer of titanium oxide having a thickness of 25-35 nm;
(Ii) a layer of zinc oxide, optionally doped with aluminum, having a thickness of 1-8 nm and in contact with layer (iii);
(Iii) a functional layer based on silver having a thickness of 10 to 16 nm;
(Iv) a zinc oxide barrier layer, optionally doped with aluminum, having a thickness of 1-18 nm, preferably 1-5 nm, in contact with the layer (iii);
(V) a layer based on titanium oxide having a thickness of 5 to 35 nm;
(Vi) optionally, a layer of zinc-tin mixed oxide;
(Vii) optionally, a layer of silicon nitride;
(Layer (vi) has a thickness of at most 35 nm in the absence of layer (vii), or layer (vii) has a thickness of at most 35 nm in the absence of layer (vi), Or layers (vi) and (vii) together have a thickness of at most 35 nm)
(Viii) layer (vi) and, if present, of silicon oxide with a thickness of at most 45 nm, preferably deposited by PECVD, for a total thickness of 20 to 45 nm with layer (vii) Layers,
(Ix) optionally comprising or consisting of at least a layer of titanium-zirconium mixed oxide having a thickness of 2 to 10 nm.

In a further embodiment of the invention, the lamination of the thin layers starts from the substrate,
(I) a layer of zinc-tin mixed oxide having a thickness of 27-45 nm;
(Ii) a layer of zinc oxide, optionally doped with aluminum, having a thickness of 1-8 nm and in contact with layer (iii);
(Iii) a functional layer based on silver having a thickness of 7 to 16 nm;
(Iv) a zinc oxide barrier layer, optionally doped with aluminum, having a thickness of 1 to 35 nm, preferably 1 to 18 nm, in contact with layer (iii);
(V) a layer of silicon oxide having a thickness of 20 to 100 nm, preferably 20 to 80 nm, advantageously deposited by PECVD;
(Vi) optionally comprising or consisting of at least a layer of titanium-zirconium mixed oxide having a thickness of 2 to 10 nm.

In a still further embodiment of the invention, the lamination of the thin layers starts from the substrate,
(I) a layer of zinc-tin mixed oxide having a thickness of 27-45 nm;
(Ii) a layer of zinc oxide, optionally doped with aluminum, having a thickness of 1-8 nm and in contact with layer (iii);
(Iii) a functional layer based on silver having a thickness of 7 to 16 nm;
(Iv) a zinc oxide barrier layer, optionally doped with aluminum, having a thickness of 1-18 nm, preferably 1-8 nm, in contact with layer (iii);
(V) optionally a layer of zinc-tin mixed oxide or a layer based on zinc oxide having a thickness of 5-20 nm;
(Vi) a layer of silicon oxide having a thickness of 20 to 125 nm, preferably 20 to 100 nm, advantageously deposited by PECVD;
(Vii) a layer of zinc oxide, optionally doped with aluminum, having a thickness of 1-8 nm and in contact with layer (viii);
(Viii) a silver-based functional layer having a thickness of 7 to 16 nm;
(Ix) a barrier layer of zinc oxide, optionally doped with aluminum, having a thickness of 1-18 nm, preferably 1-8 nm, in contact with layer (viii);
(X) a layer of zinc-tin mixed oxide or / and a layer based on zinc oxide having a thickness of 10-70 nm when combined together;
(Xi) optionally comprising or consisting of at least a layer of titanium-zirconium mixed oxide having a thickness of 2 to 10 nm.

Advantageously, such layers are based on zinc tin mixed oxide layers or zinc oxide in order to minimize or avoid recrystallization haze when thick SiO ₂ layers are used. It may be separated into two layers separated by another dielectric material such as a layer. In the above embodiment, this can result, for example, in the following sequence: (iv)-(v)-(vi)-(v)-(vi)-(vii).

In yet another embodiment of the invention, the lamination of the thin layers starts from the substrate,
(I) a layer of zinc-tin mixed oxide having a thickness of 27-45 nm;
(Ii) a layer of zinc oxide, optionally doped with aluminum, having a thickness of 1-8 nm and in contact with layer (iii);
(Iii) a functional layer based on silver having a thickness of 7 to 16 nm;
(Iv) a zinc oxide barrier layer, optionally doped with aluminum, having a thickness of 1-18 nm, preferably 1-8 nm, in contact with layer (iii);
(V) a layer of zinc-tin mixed oxide or / and a layer based on zinc oxide having a thickness of 10 to 70 nm when combined together;
(Vi) a layer of zinc oxide, optionally doped with aluminum, having a thickness of 1-8 nm and in contact with layer (vii);
(Vii) a functional layer based on silver having a thickness of 7 to 16 nm;
(Viii) a barrier layer of zinc oxide, optionally doped with aluminum, having a thickness of 1-18 nm, preferably 1-8 nm, in contact with layer (vii);
(Ix) optionally a layer of zinc-tin mixed oxide or a layer based on zinc oxide having a thickness of 5-20 nm;
(X) a layer of silicon oxide having a thickness of 10 to 125 nm, preferably 20 to 100 nm, advantageously deposited by PECVD;
(Xi) optionally comprising or consisting of at least a layer of titanium-zirconium mixed oxide having a thickness of 2 to 10 nm.

  The glazing panel according to the invention is preferably used in multiple glazings, for example as double or triple glazing. They can advantageously exhibit the following properties:

  According to some embodiments of the invention, the coating stack is “self-compatible”. This means that the coated substrate undergoes little or no change in optical and / or energy properties when subjected to tempering or bending heat treatment. This has the advantage that an unheated product and a heat-treated product can be arranged next to each other, for example in the building front, for the same application. Previously, conversely, it was necessary to develop and manufacture two types of coating laminates in parallel, one for non-proper glass and the other for tempered or bent glass, Complex both in terms of research and development efforts and in terms of logistics.

  According to another aspect, the present invention provides a method for coating a transparent substrate by laminating thin layers, as defined by claim 16. The dependent claims define preferred and / or other aspects of the invention.

  In this regard, the invention relates to n functional layers and n + 1 dielectric layers reflecting infrared radiation, where n ≧ 1, each functional layer being surrounded by a dielectric layer, n layers reflecting infrared radiation A method for coating a transparent substrate by laminating a thin layer comprising functional layers and n + 1 dielectric layers is provided. Such a method includes depositing a layer consisting essentially of silicon oxide by plasma enhanced chemical vapor deposition (PECVD) as part of at least one dielectric layer above the functional layer, Depositing a zinc oxide based barrier layer over and in direct contact with any functional layer having a silicon oxide layer directly over the dielectric layer.

  Plasma enhanced chemical vapor deposition (PECVD) is a commonly used process for depositing thin films from a gas state (vapor) to a solid state on a substrate. A chemical reaction is involved in this process, which occurs after creation of a plasma of the reacting gas. PECVD can be performed using any plasma: non-thermal plasma (out of equilibrium) or thermal plasma (equilibrium). Non-thermal plasma is generally preferred. Plasma active entities such as electrons, ions or radicals can lead to dissociation or activation of chemical precursors. It is often necessary to operate at a reduced pressure to keep the plasma out of equilibrium. Many of the known PECVD techniques therefore use low pressure plasma. Preferably, the deposition of the layer consisting essentially of silicon oxide according to the invention is produced by low pressure PECVD.

The plasma can be generated through a source utilizing known devices that are commercially available. As the plasma source, a PBS (plasma beam source) source, a PDP (penning discharge plasma) source, a microwave source, and an ICP (inductively coupled plasma) source may be described. PBS sources include hollow cathode plasma sources (see, for example, WO 2010/017185) and linear dual beam plasma sources (dual beam PBS ^™ ), particularly from GPi (General Plasma Inc.) may be described. Compared to magnetoelectric sputtering, PECVD approaches a plasma with a lower temperature, which allows the deposition of more different materials.

  Preferably, the deposition of the layer consisting essentially of silicon oxide is produced by PECVD using a microwave source, a hollow cathode source or a dual beam plasma source. The deposition of thin laminated layers other than those consisting essentially of silicon oxide is preferably produced by magnetoelectric sputtering. Advantageously, both processes, PECVD and magnetron sputtering can be integrated on the same production line, and the PECVD source is located in the coating area of the magnetron coating apparatus.

  The silicon precursors that can be used in the PECVD process according to the present invention are silane, disilane, siloxane (among others TMDSO (tetramethyldisiloxane) and HMDSO (hexamethyldisiloxane) are preferred), silazane, silylamine (among others) TSA (trisilylamine) is preferred), silicon alkoxide (among others, TEOS (tetraethylorthosilicate)) is preferred, and silanol. Silane, TMDSO, HMDSO and TSA are preferred.

Embodiments of the present invention will be further described, by way of example only, with reference to Examples 1-10, along with Comparative Examples 1-15. All thickness values for the examples and comparative examples are given in nm. Unless otherwise specified, silicon oxide layers were deposited by PECVD. Some with a hollow cathode source of the type described in WO 2010/017185 in a 1 meter wide configuration were under the following conditions: 20 kW AC, TSA precursor flow about 95 sccm from the central feed , Recorded dynamic deposition rate at 300 nm / m / min. Others with the microwave source were under the following conditions: 3 kW, 120 sccm HMDSO precursor, 1000 sccm O ₂ , dynamic deposition rate of 60 nm / m / min.

The following abbreviations are used in the following table.
ZnSnO _x zinc tin mixed oxide ZSO ₅ zinc tin mixed oxide ZnO in proportion of about 52-48% by weight zinc tin ZnO: Al doped zinc oxide AZO deposited from metal target in oxygen atmosphere Neutral atmosphere Aluminum doped zinc oxide AlSiN aluminum silicon mixed nitride ZnSnO _x : Al aluminum doped zinc tin mixed oxide TiO _x titanium substoichiometric oxide AlN aluminum nitride SiN Silicon nitride

Comparative Example 1
The following thin layer stacks not according to the invention were deposited on a glass substrate by magnetoelectric sputtering.

  This corresponds to a coating lamination according to the teaching of EP 1140721. This indicates the sheet resistance before and after heat treatment of 3.34 Ω / □ and 3.80 Ω / □, respectively. On visual inspection, the heat treated product shows unacceptable haze and spots.

  Compared to Example 9, this demonstrates the advantage of having a silicon oxide layer in the second dielectric layer to minimize or avoid haze and spots after heat treatment.

Comparative Examples 2 and 3
The following thin layer stacks not according to the invention were deposited on a glass substrate by magnetoelectric sputtering.

  Prior to any heat treatment, a Cleveland test is performed to measure their chemical resistance. The result is poor, the discoloration can be seen with the naked eye already after one day, and it is even clearer after three days.

  By comparison, the examples according to the invention do not show any discoloration visible to the naked eye after 1 or 3 days of the Cleveland test. This demonstrates the advantage of having a layer of oxide, particularly in direct contact with the substrate, with respect to better chemical resistance of the unheated product.

Comparative Examples 4-9
Single silver and double silver coating stacks according to Table I containing metallic titanium barriers were deposited on 3 mm thick glass substrates. The silicon oxide layer was deposited by hollow cathode PECVD and the other layers of the stack were deposited by magnetoelectric sputtering. These are not coating laminates according to the present invention.

  The heat-treated sample brush test (AB brush), haze (AB haze), emissivity (AB E) and sheet resistance (AB Rs [Ω / □]) are shown in the table (heat treatment is at 730 ° C., (3 min 15 sec for single silver stack and 4 min for double silver stack). All comparative examples show at least one unacceptable value (underlined values in the table) for these properties. By comparing Comparative Example 4 and Comparative Example 5 or Comparative Example 6 and Comparative Example 7, it can be seen that, for example, a slight increase in Ti barrier thickness improves brush score but increases haze.

  This indicates that it is impossible to simultaneously achieve low haze values and good wear resistance for a coating stack incorporating a PECVD silicon oxide layer and having a metallic barrier.

Moreover, by comparing the color in the reflection of the coatings according to Comparative Examples 6-9 before and after heat treatment, we found that such a stack is far from self-compatible with a ΔE ^* higher than 10. Noticed.

Examples 1-5 and Comparative Examples 10 and 11
A single silver coating stack according to Table II was deposited on a 3 mm thick glass substrate. The silicon oxide layers of Examples 1-5 according to the present invention were deposited by hollow cathode PECVD, and the silicon oxide layers of Comparative Examples 10 and 11 not according to the present invention were deposited by magnetoelectric sputtering. The other layers of the stack were deposited by magnetoelectric sputtering.

The heat-treated sample brush test (AB brush), haze (AB haze), emissivity (AB E) and sheet resistance (AB Rs [Ω / □]) scores along with ΔE ^* values in reflection on the coating side The heat treatment was carried out at 730 ° C. for 3 minutes and 15 seconds.

All examples according to the invention show good results with regard to resistance to wear after heat treatment, haze, emissivity and sheet resistance. They further show good results with a ΔE ^* of less than 5.0, preferably less than 3.0, more preferably less than 2.0 in terms of self-compatibility. Conversely, samples incorporating silicon oxide deposited by magnetoelectric sputtering exhibit at least one unacceptable value (underlined values in the table) for these properties.

  In addition, the following characteristics were measured in Example 1.

Examples 6-8 and Comparative Examples 12 and 13
The double silver coating stack according to Table III was deposited on a 3 mm thick glass substrate. The silicon oxide layers of Examples 6-8 according to the present invention were deposited by hollow cathode PECVD, and the silicon oxide layers of Comparative Examples 12 and 13 not according to the present invention were deposited by magnetoelectric sputtering. The other layers of the stack were deposited by magnetoelectric sputtering.

  The heat-treated sample brush test (AB brush), haze (AB haze), emissivity (AB E) and sheet resistance (AB Rs [Ω / □]) are shown in the table (heat treatment is 4 at 730 ° C.). Run for a minute).

  All examples according to the invention show good results with regard to resistance to wear after heat treatment, haze, emissivity and sheet resistance. Conversely, samples incorporating silicon oxide deposited by magnetoelectric sputtering exhibit at least one unacceptable value (underlined values in the table) for these properties.

  In addition, the following characteristics were measured in Example 6.

Example 9
The following thin layer stack according to the present invention was deposited on a 4 mm thick glass substrate.

  Except for the silicon oxide layer deposited by microwave PECVD, all coatings were deposited by magnetoelectric sputtering.

  In Example 9, the following characteristics were measured before and after the heat treatment at 700 ° C. for 4 minutes. Moreover, the heat-treated product did not show unacceptable haze and spots on visual inspection.

Comparative Example 14
Similar to Example 9, but without SiO ₂ , a laminate not according to the invention was thus deposited on a 4 mm thick glass substrate by magnetoelectric sputtering.

Performance for various tests (described below) was compared between Example 9 and Comparative Example 14 and showed the beneficial effect of PECVD SiO ₂ topcoat on coating hardness.

Example 10
The following thin layer stack according to the present invention was deposited on a 4 mm thick glass substrate.

  Except for the silicon oxide layer deposited by microwave PECVD, all coatings were deposited by magnetoelectric sputtering.

Comparative Example 15
Similar to Example 10, but without SiO ₂ , a laminate not according to the invention was thus deposited on a 4 mm thick glass substrate by magnetoelectric sputtering.

When the performance for the AWRT test (described below) was compared between Example 10 and Comparative Example 15, the beneficial effect of the PECVD SiO ₂ topcoat on the coating hardness was again shown.

Finally, the samples of Example 10 and Comparative Example 15 were immersed in solutions of various pH for 5 minutes and then dried. The color was measured before and after soaking and drying, and the color change ΔE ^* was calculated and showed the beneficial effect of PECVD SiO ₂ topcoat on coating chemical resistance.

Brush test "Brush test" or "wet brush test" is used to evaluate the resistance of a coating to erosion caused by scrubbing. Full details of this test are disclosed in ASTM standard D2486-00. Test method A was performed on the coated glass samples. The sample was wet scrubbed (with demineralized water) using a bristle brush for 1000 cycles. Then, the deterioration was observed with the naked eye and compared. Scores are assigned from 1 to 5, 1 means no degradation, 5 means very degraded (total coating stripping).

Cleaning Test The “cleaning test” is used to assess the resistance of a coating to erosion caused by cleaning. A 40 × 50 cm square sample is introduced into an industrial glass washing machine operated with demineralized water. While the sample is in contact with the rotating brush, the forward movement is stopped for 60 seconds. In test 1, the brushes are switched off simultaneously, but in test 2, they continue to rotate. In both cases, the water continues to operate.

  Observe the deterioration with the naked eye and compare. Scores are assigned from 1 to 6, with 1 meaning no degradation and 6 meaning very degraded (total coating removal).

Taber Test The “Taber Test” is another test used to evaluate the resistance of a coating to erosion caused by friction. A 10 × 10 cm square sample is maintained on a sheet metal rotating at a speed of 65-75 rpm. Each of the two parallel weighted arms has one specific small abrasive wheel that rotates freely about a horizontal axis. The wheel is covered by a felt stripe (attached to the wheel according to DIN 68861 and supplied by Erichsen). Each wheel sits on top of a sample to be tested under the weight applied to each arm, which is a mass of 500 g. The sample may be scrubbed wet (with demineralized water) or dried. The combination of the abrasive wheel and the rotating support plate creates an abrasive crown on the sample, which corresponds somewhat to the coating hardness. Each sample tested after a total of 500 revolutions was given a score of 1-6, with 1 being the best score showing a highly resistant coating and 6 being the lowest score.

AWRT
The “Automatic Web Friction Test” (AWRT) is again a test used to evaluate a coating's resistance to erosion. A cotton-coated piston (see: CODE 40700004 supplied by ADSOL) is brought into contact with the coating and vibrated on the surface. The piston is heavy so that it has a force of 33N acting on a finger with a diameter of 17 mm. Cotton wear on the coated surface will damage (peel) the coating after a certain number of cycles. The test is run at 250 and 500 cycles at a distance on the sample. The sample is observed under an artificial sky to determine if discoloration and / or scratches are seen on the sample. AWRT scores are given on a scale of 1 to 10, with 10 being the best score showing a highly resistant coating.

Claims (17)

N functional layers and n + 1 dielectric layers reflecting infrared rays, where n ≧ 1, each functional layer being surrounded by a dielectric layer, n functional layers reflecting infrared rays and n + 1 layers In a glazing comprising a transparent substrate coated with a laminate of thin layers comprising a dielectric layer, at least one dielectric layer on the functional layer comprises a layer consisting essentially of silicon oxide , before Symbol lamination, and be any functional layer, located on top of any of the functional layer having any of the functional layer a silicon oxide layer on the dielectric layer on direct, and one of the functional layer to become zinc oxide directly contacts include a barrier layer deposited based, the layer consisting essentially of the silicon oxide, can be obtained by plasma enhanced chemical vapor deposition (PECVD), and from the silicon oxide Manner to become layer, and having an attenuation coefficient of less than 1E-4 at a wavelength of 632 nm, the refractive index of at least 1.466, and all three atomic percent many carbon content, glazing.   2. Glazing according to claim 1, characterized in that the layer consisting essentially of silicon oxide has a thickness of more than 10 nm.   Glazing according to claim 1 or 2, characterized in that the stack comprises a barrier layer based on zinc oxide on and in direct contact with each functional layer.   4. Glazing according to any one of the preceding claims, characterized in that the barrier layer consists of zinc oxide optionally doped with aluminum.   Glazing according to any one of the preceding claims, characterized in that the barrier layer has a thickness of at most 35 nm, preferably 1 to 25 nm. The first dielectric layer, starting from the substrate, prior Symbol substrate and characterized in that it comprises a layer of direct contact oxide, glazing according to any one of claims 1 to 5.   The glazing according to claim 6, wherein the oxide layer in direct contact with the substrate is a zinc tin mixed oxide layer or a titanium oxide layer.   8. Glazing according to claim 6 or 7, characterized in that the oxide layer in direct contact with the substrate has a thickness of at least 10 nm.   The glazing according to any one of claims 1 to 8, wherein the functional layer that reflects infrared rays is a layer based on silver.   10. Glazing according to any one of the preceding claims, characterized in that each dielectric layer under the functional layer comprises a layer based on zinc oxide in direct contact with the functional layer. .   Glazing according to claim 10, characterized in that the zinc oxide based layer has a thickness of at most 15 nm, preferably 1 to 10 nm.   A layer consisting essentially of the barrier layer and the silicon oxide between the barrier layer based on zinc oxide and the layer consisting essentially of silicon oxide, wherein the at least one dielectric layer above the functional layer is 12. Glazing according to any one of the preceding claims, characterized in that it comprises at least one layer of different metal oxides.   The last dielectric layer comprises at least one layer of zinc tin mixed oxide or titanium oxide between a barrier layer based on zinc oxide and a layer consisting essentially of silicon oxide The glazing according to any one of claims 1 to 12. N functional layers and n + 1 dielectric layers reflecting infrared rays, where n ≧ 1, each functional layer being surrounded by a dielectric layer, n functional layers reflecting infrared rays and n + 1 layers In a method of coating a transparent substrate by laminating a thin layer comprising a dielectric layer, it consists essentially of silicon oxide by plasma enhanced chemical vapor deposition (PECVD) as part of at least one dielectric layer above the functional layer. a step of depositing a layer, be any of the functional layer, is on one of the functional layer having a silicon oxide layer on the dielectric layer directly on one of the functional layer, and any one of functional layers Depositing a zinc oxide-based barrier layer in direct contact with the substrate. 15. Method according to claim 14 , characterized in that the deposition of the layer consisting essentially of silicon oxide is carried out by low pressure PECVD. Deposition of a layer consisting essentially of the silicon oxide, a microwave source, characterized in that it is performed by PECVD of using hollow cathode source or dual-beam plasma source according to claim 14 or 15 Method. The method according to any one of claims 14 to 16 , characterized in that the deposition of the thin layer of the stack other than the layer consisting essentially of silicon oxide is performed by magnetoelectric sputtering.